JP4783466B2 - Pharmacologically functional water and its use - Google Patents

Description

  The present invention catalyzes a hydrogen-dissolved water obtained by containing molecular hydrogen as a substrate in raw water, and a reaction that is contained in the hydrogen-dissolved water and decomposes the molecular hydrogen into atomic hydrogen as a product. The present invention relates to a novel pharmacologically functional water that contains an antioxidatively functional water consisting of a precious metal colloid and an active ingredient and exhibits a pharmacological function without side effects, and its use.

  For example, oxygen is a double-edged sword for a living body. Oxygen is used to oxidize nutrients to gain energy, or to perform various oxygenation reactions essential for the body, but with the risk of causing various tissue disorders due to its oxidizing power Has been pointed out.

In particular, active oxygen radicals generated through metabolism, etc., and free radicals such as nitric oxide (NO) are highly reactive atoms and molecules with unstable unpaired electrons. Or try to keep the stability by giving in reverse. In general, four types of superoxide anion radical (.O ₂ ⁻ ), hydroxy radical (.OH), hydrogen peroxide (H ₂ O ₂ ), and singlet oxygen ( ¹ O ₂ ) are called active oxygen radicals . The following, collectively these active oxygen radicals may be referred to as "reactive oxygen species". In addition, the active oxygen species mentioned here and free radicals such as nitric oxide (NO) may be collectively referred to simply as “radicals”.

  Such reactive oxygen species are used in the context of bactericidal action by cells, etc. in the living body, intracellular signal transduction mechanisms through redox control, degradation of unnecessary proteins, apoptosis, etc. It can be said that it is a thing. For example, in the scene of an inflammatory reaction, macrophages of immune cells themselves generate active oxygen, which is used as a means of cytotoxic action to attack foreign bacterial cells and the like.

  However, the excessive amount of reactive oxygen species generated by oxidative stress becomes extremely harmful to the living body due to its high reactivity. From such active oxygen species, new active oxygen species are generated as a secondary (radical chain reaction) in the presence of, for example, iron ions or copper ions. It has become clear that the reactive oxygen species generated in an accelerated manner are involved in many diseases and diseases by damaging cells and DNA and producing lipid peroxides which are aging promoting factors. Of these, the hydroxy radical (.OH) is known to be the most reactive and reactive oxygen species having a large damage effect such as cell damage. Furthermore, it has been confirmed that hydroxy radicals (.OH) are generated and involved in the occurrence of inflammation in the skin or the like due to ultraviolet rays (UV). Virus infection is also known to have a toxic effect on the living body as a result of an excessive immune response of the infected person, and reactive oxygen species are generated in excess of the amount necessary to maintain the living body balance.

  The reactive oxygen species that exert such toxic effects on the living body are usually eliminated in vivo by an enzyme such as superoxide desmutase (SOD) or catalase.

  However, when the balance of the living body is lost due to various factors such as stress, alcohol consumption, smoking, intense exercise, and aging, SOD decreases, lipid peroxide increases due to reactive oxygen species, cerebral infarction, myocardial infarction, arteriosclerosis Cause various diseases such as diabetes, cancer, stroke, cataracts, stiff shoulders, coldness, hypertension, and senile dementia, decrease physiological functions of the body, and reduce the appearance of beauty such as spots, freckles, wrinkles, etc. Problems such as bringing about are pointed out.

  Antioxidants and free radical scavengers such as ascorbic acid, α-tocopherol, cysteine, glutathione, ubiquinone, BHA (butylhydroxyanisole), BHT (butylhydroxytoluene) are substances that improve various problems derived from such reactive oxygen species. It has been known.

  However, since these antioxidants are chemically synthesized products, when they are applied in large quantities to an antioxidant target (for example, living cells), the safety of such antioxidant target remains a question. There's a problem. In addition, these antioxidants and the like are oxidized themselves through the process of reducing the other party, but there is also a problem that safety (for example, radical chain reaction) of such by-product oxides against the oxidation target is concerned. is there.

  Therefore, the development of an innovative technology that exhibits a pharmacological function without side effects, which is completely different from existing therapeutic agents that necessarily have side effects, has long been desired.

  The present invention has been made in order to solve such problems, and hydrogen-dissolved water obtained by adding molecular hydrogen as a substrate to raw water, and the hydrogen-dissolved water contains the molecular hydrogen. To provide a pharmacologically functional water that exhibits an pharmacological function without any side effects, and uses thereof, containing as an active ingredient an antioxidant functional water comprising a noble metal colloid that catalyzes a reaction that decomposes into atomic hydrogen as a product. With the goal.

  Prior to the description of the outline of the present invention, the background that the present inventors have conceived of the present invention will be described.

1. Background of Thinking of the Present Invention The applicant of the present invention has previously filed an application and has already been published. In the republished patent WO99 / 10286, the content of which is incorporated in the present invention by this citation, the hydrogen ion index (hereinafter referred to as “pH”). .) And an oxidation-reduction potential (hereinafter referred to as "ORP") are disclosed. The outline of the application is as follows. That is, an electrolysis chamber into which raw water to be electrolyzed is introduced, one or more diaphragms partitioning the electrolysis chamber and the outside of the electrolysis chamber, and at least one or more provided between the electrolysis chamber and the outside with the diaphragm interposed therebetween A pair of electrode plates, and a power supply circuit that applies a voltage between both electrodes using the electrode plate provided outside the electrolysis chamber as an anode while using the electrode plate provided outside the electrolysis chamber as an anode, This is a reduction potential water generating device in which the electrode plate is provided in contact with the diaphragm or through a slight gap. On the cathode side of the apparatus, electrolytic reduction potential water (hereinafter sometimes referred to as “reduction potential water”) in which ORP is greatly reduced to a negative value is generated without largely changing the pH of the raw water. In the following, unless otherwise specified, “electrolytic treatment” refers to electrolytic treatment in a continuous water flow method using the above-described reducing potential water generating device at a flow rate of 1 liter per minute under electrolysis conditions of 5 A constant current. Say.

  The present inventors have arrived at the present invention through a performance evaluation test of reducing potential water generated by the above-described reducing potential water generating apparatus.

  Here, the reduction potential water indicates a value in which ORP has a negative value and the ORP value corresponding to pH exceeds a predetermined value. Whether or not the ORP value exceeds a predetermined value is determined from the following Nernst equation (approximate equation).

ORP = −59pH−80 (mV) (Nernst equation)
As shown in FIG. 1, this expression indicates that pH and ORP are in a proportional relationship (the ORP value is more negative as the pH is inclined toward the alkali side). Here, that the ORP value corresponding to pH indicates a value exceeding a predetermined value means that the ORP value falls below a value according to the Nernst equation. Here, water satisfying these conditions is referred to as reduction potential water. For example, when pH 7 is substituted into the Nernst equation, the ORP is about -493 (mV). That is, at pH 7, water having an ORP of about −493 (mV) or less corresponds to reduction potential water. However, there is a slight difference in dissolved hydrogen concentration among those belonging to the category of reduction potential water defined here, but this will be described in detail later together with a quantitative analysis method for the dissolved hydrogen concentration. .

  The reduction potential water contains a considerable amount of high-energy electrons. This is apparent when measured with an ORP meter. The ORP is an index indicating the abundance ratio of the oxidizing substance and the reducing substance contained in the liquid to be measured, and generally uses millivolts (mV) as the unit. In general, in the ORP meter, when the measurement electrode is negatively charged, a negative ORP value is observed, and conversely, when the measurement electrode is positively charged, a positive ORP value is observed. Here, in order for the measurement electrode to be negatively charged, the liquid to be measured needs to contain electrons with high energy. Therefore, the ORP value indicating a value having a large negative absolute value inevitably indicates that the liquid to be measured contains electrons with high energy.

  Here, a lighting test using a light emitting diode (hereinafter abbreviated as “LED”) was performed in order to evaluate the performance of how much high-energy electrons are contained in the reduction potential water. This uses the principle of a battery. Specifically, in a test cell 209 having electrodes 201 and a diaphragm 203 alternately made of platinum and having about three chambers of cathode chambers 205 and anode chambers 207, the cathode chamber has an ORP of about −600 (mV), for example. In the anode chamber, for example, tap water having an ORP of about +400 (mV) is introduced into the anode chamber, the negative terminal of the LED 211 is connected to the electrode contacting the cathode chamber 205, and the positive side of the LED 211 is connected to the anode chamber. When the terminals were connected, continuous lighting of the LED 211 was observed. This means that a current flows from the anode to the cathode of the cell 209 via the LED 211, and moreover, that a current flows means that electrons are flowing. At this time, considering that the electrons flowing through the LED 211 flow from the cathode of the cell 209 to the anode, it was experimentally evaluated that the electron group with high energy was certainly included in the reduction potential water.

  As a reference example, in the cell 209 described above, alkaline electrolyzed water (for example, ORP is about -50 mV) or natural mineral water generated by a commercially available electrolyzed water generator is used for the cathode chamber, and tap water is used for the anode chamber. As in the case described above, when the negative terminal of the LED was connected to the electrode of the cathode chamber and the positive terminal of the LED was connected to the anode chamber, lighting of the LED was not observed in this case. This is presumably because the existing alkaline electrolyzed water or natural mineral water does not contain an electron group with high energy enough to light the LED.

  Moreover, in a commercially available electrolyzed water generating apparatus, even if the ORP value is largely moved to the negative side by reducing the flow rate, according to the Nernst equation, if the absolute value of the ORP value at that time is small, Again, the lighting of the LED is not observed. This is because, for example, in a commercially available electrolyzed water generator, even if the pH is about 10 and the ORP value is -500 to -600 (mV) as a result of reducing the flow rate, the ORP value is small instead of the pH value. Therefore, in terms of electronic energy, in the above Nernst equation, if the pH value is about 10, the ORP value is not lowered to at least about -670 (mV) or less, so that the LED can be turned on. It is thought that it may not be possible.

  There are also several types of LEDs, but when using the cell 209 in which the chambers are alternately arranged in a three-layer structure as described above, the reduction potential water requires a high terminal voltage of about 3 V or more. Continued lighting of diodes showing blue or green color was observed.

  Therefore, as a result of diligent research on industrial applicability that high-energy electrons are contained in reduction potential water, reduction potential water may have a “potential reduction power”. And got a hint. In particular, since the ORP value is inclined so as to be negative so that the LED can be turned on, the reducing potential water has a considerably strong reducing power. I came to believe that it could be used in a wide range of industrial fields, including industry, food, agriculture, automobiles, and energy.

  Here, the state of “potential reducing power” will be described.

  For example, when a reducing agent such as vitamin C (ascorbic acid) is added to normal water such as tap water and then an oxidizing agent is added, the reducing agent immediately reduces the oxidizing agent. On the other hand, even if an oxidizing agent is added to the reducing potential water, the oxidizing agent is not immediately reduced. The state at this time is considered to be in a state where the ORP value which is larger in the negative direction of the reducing potential water remains as it is, and the oxidant also remains as it is and both coexist. At this point, the reducing power has not yet been demonstrated.

  In other words, no matter how high-energy electrons exist in the reduction potential water, in other words, no matter how large the ORP has a negative value, electrons immediately discharge from the reduction potential water to reduce the oxidizing agent. I was faced with the fact that there was no reaction. Therefore, it was considered that the magnitude of the electron energy contained in the reducing potential water and the ease of electron discharge, that is, the display of the reducing power, would be different problems.

  So what should reduction potential water do to exert its reducing power? The present inventors have conducted further research on this proposition, and have come up with an inspiration as to whether or not some kind of catalyst is allowed to act. Although there are various types of catalysts in a mouthpiece, in particular, on the premise of applying to a living body, for example, some enzyme or noble metal colloid (fine particles of noble metal clusters) described later can be used as a catalyst. It came to the idea that there was not.

  Here, particularly when referring to an enzyme, the essence of the enzyme action is a catalyst for a chemical reaction, and the activity of the enzyme is measured by the speed of the catalyzed reaction. When catalyzing the reaction A → B, A is a substrate and B is a product. When this is applied to the case of the present invention, molecular hydrogen contained in hydrogen-dissolved water corresponds to a substrate, while active hydrogen corresponds to a product. And I thought that the mechanism of action of these enzymes can be explained as follows.

  Now, it is assumed that a group of electrons having high energy contained in the reduction potential water crawls over the oxidant and it is necessary to reduce the oxidant. In order for the electron group contained in the reduction potential water to move to the oxidant, there is an energy wall that must first be exceeded. This energy barrier is generally called “potential barrier” or “activation energy”. The higher this energy, the higher the wall height that must be exceeded. And since the energy that can be expressed by the height of this wall is larger than the energy of the electron group, the electron group usually cannot cross this wall and consequently cannot move to the oxidant. In other words, I thought that the oxidant could not be reduced.

  However, when a catalyst such as an enzyme acts, for example, the activation energy corresponding to the height of the wall can be reduced. As a result, the group of electrons contained in the reduction potential water is less than that without a catalyst. Therefore, the reduction potential water can reduce the oxidant when the transfer is completed.

  Thus, when a catalyst such as an enzyme acts, a group of electrons with high energy contained in the reduction potential water is likely to be discharged, and as a result, a reducing power can be exhibited. That is, this means that reducing potential water has “potential reducing power”, and this can be said that “reducing power of reducing potential water is sealed” if the expression is changed. Through these various thought processes, we came to the idea that “the catalyst is the key to unlocking the reducing power of reducing potential water”.

  Now that the idea of the present invention has been clarified, the outline of the present invention will be described.

2. Summary of the Invention 2.1 Antioxidation Method According to the present invention, through a process in which hydrogen oxidoreductase (excluding those previously present in the living body) or a catalyst that is a noble metal colloid is allowed to act on hydrogen-dissolved water, By promoting the reaction of decomposing (activating) molecular hydrogen as a substrate contained in the hydrogen-dissolved water into active hydrogen as a product, it is in an oxidized state due to electron deficiency or is oxidized There is provided an antioxidant method characterized in that an antioxidant object to be protected from is brought into a reduced state filled with electrons.

  The present inventors have convinced that the essence of the ORP value of hydrogen-dissolved water such as electrolytically treated water and hydrogen bubbling water being negative is hydrogen dissolved in the water. The fact that hydrogen is the ultimate reducing substance, and further, the fact that hydrogen is generated on the cathode side during the electrolytic treatment supports the above-mentioned belief.

  However, as clarified in the thought process of the present invention, the original reducing power remains sealed with the hydrogen-dissolved water as it is.

  Therefore, in order to release the sealing of the reducing power of hydrogen-dissolved water, it has been found that the process of causing a catalyst to act on hydrogen-dissolved water is extremely important as defined in the antioxidant method according to the present invention.

  Another important factor is the existence of antioxidant targets. This is because there is no scene that exhibits the antioxidant function according to the present invention unless there is an antioxidant target.

  That is, the important elements in the present invention are firstly hydrogen-dissolved water, secondly a catalyst, and thirdly an antioxidant object. Only when these three elements are combined organically will the hydrogen's potential reducing power be released, and a broadly defined antioxidant function including a reducing function will be manifested. The expression of the antioxidant function in the present invention means that an antioxidant target that is in an oxidized state due to electron deficiency or that is to be protected from oxidation is brought into a reduced state in which electrons are satisfied. In addition, when an antioxidant target is in a reduced state in which electrons are satisfied, the antioxidant target itself in the oxidized state is reduced, and the oxidation of reactive oxygen species that attempt to oxidize the antioxidant target that is to be protected from oxidation. It is a concept that includes both the case of reducing the substance itself.

  Now, the magnitude of the reducing power here can be estimated once based on the state of the ORP value or the like (the stability of the ORP measurement value, the relationship with the Nernst equation described above, etc.), but ultimately, It is determined depending on the effective value of the dissolved hydrogen concentration DH obtained by using the method for determining the dissolved hydrogen concentration using the redox dye described in detail later.

  Next, the range of the technical scope assumed to belong to the present invention will be mentioned with respect to these three elements.

2.1.1 Hydrogen-dissolved water Hydrogen-dissolved water assumes all water containing hydrogen. In addition, the water here (also referred to as raw water) is tap water, purified water, distilled water, natural water, activated carbon treated water, ion-exchanged water, pure water, ultrapure water, commercially available PET bottle water, It includes all water such as biological water described later and water in which molecular hydrogen is generated by chemical reaction in water. Furthermore, all the water which added the electrolysis adjuvant and the reducing agent mentioned later to such water is also grasped in the range of the technical scope of the present invention. Furthermore, as long as the condition of water containing hydrogen is satisfied, whether the liquidity is acidic, neutral, or alkaline, the dissolved concentration is high or low. It doesn't matter in principle. However, the antioxidant function expressed by applying the present invention is derived from electrons released in the process of replacing molecular hydrogen with active hydrogen via a catalyst, so the dissolved concentration of molecular hydrogen is high. This can be expected to express a larger antioxidant function.

  Furthermore, hydrogen-dissolved water means electrolytic water produced on the cathode side when raw water is electrolyzed between the anode and the cathode through a diaphragm, or bubbling (aeration) or pressurizing and filling hydrogen into the raw water. Including treated water. Such definitions include electrolyzed water such as so-called alkaline ionized water produced by an existing continuous-flow or batch-type electrolyzed water generator, and hydrogen-dissolved water produced by adding hydrogen to raw water by external operation. Is also intended to clarify that the scope of the technical scope of the present invention is grasped. What was enumerated here as hydrogen-dissolved water is merely an example, and is not intended to be limited to these. Therefore, even if it is natural water, if hydrogen is contained therein, it is clarified that such water is not intended to be excluded from the scope of the technical scope of the present invention.

  Moreover, hydrogen-dissolved water is a reduction potential water in which the ORP has a negative value and the ORP value corresponding to the pH is lower than the value according to the Nernst equation; ORP = −59pH−80 (mV). Is also included. The reducing potential water here is an electrolysis chamber into which electrolyzed raw water is introduced, one or more diaphragms that partition the electrolysis chamber and the outside of the electrolysis chamber, and each outside and inside the electrolysis chamber, developed by the present applicant. In addition, at least one electrode plate pair provided across the diaphragm and an electrode plate provided in the electrolysis chamber as a cathode while an electrode plate provided outside the electrolysis chamber is used as an anode between the two electrodes A power supply circuit for applying a voltage, and an electrolytic reduction potential water generated using a reduction potential water generating device in which an electrode plate outside the electrolysis chamber is provided in contact with the diaphragm or through a slight gap As a matter of course, it is clarified that the water generated by the other apparatus is not intended to exclude the water satisfying the above-mentioned conditions as the reduction potential water. In the reduction potential water generator, when the circulating electrolysis technique is used such that the water once generated is recirculated to the electrolytic cell (electrolytic chamber) again, and this recirculation step is repeated for a predetermined time, As shown in Table 1 and the like to be described later, it is added that reduced potential water having a high dissolved hydrogen concentration and a lower ORP value can be obtained, and such reduced potential water can exhibit an excellent reducing power (antioxidant power). deep.

  Further, the hydrogen-dissolved water is preferably water in which hydrogen having a saturation concentration or higher (in terms of effective dissolved hydrogen concentration by a dissolved hydrogen concentration quantitative analysis method using a redox dye) is dissolved under atmospheric pressure. This is because the expression of the reducing activity and antioxidant activity derived from the antioxidant functional water according to the present invention can be expected at a high level.

  Here, various physical property values according to a reference example of hydrogen-dissolved water assumed by the present inventors and a comparative example of water in which hydrogen is not dissolved are listed. The target water for comparison includes activated carbon treated water treated by passing Fujisawa city tap water through an activated carbon column, purified organic water treated by passing Fujisawa city tap water through an ion exchange column manufactured by Organo, and plastic bottle water. As an example, “evian” (registered trademark of SAdes Eaux Minrales d'Evian) supplied in Japan by Calpis Itochu Mineral Water Co., Ltd. is illustrated. As the hydrogen-dissolved water after various treatments for dissolving hydrogen in the water to be compared, the reducing potential water generator developed by the applicant of the present application uses an electrolysis condition of 5 A constant current at a flow rate of 1 liter per minute. The first reduction potential water that has been subjected to continuous electrolytic treatment using the same electrolysis conditions (the amount of circulating water is 2 liters) in the same apparatus and the second reduction potential water that has been subjected to continuous circulation electrolytic treatment for 30 minutes. And hydrogen gas bubbling water obtained by bubbling hydrogen gas for various comparison target waters for 30 minutes, and electrolysis conditions of electrolysis range “4” with Miz Co., Ltd. electrolyzed water generator “Mini Water” with standard water amount And alkaline electrolyzed water that has been subjected to a continuous electrolytic treatment using the above.

  In addition, various physical properties of such water include pH, redox potential ORP (mV), electric conductivity EC (mS / m), dissolved oxygen concentration DO (mg / L), dissolved hydrogen concentration DH (mg / L ), And water temperature T (° C). In addition, as various instruments used to measure these various physical property values, the pH meter (including the thermometer) is manufactured by HORIBA, Ltd., model “D-13” of the pH meter body, and model of the probe. It is “9620-10D”, the ORP meter is manufactured by Horiba, Ltd., the ORP meter body model “D-25”, the probe is the model “9300-10D”, and the EC meter is manufactured by Horiba, Ltd. , EC meter body model “D-24”, probe model “9382-10D”, DO meter manufactured by HORIBA, Ltd. DO meter body model “D-25”, probe model “ 9520-10D ”, and DH meter (dissolved hydrogen meter) is manufactured by Toa DKK Corporation. Main body model“ DHDI-1 ”, electrode (probe) model“ H ” -5321 ", the repeater model" DHM-F2 ", and using these various instruments, various physical property values of the water to be compared were measured (the same various instruments were used in the following). .

この表１によれば、溶存水素計で計測した溶存水素濃度（ＤＨ）に注目したとき、還元電位水生成装置を用いて１回電解処理した第１の還元電位水では、電解処理した水を即時に取り出せるにもかかわらず、そのなかには０．４２５〜０．９００（ｍｇ／Ｌ）もの高濃度の水素を溶存させることができることがわかる。

According to Table 1, when attention is paid to the dissolved hydrogen concentration (DH) measured with a dissolved hydrogen meter, the first reduced potential water subjected to electrolytic treatment once using the reduced potential water generator is used for the electrolytically treated water. In spite of being able to take out immediately, it turns out that 0.425-0.900 (mg / L) of high concentration hydrogen can be dissolved in it.

  Further, when the treatment time is set to 30 minutes, for example, when the dissolved hydrogen concentration of the circulating electrolytic reduction potential water (second reduction potential water) and hydrogen gas bubbling water in the reduction potential water generator is compared, The latter was 0.89 to 1.090 (mg / L), whereas the former was found to be able to dissolve hydrogen at a high concentration of 1.157 to 1.374 (mg / L). This measurement data should be used only as a reference because its performance has been improved in each stage as described in the examples and reference examples described later by partially improving the reduction potential water generator.

  By the way, the antioxidant functional water (pharmacological functional water) contains at least one reducing agent selected from the group comprising sulfite, thiosulfate, ascorbic acid, and ascorbate, if necessary. Is preferred. When it is necessary to prevent rapid oxidation of the active hydrogen generated by the catalytic action due to dissolved oxygen, the dissolved oxygen concentration in the hydrogen-dissolved water is kept as low as possible (the dissolved oxygen concentration in the hydrogen-dissolved water is 3.5 mg). / L or less, 3.4 mg / L or less, 3.3 mg / L or less, 3.2 mg / L or less, 3.1 mg / L or less, 3.0 mg / L or less, 2.5 mg / L or less, 2 mg / L or less 1.5 mg / L or less, 1 mg / L or less, 0.5 mg / L or less, and 0 mg / L in the order of 0 mg / L.

  This will be further explained. When the reducing agent is added to the hydrogen-dissolved water in which the catalyst is actuated, the amount of the reducing agent is less than the chemical equivalent that can just reduce the dissolved oxygen, the dissolved oxygen concentration DO (mg / L). Can be reduced to almost 0 (mg / L).

  As a comparative example at this time, when a similar amount of reducing agent is added to hydrogen-dissolved water that does not act on the catalyst, the dissolved oxygen concentration DO (mg / L) cannot be greatly reduced. This is considered to be a result of the intrinsic reducing power of the hydrogen-dissolved water whose seal has been released pulling out the reducing power of the reducing agent more strongly.

  Therefore, when the antioxidant functional water (pharmacological functional water) according to the present invention is bottled in the state of coexisting with additives such as reducing agents and water-soluble vitamins, these additives are placed in an antioxidant environment. As a result, it should be added that there is an aspect in which the antioxidant and pharmacological action inherent in the additive are further enhanced and the amplification activity can be expected. This is because when the antioxidant functional water (pharmacological functional water) according to the present invention is bottled in a state where it coexists with reduced ascorbic acid, for example, such ascorbic acid is placed in an antioxidant environment, so that it is reduced. As a result of this, it means that the antioxidant and pharmacological actions inherent in reduced ascorbic acid can be further enhanced (for details, see “Antioxidative functional water (AOW)” described later on the oxidation of reduced vitamin C. See the section “Does it suppress?”). In this case, for example, it is preferable to contain a reducing agent such as reduced ascorbic acid in an excessive amount after reducing and neutralizing oxides such as dissolved oxygen in the coexisting system. However, the content of ascorbic acid is preferably contained in consideration of the pH exhibited by the antioxidant functional water, the lower limit recommended for intake per day, and the like.

2.1.2 Catalyst The catalyst is assumed to be any catalyst having a function of catalyzing a reaction of decomposing molecular hydrogen as a substrate contained in the hydrogen-dissolved water into active hydrogen as a product. That is, the essence of the catalytic function according to the present invention is to smoothly promote the activation of molecular hydrogen, and in that function, an electron is received from molecular hydrogen (activates one molecular hydrogen). Two electrons are obtained; H ₂ → 2e ⁻ + 2H ⁺ ), and the received electrons are once pooled (including the concept of adsorption and occlusion on the catalyst) or antioxidants without pooling Donating to the subject. To donate electrons to an antioxidant target is to reduce the antioxidant target itself in an oxidized state, and to reduce the oxidized substance itself such as reactive oxygen species that intends to oxidize the antioxidant target to be protected from oxidation. It is a concept that includes both cases.

As the catalyst according to the present invention, noble metal colloids are captured within the technical range. The noble metal colloids assumed in the present invention include platinum, palladium, rhodium, iridium, ruthenium, gold, silver, rhenium, and colloidal particles such as salts, alloy compounds, complex compounds of these noble metal elements themselves, Is a concept that includes these mixtures. In producing or using such a precious metal colloid, the description is incorporated into the present invention by this citation, “How to make and use Pt colloid” by Seitaro Namba and Ichiro Okura, Surface Vol. 21 No. 8 (1983 ), Etc. may be referred to. In addition, the colloid referred to in the present invention is assumed to be a particle having a diameter of 1 nm to 0.5 μm, which is generally said to exhibit an essential behavior as a colloid. However, for example, when a Pt colloid is employed as the noble metal colloid, the particle diameter that increases the catalytic activity of the Pt colloid is preferably 1 to 10 nm, more preferably 2 to 6 nm. As described in the above paper by Namba et al. “How to make and use Pt colloids”, it demonstrates the essential properties of noble metals and increases the surface area with the aim of improving catalytic activity. The particle size can be derived from the trade-off relationship of. In addition, the colloid referred to in the present invention also conforms to the definition of “a colloid composed of 10 ³ to 10 ⁹ atoms” proposed by Staudinger in Germany. It is. Furthermore, the noble metal colloid according to the present invention preferably has a spherical particle shape in order to increase its surface area. This is because the fact that the surface area of the noble metal colloid is large means that the contact opportunity with the molecular hydrogen as a substrate is increased, which is advantageous from the viewpoint of expressing the catalytic function of the noble metal colloid.

2.1.2.1 Candidates for electron carriers The following are candidates for electron carriers. It does not matter whether the electron carrier is an oxidized type or a reduced type, but the reduced type electron carrier has an excess electron in advance and is advantageous in that it is easier to emit electrons. I can say that.

(A) Methylene blue (usually oxidized)
Methylthionine chloride, tetramethylthionine chloride Chemical formula = C16H18ClN3S ・ 3 (H2O)
Reduced methylene blue is referred to as leucomethylene blue.

(B) Pyocyanin
Chemical formula = C13H10N2O
It is one of the antibiotics produced by Pseudomonas aeruginosa. Pyocyanin undergoes a reversible oxidation-reduction reaction, and there are two types of oxidized forms: alkaline and blue-colored, and acidic and red-colored. Further, the reduced type is colorless like the reduced type methylene blue (leucomethylene blue).

(C) Phenazine methosulfate
Abbreviation = PMS
Chemical formula = C14H14N2O4S
Phenazine methosulfate tends to be easily photodegraded.

(D) 1-methoxy PMS
Developed as an alternative to the above-mentioned PMS which is unstable to light, it is stable to light.

(E) Compounds containing iron (III) ions For example, there are many such as FeCl3, Fe2 (SO4) 3, Fe (OH) 3. The original purpose is a reagent for obtaining Fe (3+), which is an iron (III) ion, as an ion. In the living body, the presence of erythrocyte hemoglobin as heme iron is considered. Heme iron is different in nature from independent iron ions.

  Especially in vitro, when it is conjugated with ascorbic acid, hydroxyl radicals (.OH) with strong oxidizing power are generated, so iron ions are not necessarily required. However, in vivo, it is said that iron ions may not generate hydroxyl radicals (.OH) in the presence of nitric oxide (NO).

  In particular, divalent iron Fe (2+) is a reduced form of trivalent iron Fe (3+), but the reduced form often enhances the oxidizing action. In particular, when there is lipid peroxide, a radical chain reaction easily occurs. When the iron (III) ion Fe (3+) is reduced by ascorbic acid or the like, if a lipid peroxide coexists, a radical generation chain reaction occurs. That is, it is considered that many lipid radicals are generated and have an adverse effect on the living body.

(F) Reduced ascorbic acid (Chemical formula = C6H8O6)
Although it exists in the living body, it is absorbed from outside the body and cannot be synthesized by humans.

(G) Glutathione (Chemical formula = C10H17N3O6S)
Abbreviation = GSH
It is an SH compound that exists in large amounts in the living body, and it is speculated that humans also have genes that synthesize them. A polypeptide consisting of three amino acids (glutamic acid-cysteine-glycine = Glu-Cys-Gly), a coenzyme of glyoxalase, and functions as an intracellular reducing agent and anti-aging agent are known. . In addition, glutathione has a function of directly (non-enzymatically) reducing oxygen (O2).

(H) Cysteine (Cys)
It is an SH compound that is one of amino acids, and is a final product obtained by digestion and digestion of protein. It is an amino acid having a SH group, which is a constituent of glutathione described above. Again, like glutathione, two cysteines Cys each release one hydrogen atom and become disulfide bonds (-s-s-) to become oxidized cysteines.

(I) Benzoic acid (C7H6O2)
Although it is hardly present in the living body, it is contained in strawberry about 0.05%. It is a basic reducing agent, and has a function of scavenging hydroxyl radicals non-enzymatically and effectively into water.

(J) p-aminobenzoic acid (C7H7NO2)
(K) Gallic acid (C7H6O5) (3,4,5-trihydroxybenzoic acid)
Widely present in plant leaves, stems, roots, and the like, and is generally used as a hemostatic agent and a food antioxidant (food additive). The alkaline aqueous solution has particularly strong reducing power. It tends to react with oxygen.

Further, it is added that the active hydrogen as a product is a concept comprehensively including atomic hydrogen (H.) and hydride ions (hydride ions H ⁻ ).

2.1.3 Antioxidant targets Antioxidant targets are all targets that are in an oxidized state due to electron deficiency or that are to be protected from oxidation. The oxidation referred to here is a phenomenon in which electrons are extracted from an object by direct or indirect action such as oxygen, heat, light, pH, and ions. The antioxidant target specifically includes, for example, biological cells and biological organs, or antioxidant substances such as vitamins, foods, quasi-drugs, pharmaceuticals, cosmetics, feeds, redox dyes described later, and The water itself is captured within the scope of the technical scope of the present invention. It should be clarified that the items listed as antioxidant targets are merely examples and are not intended to be limited to these.

  Next, the relationship between the catalyst and the antioxidant target will be mentioned from the viewpoint of the catalyst.

  In the present invention, the noble metal colloid catalyzes a reaction of decomposing molecular hydrogen as a substrate contained in hydrogen-dissolved water into active hydrogen as a product.

  Now, let us consider a noble metal colloid such as platinum (Pt) or palladium (Pd) colloidal particles in reduction potential water (that is, a noble metal colloid catalyst-containing antioxidant functional water). For example, when drinking Pt colloid or Pt colloid containing weak alkaline reducing potential water, oxidants such as reactive oxygen species coexist in gastrointestinal living cells (antioxidant) In the meantime, these oxidizing agents are immediately reduced. In addition, when other additives such as fruit juice and vitamins (antioxidation target) coexist, the reduced potential water is used as an antioxidant for these additives under the condition that Pt colloid and Pd colloid coexist. Works. The mechanism of action is caused by the molecular hydrogen dissolved in the reduction potential water adsorbed on the surface of the fine particles of the Pt colloid or Pd colloid and dissociated into two atomic hydrogens (H.) and activated. It is considered that atomic hydrogen (H.) is split into protons and electrons in the presence of water, and the electrons thus generated are donated to the antioxidant target. Here, an electron is donated to an antioxidant object includes a case where the antioxidant object itself in an oxidized state is reduced, and an oxidized substance such as a reactive oxygen species which intends to oxidize the antioxidant object to be protected from oxidation. It is a concept that includes both the case of reducing itself.

  Such an antioxidant function is manifested only when all three of hydrogen-dissolved water such as reduction potential water, a noble metal colloid as a catalyst, and an antioxidant target such as a digestive system living cell are collected. In other words, the reducing power is expressed only when necessary, and there is no effect when it is unnecessary. Moreover, when paying attention to the chemical component composition, for example, the reduction potential water is only ordinary water obtained by electrolyzing raw water. Therefore, it should be noted that even after the reducing power is expressed, it merely acts as ordinary water and does not have any adverse effect on the living body. In other words, it can be said that a decisive difference from conventional antioxidants and radical scavengers is that the targeted positive action can be obtained but there is no negative action, so-called side effects.

  Therefore, the antioxidant functional water (pharmacological functional water) according to the present invention is a disease related to or caused by the function of monocyte / macrophage cell, in particular, a disease related or caused by enhancement or decrease of the function of macrophage cell, It is thought that the path as a pharmaceutical for the prevention, improvement or treatment of tissue or organ dysfunction or pathology is also open.

  In addition, the specific example as a pharmaceutical is as follows. In other words, water generally has the property that it can quickly reach any part of the living body, including lipid membranes, cell membranes, or the brain-blood barrier, so that it can be injected or instilled into damaged parts of living cells derived from reactive oxygen species. By injecting hydrogen-dissolved water (antioxidation functional water or pharmacological functional water) containing a noble metal colloid through an operation such as dialysis, the healing effect of the damaged site can be expected.

  Here, the noble metal colloid catalyst is a foreign substance even if it is an inorganic substance, and it is assumed that such a catalyst is sent to an injured part of the living body through an operation such as injection, drip, or dialysis. There is a problem that an antigen-antibody reaction may occur due to recognition of the immune mechanism of the living body as non-self. In order to solve this problem, the principle of oral tolerance that a living body has may be applied clinically. Oral tolerance refers to antigen-specific T / B cell unresponsiveness induced against foreign antigens that enter orally / enterally. To put it simply, even if the substance taken from the mouth is a foreign substance that can be an antigen, if it is absorbed from the small intestine, the phenomenon that immune tolerance is established against that substance is oral tolerance, A treatment using this principle has already been attempted. Thus, clinical application of this principle of oral tolerance could open the door to a new therapeutic strategy called antioxidants.

2.2 Pharmacologically functional water and use thereof According to the present invention, hydrogen-dissolved water in which molecular hydrogen as a substrate is contained in raw water and the hydrogen-dissolved water are contained in the molecular water. Provided is a pharmacologically functional water characterized in that it contains an antioxidant functional water consisting of a noble metal colloid that catalyzes a reaction that decomposes into atomic hydrogen as a product, and exhibits a pharmacological function without side effects. .

  Pharmacologically functional water having such a configuration includes hydrogen-dissolved water and a precious metal colloid catalyst among the three important elements in the present invention. The sealing of reducing power is released, and the antioxidant function and pharmacological function peculiar to the present invention are expressed. In addition, the antioxidant function that makes an antioxidant object in a reduced state filled with electrons means reducing the antioxidant object itself in the oxidized state and reactive oxygen that attempts to oxidize the antioxidant object that you want to protect against oxidation. It is a concept that includes both the case of reducing the oxidizing substance itself such as seeds.

  By the way, when the pharmacological functional water having the above-described configuration is used for drinking, for example, assuming the large intestine as an antioxidant target, the sealing of the reducing power that hydrogen potentially has before reaching the large intestine is almost released. If this happens, there is a problem that the original purpose cannot be achieved.

  Therefore, the precious metal colloid as the catalyst is preferably subjected to treatment or operation for adjusting the activity and / or reaction time of the catalyst.

  Here, the treatment or operation for adjusting the activity and / or reaction time of the catalyst is related to, for example, a noble metal colloid or a combination of noble metal colloid and ascorbic acid (AsA) as shown in FIG. 3 or FIG. The process of encapsulating the active ingredient element in an enteric capsule or the like with the aim of starting the original catalytic action when the active ingredient element reaches a target site such as the large intestine or the small intestine. The range of the target range.

  In addition, according to the present invention, pharmacological functional water is contained as an active ingredient, and is used for various purposes including drinking, injection, infusion, dialysis, external use (application to skin and mucous membranes), cosmetics, and cosmetics. A biological application liquid characterized by being prepared for use in the present invention is provided.

  That is, for example, when the pharmacologically functional water according to the present invention is applied to a living body for use in injection, infusion, and dialysis, and in particular in a form that is directly applied to the bloodstream, Osmotic pressure adjustment, which is almost isotonic with blood, to a physiological liquid range (for example, pH 4.5 to 8.0, preferably pH 7.0 to 7.8, more preferably pH 7.1 to 7.5) It is necessary to adjust the pH. In this case, the osmotic pressure adjusting substance is not particularly limited as long as it is physiologically acceptable. For example, various electrolytes (for example, sodium, potassium, calcium, magnesium, zinc, iron, copper, manganese, iodine, phosphorus) Etc.), sugars such as glucose and hyaluronic acid, proteins such as albumin, amino acids and the like. The pH adjuster is not particularly limited as long as it is physiologically acceptable. For example, various organic acids, inorganic acids, organic bases, inorganic bases, and the like can be used. Preferably used. As this organic acid, for example, citric acid, acetic acid, succinic acid, gluconic acid, lactic acid, malic acid, maleic acid, malonic acid and the like can be used, and as the inorganic acid, for example, hydrochloric acid, phosphoric acid and the like should be used. Can do. On the other hand, as the organic base, for example, sodium citrate, sodium gluconate, sodium lactate, sodium malate, sodium acetate, sodium maleate, sodium malonate and the like can be used, and as the inorganic base, for example, water An alkali metal oxide or the like can be used.

  Furthermore, for the purpose of improving symptoms in living bodies, specifically humans, as optional components of pharmacological functional water (antioxidant functional water) according to the present invention, various electrolytes, amino acids, high-calorie components, enteral nutrients It is preferable to prepare and use medicinal solution components such as vitamins and drug components such as vitamins and antibiotics and use them as infusion solutions. As various electrolytes, for example, water-soluble salts of inorganic components such as sodium, potassium, calcium, magnesium, zinc, iron, copper, manganese, iodine, and phosphorus can be used. Moreover, as an amino acid, an essential amino acid, a non-essential amino acid, and / or a salt, ester, or N-acyl body of these amino acids etc. can be used, for example. Furthermore, as the high calorie component, for example, monosaccharides such as glucose and fructose, disaccharides such as maltose and the like can be used.

  Here, in the pharmacological functional water (antioxidant functional water) according to the present invention, for example, vitamins such as vitamin C and / or amino acids (good quality protein) are prepared and prepared for drinking, for injection, for infusion, for dialysis, It is considered that biological application liquids for various uses including external use (application to skin and mucous membranes), cosmetics, and cosmetics can also stimulate the immunity of the living body according to the following mechanism of action. That is, for example, vitamins such as vitamin C have radical scavenging activity similar to the pharmacological functional water (antioxidant functional water) of the present invention, while biological enzymes (for example, SOD, catalase, glutathione peroxidase) that control metabolism in the living body. , Interferon synthase, etc.) and interferon (a substance made of sugar and protein, which exerts immunity) plays a coenzyme role for synthesizing or displaying essential functions. In addition, amino acids (good quality proteins) play an important role as raw materials for biological enzymes and interferons.

Assume that an excessive amount of (.O ₂ ⁻ ) is locally generated in a living body, for example. Then, vitamins such as vitamin C and vitamin E, and biological enzymes such as SOD, catalase, and glutathione peroxidase cooperate with each other to eliminate (.O ₂ ⁻ ). At this time, vitamins such as vitamin C and vitamin E are oxidized in the process of reducing and eliminating (.O ₂ ⁻ ), so that they cannot perform their original work including a coenzyme role. Then, as a result of a decrease in synthesis or an intrinsic function in a living body such as a biological enzyme or interferon, a decrease in immunity is caused.

On the other hand, in a biological application liquid in which a pharmacological functional water (antioxidant functional water) according to the present invention contains vitamins such as vitamin C and amino acids (good quality protein), the pharmacological functional water is (· O ₂ ⁻ As a result of promoting the synthesis or intrinsic functions of biological enzymes and interferons derived from the supply of amino acids, as well as dedication of original work including coenzyme function of vitamins It is thought that the immunity activation of a living body can be expected.

  The pharmacologically functional water (antioxidant functional water) according to the present invention containing no vitamins and amino acids, the biologically applicable liquid according to the present invention containing vitamins, or the biologically applicable liquid according to the present invention containing amino acids. However, in the sense that the consumption of vitamins originally present in the living body is suppressed and the vitamins can concentrate on their original work including coenzyme function, the immune system is activated in accordance with the action mechanism illustrated here. It is thought that it can be expected.

  On the other hand, when using a precious metal colloid as a catalyst and applying it to a living body, it is essential to ensure safety. Specifically, it is necessary to consider biocompatibility issues including the acute toxicity of the noble metal colloid itself. Regarding platinum and palladium, for example, most of them are rapidly excreted as urine via the kidneys even if they are ingested by humans, and are approved by the Ministry of Health, Labor and Welfare as food additives ( In view of the fact that there is no restriction on the amount of addition), it is considered that there is almost no problem with biocompatibility. As another problem to be considered, in order to disperse the precious metal colloid stably and uniformly in the antioxidant functional water, it is preferable to contain some kind of dispersant. In this regard, for example, in the case of drinking or cosmetic / beauty use, a food additive having a function of a dispersant may be appropriately selected from those that have been approved by the Ministry of Health, Labor and Welfare. In this case, for example, sucrose fatty acid ester, polyvinyl pyrrolidone (PVP), gelatin and the like, which are hypoallergenic and widely used for cosmetics and pharmaceuticals, are preferably used. It should be noted that as a dispersant or protective film forming component for the noble metal colloid (responsible for adjusting the catalytic activity), the antioxidant functional water contains sucrose fatty acid ester, polyvinylpyrrolidone (PVP), gelatin, etc. Included in the category of treatments or operations to adjust catalyst activity and / or reaction time in relation to the claims.

  Such antioxidant functional water (pharmacological functional water) is considered to be applicable in the following industrial fields, for example.

  The first is application in the medical and pharmaceutical fields. For example, it can be used as a base water in infusion production and other pharmaceutical production processes. It can also be used as an artificial dialysis solution, a peritoneal fluid, or a disease treatment agent. Furthermore, for example, it can also be suitably used as a preservation solution for transplanted organs during transplantation of living organs (in this case, it is preferable to separately adjust osmotic pressure). Thereby, effects such as prevention / treatment of all diseases derived from reactive oxygen species, reduction of side effects and prevention of aging of pharmaceuticals, and improvement of preservation of transplanted organs can be expected.

  The second is application as a preventive / therapeutic agent for aging / degeneration caused by oxidation of skin tissue. For example, it can be used in the manufacturing process of lotion and other cosmetics.

  The third is application as an antioxidant food, functional food, and health food. For example, the use in a foodstuff manufacturing process can be considered.

  The fourth is application in drinking water, processed drinking water and others. For example, use as drinking water (antioxidant water) and health drinks, and use as base water for processed drinking water such as can juice, can coffee, plastic bottle water, and soft drinks are conceivable.

  Fifth is the application to the improvement of contamination and deterioration of food ingredients by pesticides, herbicides, insecticides, etc., and to maintain freshness. For example, it can be used as a washing liquid before shipment of vegetables and fruits.

  The sixth is application as a substitute for antioxidants, quality deterioration inhibitors, antiseptics, antifouling agents, deodorants, freshness-preserving agents, etc. in the processed food manufacturing process. Specifically, for example, use as a substitute for 347 types of food additives is conceivable.

  To explain this further, the involvement of radicals containing reactive oxygen species in oxidation, aging, quality deterioration, decay, pollution, deodorization, and reduction in freshness is pointed out as one of the important factors in their expression and malignant mechanisms. Has been. As a result, radicals containing reactive oxygen species can cause serious damage such as health problems, disease onset, decline in physiological function, degradation of beauty appearance, decline in product value, decline in productivity, and increase in lifestyle and natural environment load. Giving. This also contributes to an increase in medical costs due to illness that is likely to occur and difficult to cure, and industrial losses such as opportunity loss and high cost burden in production and distribution. Examples where the involvement of reactive oxygen species is desirable are just a limited number of examples such as sterilization, disinfection, and bleaching, and in most instances reactive oxygen species have only a negative impact. The present invention provides the most efficient and low-cost solution with a wide range of applications for various industrial problems caused by radicals containing these active oxygen species.

  Cases in which living organisms are exposed to reactive oxygen species suddenly or in large quantities are relatively limited cases such as sudden blood recirculation during surgery, organ transplantation, whole body burns, and pulmonary emphysema that suddenly floats during diving. In this example, a small amount of reactive oxygen species becomes fire and eventually causes widespread harm.

  Metabolism of living organisms, accumulation of waste products, exposure to direct sunlight, ultraviolet rays and radiation, contact with carcinogenic and mutagenic substances and heavy metals, burns and viral infections, cuts and cell destruction There are many opportunities to activate normal or inactive oxygen, oxygen molecule-containing compounds, and the like when they are covered, and to be radicalized. In addition, when exposed to food and drink with active oxygen species, cigarette smoke, smoke exhaust gas, chlorinated organic solvents, etc., they are not only directly affected by radicals, but also on the living body side. The generation of reactive oxygen species is induced or induced. Although the amount of reactive oxygen species produced at the beginning is very small and local, the reactive oxygen species gradually and accelerate as the production continues beyond the normal range or cannot be removed after the production continues. It begins to increase and begins to develop adverse effects as in the above example.

  In other words, reactive oxygen species are different in how they are damaged from normal chemical reactions (non-radical reactions) such as redox reactions and enzymatic reactions in that their generation and influence increase in a chain. To. In other words, due to the generation of reactive oxygen species, a decrease in physiological function or degeneration is potentially progressing, and as soon as it suddenly becomes apparent when there is a certain day, it appears as a major damage rapidly. It will come.

  For example, in the case of human disease, chronic oxidative stress caused by reactive oxygen species causes cardiovascular diseases such as diabetes (especially insulin-independent type), cirrhosis (especially fatty liver type), angina pectoris (especially arteriosclerosis). Type), dementia (especially cerebral infarction type), malignant tumor (mainly chemical carcinogenesis) and is said to be the main criminal involved in the pathogenesis of various diseases. In addition, aging, aging, or fatigue due to deterioration of physiological functions due to aging (aging) or physical exhaustion, increased metabolism or respiratory abnormalities due to continuous intense movements, excessive or insufficient nutritional balance or intake, and lack of sleep or exercise. It appears as a phenomenon. In these phenomena, metabolic waste products are likely to accumulate, or the generation of reactive oxygen species or an increase in the residual accumulation amount has been observed due to poor regeneration and functional deterioration of cellular tissues, skin, etc. It is a major factor in promoting and delaying recovery.

  To illustrate the case of animals and plants other than humans, excessive production or residual accumulation or exposure of reactive oxygen species not only causes various health and growth disorders similar to those in humans, but as a result thereof. In the livestock breeding, pet breeding, aquaculture and plant cultivation industries, lower milk production, lower meat quality and fattening rate, lower egg production rate, hair loss such as hair loss, reduced breeding efficiency, increased difficulty of pest damage, appreciation value This also leads to a decrease in productivity and a decrease in commercial value, such as a decrease, a cultivated harvest amount, aquaculture landing amount and a decrease in the quality of these.

  In the case of food and drink and feed itself, for example, reactive oxygen species generation by exposure to ultraviolet rays, mixing of raw materials with active oxygen species, etc., active oxygen species raw material, sterilization and bleaching in the manufacturing process Depending on the residual hydrogen peroxide used, oxidative degradation of vitamins and other nutritive and edible ingredients, fat and oil breakdown and emulsion breakdown for those containing and using fat, fading and discoloration for those containing and using pigment, and wounds for fresh food Degradation from the above, and accompanying this, the unpleasant odor and the reduction in taste and texture are accelerated at an accelerated rate, resulting in significant quality degradation.

  For example, in the case of the environment, the presence of a floating substance with or containing radicals containing reactive oxygen species brings an unpleasant odor, allergy or inflammation to the living space or work space, and promotes water quality changes. Is done.

  Although damage such as these cases can proceed without involvement of reactive oxygen species, there is no doubt that the progression is greatly promoted by involvement of reactive oxygen species.

  When radicals containing reactive oxygen species are involved in damage increase, damage is prevented with conventional antioxidants, anti-aging agents, anti-degradation agents, anti-corrosion agents, anti-fouling agents, deodorants and freshness-keeping agents. It is difficult to prevent or suppress this, and the inventors are strongly convinced that the only solution is the present invention related to antioxidant methods, antioxidant functional water, and their uses.

  The present invention has the main effect of antioxidation as compared with the use of reactive oxygen species scavengers such as conventional antioxidants, but does not cause any side effects associated therewith. Therefore, both safety and radical scavenging efficiency are achieved. At the same time, it is possible to solve many problems such as difficulty in use and limitation of applications such as deterioration in flavor and color, destruction of physical properties, cost increase, and concern about secondary infection, which were difficult to solve with conventional products. It is.

  In addition, as shown in the examples described later, the present invention is not easily affected by pH, so that it can be widely applied in a liquid region from acidic to alkaline, unlike cases such as enzymes and antioxidants. Moreover, by exhibiting a high effect at room temperature, it is extremely useful industrially in a wide range of fields including the food and pharmaceutical fields.

  As described above, the important elements in the present invention are firstly the hydrogen-dissolved water, secondly the noble metal colloid catalyst, and thirdly the antioxidant object. Only after these three elements are combined organically, the hydrogen's potential reducing power seal is released and the antioxidant and pharmacological functions are manifested.

  According to the pharmacological functional water according to the present invention, the hydrogen-dissolved water in which molecular hydrogen as a substrate is contained in raw water, and the hydrogen-dissolved water contains the molecular hydrogen as an atomic product. It contains an antioxidant functional water composed of a noble metal colloid that catalyzes a reaction that decomposes into hydrogen as an active ingredient, and can exhibit a pharmacological function without side effects.

  That is, the pharmacologically functional water and the present invention relating to its use exhibit an excellent radical scavenging function in a wide pH range from acidic to alkaline and at room temperature.

  Accordingly, the present invention is intended to prevent various disorders such as oxidative stress and aging that are easily caused by the involvement of reactive oxygen species in physiological functions in living organisms such as humans, non-human animals, plants, fermenting microorganisms, and cultured cells. Quality for quality improvement, degradation, degradation, rot, pollution, heterobromination, reduced freshness, reduced efficacy, reduced efficiency, etc. for improvement or in breeding, aquaculture, cultivation, fermentation, culture, processing, storage, etc. In particular, it is expected to be used in fields where it is required to prevent deterioration and decrease in activity.

  In addition, food, feed, pharmaceutical and medical supplies, quasi-drugs, cosmetics, detergents, deodorants, hygiene products, clothing products, freshness-keeping materials and packaging containers, animal breeding, aquaculture, plant cultivation, fermentation, Its usefulness is also expected in various industrial fields such as culture.

  Moreover, specific examples that can be provided to the user so that the usefulness of the present invention can be easily demonstrated and utilized are as follows.

  For example, in the food field, as a food additive having a high function of removing reactive oxygen species, it can improve the quality and shelf life of processed foods and maintain freshness in fresh foods, or use the pharmacologically functional water of the present invention as an active ingredient. By providing foods for specified health use and health foods, they can be used for health maintenance and disease prevention, respectively. In the feed field, it can be used as a feed additive or pet food for health management, feed efficiency and productivity improvement.

  In the fields of pharmaceuticals, quasi-drugs, cosmetics and medical devices as prescribed in each item of Article 2 of the Pharmaceutical Affairs Law, not only can it be used to improve the quality of pharmaceutical preparations as pharmaceutical additives and cosmetic additives, It can be used as an active ingredient for treatment and prevention of diseases, improvement of physical condition, maintenance and improvement of beauty, ensuring hygiene and comfortable environment. Among these, in the case of pharmaceuticals, medical treatment water for diseases that cause onset or recovery delay or worsening of symptoms due to involvement of reactive oxygen species, or for general use, nourishing tonic health medicine, gastrointestinal medicine, cold medicine, oral rhinitis medicine, Particularly useful in the field of eye drops and skin drugs. For quasi-drugs, in the fields of medicated toothpastes, mouth fresheners, medicinal cosmetics, hair preparations, bath preparations, anti-odor agents and physiological treatment products, and in cosmetics, hair cosmetics and hair-washing cosmetics It is highly useful in the fields of lotions, cream emulsions, packs, foundations, lipsticks, facial cleansers, soaps, and toothpastes.

  In addition to the examples described above, it is possible to provide the pharmacologically functional water according to the present invention in a specific manner, and the embodiment and utility of the present invention are not limited to the above examples. I will add that.

FIG. 1 is a graph showing the Nernst equation. FIG. 2 is a diagram for explaining a lighting experiment using LEDs. FIG. 3 is a diagram for explaining an application example of the present invention. FIG. 4 is a diagram for explaining an application example of the present invention. FIG. 5 is a longitudinal sectional view showing a basic structure of the reducing potential water generating device 11 used for generating the base water (hydrogen-dissolved water) of the antioxidant functional water according to the present invention. FIG. 6 is a view showing the reduction activity evaluation test result of Pt colloid catalyst-added electrolyzed water by methylene blue color change. FIG. 7 is a view showing the reduction activity evaluation test result of Pt colloid catalyst-added electrolyzed water by methylene blue color change. FIG. 8 is a diagram showing a reduction activity evaluation test result of Pt colloid catalyst-added hydrogen-dissolved water based on a color change of methylene blue. FIG. 9 is a diagram showing a reduction activity evaluation test result of Pt colloid catalyst-added hydrogen-dissolved water based on a color change of methylene blue. FIG. 10 is a diagram showing the reduction activity evaluation test result of Pd colloid catalyst-added hydrogen-dissolved water based on the color change of methylene blue. FIG. 11 is a diagram showing the reduction activity evaluation test result of Pd colloid catalyst-added hydrogen-dissolved water based on the color change of methylene blue. FIG. 12 is a graph showing the reduction activity evaluation test result of the noble metal mixed (Pt + Pd) colloid catalyst-added hydrogen-dissolved water based on the color change of methylene blue. FIG. 13 is a view showing a reduction activity evaluation test result of mixed noble metal (Pt + Pd) colloid catalyst-added hydrogen-dissolved water by methylene blue color change. FIG. 14 is a diagram showing a reduction activity evaluation test result of Pt colloid catalyst-added electrolytically treated water (added before electrolytic treatment / added after electrolytic treatment) due to color change of methylene blue. FIG. 15 is a diagram showing the antioxidative activity evaluation test results of Pt colloid catalyst-added electrolyzed water by color change of DPPH radicals. FIG. 16 is a diagram showing the antioxidant activity evaluation test result of Pt colloid catalyst-added electrolyzed water by the change in color of DPPH radicals. FIG. 17 is a diagram showing the results of an evaluation test of the antioxidant activity of catalyst-added hydrogen-dissolved water (degassing process + hydrogen gas sealing process) due to color change of DPPH radicals. FIG. 18 is a graph showing the antioxidant activity evaluation test result of catalyst-added hydrogen-dissolved water (degassing treatment + hydrogen gas sealing treatment) due to color change of DPPH radicals. FIG. 19 is a diagram showing a reduction activity evaluation test result of enzyme hydrogenase-catalyzed hydrogen-dissolved water (degassing process + hydrogen gas sealing process) due to a color change of methylene blue. FIG. 20 is a diagram showing a reduction activity evaluation test result of hydrogen water dissolved in an enzyme hydrogenase catalyst (degassing treatment + hydrogen gas sealing treatment) due to a color change of methylene blue. FIG. 21 is a diagram for explaining a dissolved hydrogen concentration quantitative analysis method by oxidation-reduction dye oxidation-reduction titration. FIG. 22 is a diagram for explaining a dissolved hydrogen concentration quantitative analysis method by oxidation-reduction dye oxidation-reduction titration. FIG. 23 is a diagram for comparison of the actual measurement value and effective value of the dissolved hydrogen concentration DH of various sample waters. FIG. 24 is a diagram for explaining the cytochrome c reduction method. FIG. 25 is a diagram for explaining the epinephrine oxidation method. FIG. 26 is a graph showing the time-dependent change characteristic of radical scavenging activity expressed by the Pt colloid catalyst-containing hydrogen-dissolved water with the Pt colloid concentration as a main parameter. FIG. 27 is a graph showing the time-dependent change characteristics of radical scavenging activity expressed by Pd colloid catalyst-containing hydrogen-dissolved water with the Pd colloid concentration as a main parameter. FIG. 28 is a graph showing a time-dependent change characteristic of radical scavenging activity expressed by Pt colloid catalyst-containing hydrogen-dissolved water with the Pt colloid concentration as a main parameter. FIG. 29 is a diagram showing a time-dependent change characteristic of radical scavenging activity expressed by (Pt + Pd) mixed colloid catalyst-containing hydrogen-dissolved water, with (Pt + Pd) mixed colloid concentration as a main parameter. FIG. 30 shows the time-dependent change characteristics of the radical scavenging activity expressed by the (Pt + Pd) mixed colloid catalyst-containing hydrogen-dissolved water with the (Pt + Pd) mixed colloid concentration as the main parameter and the mixed molar ratio of Pt: Pd as the secondary main parameter FIG. FIG. 31 shows the time-dependent change characteristics of radical scavenging activity expressed by (Pt + Pd) mixed colloid catalyst-containing hydrogen-dissolved water with (Pt + Pd) mixed colloid concentration as the main parameter and Pt: Pd mixed molar ratio as the sub-main parameter. FIG. FIG. 32 is a graph showing the time-dependent change characteristic of radical scavenging activity expressed in Pt colloid catalyst pre-added 1-pass electrolyzed water with Pt colloid concentration as a main parameter. FIG. 33 is a diagram showing a time-dependent change characteristic of radical scavenging activity expressed by Pd colloid catalyst pre-added 1-pass electrolyzed water with Pd colloid concentration as a main parameter. FIG. 34 is a diagram showing a time-dependent change characteristic of radical scavenging activity expressed in Pt colloid catalyst pre-added circulating electrolyzed water with Pt colloid concentration as a main parameter. FIG. 35 is a graph showing a time-dependent change characteristic of radical scavenging activity expressed in Pd colloid catalyst pre-added circulating electrolyzed water with Pd colloid concentration as a main parameter. FIG. 36 is a diagram showing a time-dependent change characteristic of radical scavenging activity expressed by an AsA aqueous solution, with the AsA aqueous solution concentration as a main parameter. FIG. 37 is a graph showing the time-dependent change characteristics of radical scavenging activity expressed by catalyst-containing hydrogen-dissolved water, with the difference in the type of noble metal catalyst as a main parameter (concentration is fixed). FIG. 38 is a diagram showing the action mechanism of the Pt colloid catalyst in a hydrogen / oxygen coexisting aqueous solution system. FIG. 39 is a diagram showing the mechanism of action of the Pd colloid catalyst in a hydrogen / oxygen coexisting aqueous solution system. FIG. 40 is a diagram illustrating an effective value of the dissolved hydrogen concentration DH according to the example. FIG. 41 shows that Pt colloid catalyst-containing two-stage electrolyzed water (AOW) is C. elegans C.I. It is a figure which shows the influence which it has on the lifetime of elegance. FIG. 42 shows that two-stage electrolyzed water containing Pt colloid catalyst (AOW) It is a figure which shows the influence which it has on the lifetime of elegance. FIG. 43 is a graph showing the time-dependent characteristics of the reduced vitamin C residual rate (%) when reduced vitamin C is contained in various test waters having a neutral liquidity with a buffer solution (pH 7.4). It is. FIG. 44 is a graph showing the time-dependent characteristics of reduced vitamin C residual rate (%) when various types of test water whose basicity is made basic with buffer solution (pH 9.0) contain reduced vitamin C. It is. FIG. 45 is a graph showing the time-dependent characteristics of reduced vitamin C residual rate (%) when various types of test water whose acidity is made acidic with a buffer solution (pH 2.2) contain reduced vitamin C. is there. FIG. 46 is a diagram showing the influence of drinking noble metal colloid (Pt or Pd) catalyst-containing electrolytic hydrogen water (AOW) on suppression of oxidative damage of rat gene DNA. FIG. 47 is a diagram showing the effect of drinking noble metal colloid (Pt or Pd) catalyst-containing electrolytic hydrogen water (AOW) on lipid peroxidation suppression in rats. FIG. 48 is a diagram showing the effect of drinking noble metal colloid catalyst-containing electrolytic hydrogen water (AOW) on the weight of rats. FIG. 49 is a diagram showing the influence of drinking noble metal colloid catalyst-containing electrolytic hydrogen water (AOW) on arthritis score transition. FIG. 50 is a diagram showing the effect of drinking noble metal colloid catalyst-containing electrolytic hydrogen water (AOW) on the sensitized limb volume transition. FIG. 51 is a diagram showing the effective value of the dissolved hydrogen concentration DH exhibited by the antioxidant functional water (pharmacological functional water) used in various test groups of the pharmacological test.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

  First, the basic structure of the reducing potential water generating device 11 used for generating the base water (hydrogen-dissolved water) of the antioxidant functional water (pharmacological functional water) according to the present invention will be described with reference to FIG.

  In the reduction potential water generator 11 of this example, an introduction port 111 for introducing raw water such as pure water and a lead-out port 112 for taking out the generated reduction potential water are formed. An electrolysis chamber 113 is formed between the outlet 112. Although there is no particular limitation, in the reduction potential water generating device 11 of this example, an inlet 111 is formed on the bottom surface of the casing 114 so that raw water is introduced in a direction perpendicular to the paper surface shown in the figure. A lead-out port 112 is formed on the surface so that electrolyzed water is taken in a direction perpendicular to the illustrated paper surface.

  In addition, porous diaphragms 115 are provided on the left and right side walls of the reduction potential water generator 11, and the electrode plates 116 are provided in contact with the outside of the diaphragm 115. The other electrode plate 117 is provided in the electrolysis chamber 113 such that the main surface thereof faces the one electrode plate 116.

  A DC power source (power supply circuit) 12 is connected to the two pairs of electrode plates 116 and 117, and an anode is provided on one of the pair of electrode plates 116 and 117 facing each other with the diaphragm 115 interposed therebetween, and the other electrode plate is provided on the other electrode plate. A cathode is applied. For example, when reducing potential water is generated in the electrolysis chamber 113, the cathode of the DC power source 12 is connected to the electrode plate 117 provided in the electrolysis chamber 113 as shown in FIG. The anode is connected to the electrode plate 116 provided on the substrate.

  When electrolytically oxidized water is generated in the electrolysis chamber 113, the anode of the DC power supply 12 is connected to the electrode plate 117 provided in the electrolysis chamber 113, and the electrode plate 116 provided outside the electrolysis chamber 113 is connected to the electrode plate 116. What is necessary is just to connect a cathode.

  The electrode plates 116 and 117 used in this example are configured by firing and coating one or more noble metals selected from the group of platinum, iridium, palladium and the like over the entire surface of the titanium material. The electrode plates 116 and 117 have a plurality of punch holes as will be described later.

  The diaphragm 115 used in this example preferably has a property that the water flowing into the electrolysis chamber 113 is easily soaked and the soaked water is difficult to drip. That is, in the reduction potential water generating apparatus 11 of this example, a water film is formed in the diaphragm 115 itself and a slight gap S between the diaphragm 115 and the electrode plate 116 during electrolysis, and both electrode plates 116, A current flows through 117. Therefore, it is important to increase the electrolysis efficiency that the water constituting the water film is sequentially replaced. Further, since the water soaked into the diaphragm 115 needs to be treated when it leaks from between the diaphragm 115 and the electrode plate 116, it is preferable that the water soaked in the soaked water does not sag. However, when, for example, a solid electrolyte membrane is employed as the diaphragm, the solid electrolyte membrane itself has electrical conductivity. In this case, a slight gap S is formed between the diaphragm 115 and the electrode plate 116. Can be omitted.

As an example of the diaphragm 115, the aggregate is polyester non-woven fabric or polyethylene screen, the membrane material is chlorinated ethylene or polyvinylidene fluoride and titanium oxide or polyvinyl chloride, the thickness is 0.1 to 0.3 mm, and the average pore diameter is Examples thereof include a porous membrane having a thickness of 0.05 to 1.0 μm and a water permeability of 1.0 cc / cm ² · min or less, or a solid electrolyte membrane. When a cation exchange membrane is used as the diaphragm 115, for example, a cation exchange group perfluorosulfonic acid membrane whose base material is polytetrafluoroethylene such as a Nafion membrane manufactured by Du Pont, or a Flemion membrane manufactured by Asahi Kasei. A copolymer of a cation exchange group vinyl ether and tetrafluoroethylene can be used.

  On the other hand, the distance between the pair of electrode plates 116 and 117 arranged to face each other with the diaphragm 115 interposed therebetween is 0 mm to 5.0 mm, more preferably 1.5 mm. Here, the distance between the plates of the electrode plates 116 and 117 is 0 mm, for example, in the case of using a zero gap electrode in which an electrode film is directly formed on each of both main surfaces of the diaphragm 115. Having a distance of a minute. The zero gap electrode may be formed only on one main surface of the diaphragm 115. Further, when such a zero gap electrode is adopted, holes (for example, punch holes) or gaps for allowing gas generated from the electrode surface to escape to the back side opposite to the diaphragm 115 are provided in the electrode plates 116 and 117. It is desirable to keep it. In addition, the structure which provides a hole or a clearance gap in the electrode plates 116 and 117 is employable also in the electrode plate provided in the electrolytic cell shown in FIG.

  The distance between the electrode plates 117 and 117 provided in the electrolysis chamber 113 is not particularly limited, but is 0.5 mm to 5 mm, more preferably 1 mm.

In order to generate reduction potential water using the reduction potential water generator 11 configured as described above, first, two electrode plates 117 and 117 provided in the electrolysis chamber 113 are connected to the negative electrode (− ), And the positive electrode (+) of the DC power source 12 is connected to the electrode plates 116 and 116 provided outside the electrolysis chamber 113, and the voltage is applied to the two pairs of electrode plates 116 and 117 facing each other with the diaphragm 115 interposed therebetween. Is applied. When pure water or the like is introduced from the introduction port 111, water is electrolyzed in the electrolysis chamber 113, and on the surface of the electrode plate 117 and in the vicinity thereof,
2H ₂ O + 2e ⁻ → 2OH ⁻ + H ₂ ↑
The following reaction occurs. Further, on the surface of the electrode plate 116 outside the electrolytic chamber 113 with the diaphragm 115 interposed therebetween, that is, between the electrode plate 116 and the diaphragm 115,
H ₂ O-2e ⁻ → 2H ^{+ +} 1/2 · O ₂ ↑
The following reaction occurs.

The H ⁺ ions pass through while being stored in the diaphragm 115, and a part of them accepts the electrons e ⁻ from the cathode plate 117 and becomes hydrogen gas and dissolves in the generated electrolyzed water on the cathode side. Thereby, the electrolyzed water produced | generated by the cathode side (namely, the inside of the electrolysis chamber 113) turns into reduction potential water whose oxidation reduction potential (ORP) is lower than the electrolyzed water produced | generated using the conventional diaphragm membrane electrolysis technique.

Further, since the remainder of the H ⁺ ions that have passed through the diaphragm 115 react with the OH ⁻ ions in the electrolysis chamber 113 and return to water, the pH of the reducing potential water generated in the electrolysis chamber 113 is slightly neutral. It will be. That is, reduction potential water having a low ORP but a low pH is obtained. Reduction potential water containing hydroxide ions generated in this way is supplied from the outlet 112.

  In addition, when the reduction potential water obtained by such electrolytic treatment is desired to have a desired pH value, for example, a solution of a pH buffering salt such as phthalate, phosphate or borate is used in advance. What is necessary is just to adjust pH value of. This is because the reduction potential water generator 11 does not change the pH of the raw water greatly. Specifically, for example, if it is desired to incline the pH to alkalinity for the purpose of washing silicon substrates or using beverages, the pH value of raw water may be controlled and prepared near alkalinity, and beverages, injection solutions, If you want to make the pH almost neutral for the purpose of drip solution or dialysis solution, the pH value of raw water can be controlled and adjusted to around neutral, and furthermore, the pH can be lowered for cosmetic use. If it is desired to make it acidic, the pH value of the raw water may be controlled and adjusted around weak acidity.

  Incidentally, in the above-described embodiment, the apparatus shown in FIG. 5 has been described as the apparatus for generating the reduction potential water, but this apparatus 11 can also be applied to the case of generating the oxidation potential water. In this case, the anode (+) of the DC power source 12 is connected to the two electrode plates 117 and 117 provided in the electrolysis chamber 113, and the DC is applied to the electrode plates 116 and 116 provided outside the electrolysis chamber 113. What is necessary is just to apply a voltage to the two pairs of electrode plates 116 and 117 that are connected to the cathode (-) of the power supply 12 and face each other with the diaphragm 115 interposed therebetween.

When pure water or the like is introduced from the introduction port 111, water is electrolyzed in the electrolysis chamber 113, and on the surface of the electrode plate 117 and in the vicinity thereof,
H ₂ O-2e ⁻ → 2H ^{+ +} 1/2 · O ₂ ↑
On the surface of the electrode plate 116 outside the electrolysis chamber 113 sandwiching the diaphragm 115, that is, on the water film between the electrode plate 116 and the diaphragm 115,
2H ₂ O + 2e ⁻ → 2OH ⁻ + H ₂ ↑
The following reaction occurs.

The OH ⁻ ions pass through the diaphragm 115 while being stored therein, and a part of them passes the electron e ⁻ to the cathode plate 117 to become oxygen gas and dissolve in the generated electrolyzed water on the anode side. Thereby, the electrolyzed water produced | generated by the anode side (namely, in the electrolysis chamber 113) turns into an oxidation potential water whose oxidation reduction potential (ORP) is higher than the electrolyzed water produced | generated using the conventional diaphragm membrane electrolysis technique.

In addition, since the remaining OH ⁻ ions that have passed through the diaphragm 115 react with H ⁺ ions in the electrolysis chamber 113 and return to water, the pH of the oxidation potential water generated in the electrolysis chamber 113 is slightly closer to neutral. It will be. That is, oxidation potential water having a high ORP although the pH is not so low is obtained. The oxidation potential water containing the hydrogen ions generated in this way is supplied from the outlet 112.

Incidentally, the reduction potential water generator 11 shown in FIG. 5 is used to connect the cathode (−) of the DC power source 12 to the two electrode plates 117 and 117 provided in the electrolysis chamber 113, and to the outside of the electrolysis chamber 113. The anode (+) of the DC power source 12 is connected to the provided electrode plates 116 and 116 (effective area of the electrode plate is 1 dm ² ), and Fujisawa city tap water with a pH of 7.9 and an ORP of +473 mV is 1 per minute. The flow rate of liters (The appropriate flow rate in the reduction potential water generator 11 is 1 to 3 liters per minute, preferably 1 to 1.8 liters per minute, and particularly preferably 1.3 to 1.8 liters per minute. In this case, the electrolytic treatment was performed in a continuous water flow type under the electrolysis conditions of 5 A constant current. At this time, a Nafion membrane manufactured by Du Pont, which is a cation exchange membrane, is used as the diaphragm 115, the distance between the electrode plates 116 and 117 is 1.2 mm, and the distance between the electrode plates 117 and 117 in the electrolytic chamber 113. Was 1.4 mm.

As a result, immediately after the electrolytic treatment, reduced potential water having pH = 9.03 and ORP = −720 mV was obtained. The reduction potential water was allowed to stand, and the pH and ORP after 5 minutes, 10 minutes, and 30 minutes were measured, and after 5 minutes, pH = 8.14, ORP = −706 mV, 10 minutes. Later, pH = 8.11, ORP = −710 mV, and 30 minutes later, pH = 8.02 and ORP = −707 mV. That is, at the time immediately after the electrolytic treatment, the pH of the treated water exceeded 9, but the pH immediately dropped and stabilized at around pH 8. This is because H ⁺ ions generated in the vicinity of the water film between the diaphragm 115 and the anode plate 116 pass through the diaphragm 115 and move to the electrolysis chamber 113, and then neutralize with OH ⁻ ions in the electrolysis chamber 113. Although the reaction returns to the original water, this neutralization reaction is promoted over time until concentration chemical equilibrium is established, even when the reduced potential water after electrolytic treatment is allowed to stand. This is considered to be the cause.

《Reduction activity / radical scavenging activity evaluation test of hydrogen-dissolved water containing noble metal colloid catalyst》
In the following, when the noble metal colloid catalyst (Pt colloid / Pd colloid) is contained in the hydrogen-dissolved water according to the present invention, it is expressed by activation of chemically inactive molecular hydrogen contained in the hydrogen-dissolved water. For each evaluation test of reducing activity or radical scavenging activity to be performed, examples and reference examples will be shown.

Of the _two types of evaluation test described above, in the reduction activity evaluation test, methylene blue (tetramethylthionine chloride; C ₁₆ H ₁₈ ClN3S · 3 (H ₂ O)) is used as an antioxidant target, while radical scavenging activity is reduced. In the evaluation test, DPPH radical (1,1-diphenyl-2-picrrylhydrazyl), which is a relatively stable radical in an aqueous solution, is used as an antioxidant.

  Here, the principle of evaluation of reduction activity when methylene blue belonging to the category of redox dye is used as an antioxidant target will be described. Oxidized methylene blue aqueous solution (absorption maximum wavelength: about 665 nm, hereinafter methylene blue is referred to as “MB”) Is blue, but when it is reduced to reduced methylene blue (leucomethylene blue), the color changes from blue to colorless. The reduction activity, that is, the reducing power is evaluated by the degree of disappearance of the blue color. Although reduced methylene blue has a low solubility, a white precipitate is formed. However, when reoxidized, the original oxidized methylene blue is restored to blue. That is, the color reaction of the methylene blue aqueous solution is reversible.

  On the other hand, the principle of evaluating radical scavenging activity when DPPH radical is used as an antioxidant target will be explained. An aqueous DPPH radical solution (absorption maximum wavelength; about 520 nm, hereinafter sometimes referred to as “DPPH”) exhibits a deep red color. When such DPPH is reduced and is no longer a radical, the deep red color fades. The radical scavenging activity, that is, the antioxidant power is evaluated by the degree of fading. The color reaction of the DPPH radical aqueous solution is irreversible.

  The explanation of the evaluation test is as follows: (1) Evaluation of reduction activity of electrolyzed Pt colloid catalyst-containing electrolyzed water by methylene blue color change, (2) Pt colloid / Pd colloid catalyst-containing hydrogen-dissolved water (degassed by methylene blue color change) (3) Reduction activity evaluation of Pt colloid catalyst-containing electrolytically treated water (added before electrolytic treatment / added after electrolytic treatment) due to color change of methylene blue, (4) DPPH radical Evaluation of antioxidant activity of electrolyzed water containing Pt colloid catalyst by color change, (5) Antioxidant activity evaluation of catalyst-containing hydrogen-dissolved water (degassing + hydrogen gas encapsulating) by color change of DPPH radical It shall be done in

(1) Evaluation of reducing activity of electrolyzed Pt colloid catalyst-containing electrolyzed water by color change of methylene blue (1-A); reducing power evaluation test procedure Standard buffer solution 6.86 (phosphate aqueous solution manufactured by Wako Pure Chemical Industries, Ltd.) ) And 9.18 (borate aqueous solution) are each diluted 10-fold with purified water to prepare pH buffered aqueous solution. Hereinafter, these two types of dilution water are referred to as “basic water 6.86” and “basic water 9.18”, respectively. Also, a platinum colloid made of Tanaka Kikinzoku (whose particle size distribution is 2 to 4 nm and containing polyvinylpyrrolidone as a dispersant), 4 g of a 4% solution, was dissolved in 500 mL of distilled water manufactured by Wako Pure Chemical Industries, Ltd. This is called “Pt standard solution”. Note that the concentration C (Pt) of the platinum component in the Pt reference solution is 48 mg / L from the calculation formula C (Pt) = 0.6 g × 0.04 / 500 mL. Then, using the two types of basic water 6.86 and 9.18 and the Pt reference solution, four types of each and eight types of sample aqueous solutions were prepared. They are shown below.

i. Basic water (6.86)
ii. An aqueous solution containing Pt colloid in which 6 mL of Pt standard solution is added to 1494 mL of basic water (6.86).
iii. An aqueous solution obtained by electrolytic treatment of basic water (6.86)
iv. An aqueous solution in which 6 mL of Pt standard solution is added to 1494 mL of basic water (6.86) to form an aqueous solution containing Pt colloid, and the aqueous solution is electrolytically treated.
v. Basic water (9.18)
vi. An aqueous solution containing Pt colloid in which 6 mL of Pt standard solution is added to 1494 mL of basic water (9.18).
vii. An aqueous solution obtained by electrolytic treatment of basic water (9.18)
viii. 6 mL of Pt standard solution is added to 1494 mL of basic water (9.18) to form an aqueous solution containing Pt colloid, and the aqueous solution is subjected to electrolytic treatment. , ORP (mV), temperature T (° C.), and Pt colloid concentration are summarized in Table 2 below.

上記i〜viiiの都合８通りの各サンプル水溶液の還元活性をそれぞれ調べるために、各水溶液３５０ｍＬにメチレンブルー（１ｇ／Ｌ濃度）溶液を１０ｍＬ加え、メチレンブルーモル濃度を７４．４μＭに調製して、各サンプル水溶液のメチレンブルー吸光度（Ａ５８９；波長５８９ｎｍにおける吸光度）を分光光度計で測定した。

In order to investigate the reducing activity of each of the eight aqueous solutions of the above i to viii, 10 mL of a methylene blue (1 g / L concentration) solution was added to 350 mL of each aqueous solution, and the methylene blue molar concentration was adjusted to 74.4 μM. The methylene blue absorbance (A589; absorbance at a wavelength of 589 nm) of the sample aqueous solution was measured with a spectrophotometer.

(1-B); Disclosure of Reference Examples and Examples (Reference Example 1)
The methylene blue absorbance (A589) of the aqueous solution obtained by adding methylene blue to the catalyst-free aqueous solution, which is the basic water 6.86 of sample i, is referred to as Reference Example 1, and the results are shown in FIG.

(Reference Example 2)
The methylene blue absorbance (A589) of an aqueous solution obtained by adding methylene blue to the catalyst-containing aqueous solution (basic water 6.86 + Pt reference solution) of sample ii is referred to as Reference Example 2, and the results are shown in FIG.

(Reference Example 3)
The methylene blue absorbance (A589) of an aqueous solution obtained by adding methylene blue to catalyst-free electrolyzed water (basic water 6.86 + electrolytic treatment) of Sample iii is referred to as Reference Example 3, and the results are shown in FIG.

Example 1
Methylene blue absorbance (A589) of an aqueous solution of sample iv (basic water 6.86 + electrolytic treatment + Pt standard solution) in which methylene blue was added to the catalyst-containing electrolytically treated water was set as Example 1, and the results were compared with Reference Examples 1-3. As shown in FIG.

(Reference Example 4)
The methylene blue absorbance (A589) of the aqueous solution obtained by adding methylene blue to the catalyst-free aqueous solution, which is the basic water 9.18 of sample v, is referred to as Reference Example 4, and the results are shown in FIG.

(Reference Example 5)
The methylene blue absorbance (A589) of the aqueous solution obtained by adding methylene blue to the catalyst-containing aqueous solution (basic water 9.18 + Pt reference solution) of sample vi is referred to as Reference Example 5, and the results are shown in FIG.

(Reference Example 6)
Methylene blue absorbance (A589) of an aqueous solution obtained by adding methylene blue to catalyst-free electrolyzed water (basic water 9.18 + electrolyzed) of sample vii is referred to as Reference Example 6, and the results are shown in FIG.

(Example 2)
Methylene blue absorbance (A589) of an aqueous solution obtained by adding methylene blue to catalyst-containing electrolytically treated water (basic water 9.18 + electrolytic treatment + Pt reference solution) of sample viii was taken as Example 2, and the results were compared with Reference Examples 4-6. This is shown in FIG.

(1-C); Consideration of Examples When the results of Examples 1 and 2 are compared with Reference Examples 1 to 6, the catalyst-containing electrolytically treated water of Examples 1 and 2 is compared with Reference Examples 1 to 6. Thus, methylene blue is specifically reduced regardless of the difference in pH, and it can be said that only the catalyst-containing electrolytically treated water exhibits a large reduction activity. In addition, when the presence or absence of blue coloration of the methylene blue aqueous solution was visually confirmed, only the catalyst-containing electrolytically treated water of Examples 1 and 2 was colorless and transparent, and the disappearance of blue color of methylene blue could be visually recognized. In Reference Examples 1 to 6, no disappearance of methylene blue was visible. Further, in the catalyst-containing hydrogen-dissolved water of Examples 1 and 2, a large amount of white precipitate (reduced methylene blue) could be visually confirmed.

(2) Reducing activity evaluation of Pt colloid / Pd colloid catalyst-containing hydrogen-dissolved water (degassing treatment + hydrogen gas sealing treatment) by methylene blue color change (2-A); reducing power evaluation test procedure Nippon Gene Manufacturing Co., Ltd. 1M Tris-HCl (pH 7.4) and 1M Tris-HCl (pH 9.0) sold by Kojun Pharmaceutical Co., Ltd. are each diluted 20 times with distilled water manufactured by Wako Pure Chemical Industries, Ltd. A 50 mM aqueous solution of Tris-HCl is prepared. Hereinafter, these two types of dilution water are referred to as “basic water 7.4” and “basic water 9.0”, respectively. Also, 0.6 g of a 4% solution of palladium colloid manufactured by Tanaka Kikinzoku Co. (having a particle size distribution of 2 to 4 nm and containing polyvinylpyrrolidone as a dispersant) was dissolved in 500 mL of distilled water manufactured by Wako Pure Chemical Industries, Ltd. This is called a “Pd reference solution”. The concentration C (Pd) of the palladium component of the Pd reference solution is C (Pd) = 0.6 g × 0.04 / 500 mL = 48 mg / L concentration based on the same calculation formula as for the Pt colloid.

  Next, 84 mL each of basic water 7.4 and basic water 9.0 was sampled, 4 mL of 1 g / L aqueous MB solution was added to each, and MB containing basic water 7.4 and basic water 9. Prepare 0 for each. Furthermore, 50 mL each of these MB-containing basic water 7.4 and 9.0 was sampled into individual deaeration bottles, degassed with a vacuum pump for 10 minutes, and then filled with hydrogen gas for 10 minutes, 3 times. . This operation is aimed at removing gaseous components other than hydrogen in hydrogen-dissolved water.

  3 mL each of MB-containing basic water 7.4 and basic water 9.0 obtained in this way was collected, and these were put into a quartz cell that was previously replaced with hydrogen gas in a closed system. Changes in the absorbance of methylene blue (ΔA572; at a wavelength of 572 nm) when each of a Pt standard solution, a Pd standard solution, or a mixed solution in which the molar ratio of the Pt standard solution and the Pd standard solution is about 1 was added to the quartz cell. Absorbance change) was measured.

(2-B); Disclosure of Examples (Example 3)
Change in methylene blue absorbance (ΔA572) of an aqueous solution in which MB-containing hydrogen dissolved water (MB-containing basic water 7.4 + degassing process + hydrogen gas sealing process) was added in an amount such that the Pt colloid concentration was 190 μg / L. Example 3 is shown in FIG. 8 and FIG.

Example 4
Change in methylene blue absorbance (ΔA572) of an aqueous solution in which MB-containing hydrogen dissolved water (MB-containing basic water 9.0 + degassing treatment + hydrogen gas sealing treatment) was added in an amount that resulted in a Pt colloid concentration of 190 μg / L. Example 4 is shown in FIG. 8 while comparing the results with Example 3. In addition, the difference between each sample water of Example 3 and Example 4 is pH.

(Example 5)
Change in Methylene Blue absorbance (ΔA572) of an aqueous solution in which Pt reference solution was added to MB dissolved hydrogen water (MB containing basic water 7.4 + degassing process + hydrogen gas sealing process) in an amount such that the Pt colloid concentration was 95 μg / L. Example 5 is shown in FIG. 9 while comparing the results with Example 3. In addition, the difference of each sample water of Example 3 and Example 5 is Pt colloid density | concentration.

(Example 6)
Change in absorbance of methylene blue (ΔA572) of an aqueous solution obtained by adding a Pd standard solution to an MB-added hydrogen-dissolved water (MB-containing basic water 7.4 + degassing process + hydrogen gas sealing process) in an amount such that the palladium colloid concentration is 444 μg / L. Example 6 is shown in FIGS. 10 and 11, respectively.

(Example 7)
Change in absorbance of methylene blue (ΔA572) of an aqueous solution obtained by adding a Pd standard solution to an MB-containing hydrogen-dissolved water (MB-containing basic water 9.0 + degassing treatment + hydrogen gas sealing treatment) in an amount such that the palladium colloid concentration is 444 μg / L. Example 7 is shown in FIG. 10 while comparing the results with Example 6. In addition, the difference between each sample water of Example 6 and Example 7 is pH.

(Example 8)
Change in methylene blue absorbance (ΔA572) of an aqueous solution in which a Pd standard solution was added in an amount of 111 μg / L to a hydrogen-dissolved water containing MB (basic water containing MB + 7.4 degassing treatment + hydrogen gas sealing treatment). Example 8 is shown, and the result is shown in FIG. The difference between the sample waters of Example 6 and Example 8 is the palladium colloid concentration.

Example 9
Premixed metal mixed (Pt + Pd) colloidal concentration of MB-containing hydrogen-dissolved water (MB-containing basic water 7.4 + degassing process + hydrogen gas sealing process) with a molar ratio of the Pt reference solution to the Pd reference solution being about 1 Is the methylene blue absorbance change (ΔA572) of the aqueous solution added in an amount of 160 μg / L, and the results are shown in FIGS. 12 and 13, respectively.

(Example 10)
The same mixed solution as in Example 9 was added to MB-containing hydrogen-dissolved water (MB-containing basic water 9.0 + degassing treatment + hydrogen gas sealing treatment) in such an amount that the colloid concentration of noble metal (Pt + Pd) was 160 μg / L. The change in methylene blue absorbance (ΔA572) of the aqueous solution was taken as Example 10, and the results are shown in FIG. The difference between the sample waters of Example 9 and Example 10 is the pH.

(Example 11)
A mixed solution similar to that in Example 9 was added to MB-containing hydrogen-dissolved water (MB-containing basic water 7.4 + degassing treatment + hydrogen gas sealing treatment) in such an amount that the colloid concentration of noble metal (Pt + Pd) was 80 μg / L The change in methylene blue absorbance (ΔA572) of the aqueous solution was taken as Example 11, and the results are shown in FIG. The difference between the sample waters of Example 9 and Example 11 is the noble metal (Pt + Pd) colloid concentration.

(2-C); Consideration of Examples FIG. 8 comparing Examples 3 and 4 shows MB reduction activity of Pt colloid-added hydrogen-dissolved water at pH 7.4 and pH 9.0. According to the figure, there is no large difference in MB reduction activity due to the difference in pH, and both show high MB reduction activity.

  FIG. 9 comparing Examples 3 and 5 shows the MB reduction activity of Pt colloid-added hydrogen-dissolved water at Pt colloid concentrations of 95 μg / L and 190 μg / L. According to the figure, the MB reduction activity increases as the Pt colloid concentration increases. Therefore, it is considered effective to increase the Pt colloid concentration in order to increase the MB reduction activity.

  FIG. 10 comparing Examples 6 and 7 shows the MB reduction activity of Pd colloid-added hydrogen-dissolved water at pH 7.4 and pH 9.0. According to the figure, there is no large difference in MB reduction activity due to the difference in pH, and both show high MB reduction activity.

  FIG. 11 comparing Examples 6 and 8 shows the MB reduction activity of Pd colloid-added hydrogen-dissolved water at Pd colloid concentrations of 111 μg / L and 444 μg / L. According to the figure, the MB reduction activity increases as the Pd colloid concentration increases. Therefore, it is considered effective to increase the Pd colloid concentration in order to increase the MB reduction activity.

  FIG. 12, which compares Examples 9 and 10, shows MB reduction activity of noble metal mixed (Pt + Pd) colloid-added hydrogen-dissolved water at pH 7.4 and pH 9.0. According to the figure, there is no large difference in MB reduction activity due to the difference in pH, and both show high MB reduction activity.

  FIG. 13 comparing Examples 9 and 11 shows the MB reduction activity of noble metal mixed (Pt + Pd) colloid-added hydrogen-dissolved water at noble metal mixed (Pt + Pd) colloid concentrations of 80 μg / L and 160 μg / L. According to the figure, the MB reduction activity increases as the colloid concentration of the precious metal mixture (Pt + Pd) increases. From this, it is considered effective to increase the colloid concentration of noble metal (Pt + Pd) in order to increase MB reduction activity.

  8 (Examples 3 and 4; MB reduction activity of Pt colloid-added hydrogen-dissolved water) and FIG. 10 (Examples 6 and 7; MB reduction activity of Pd colloid-added hydrogen-dissolved water) and Example 3 are compared. 4 shows that MB reduction activity equivalent to that of Examples 6 and 7 is exhibited, despite the lower concentration of 4. Furthermore, even if the molar concentration (μM) of both is compared, the Pt colloid is 0.98 μM, whereas the Pd colloid is 4.17 μM, and the Pt colloid is lower. Therefore, in terms of MB reduction activity expected for the noble metal catalyst according to the present invention, Pt colloid has a higher catalytic activity than Pd colloid in the sense that the amount used for obtaining the equivalent MB reduction activity can be reduced. It can be said that it is excellent.

  On the other hand, FIG. 8 (Examples 3 and 4; MB reduction activity of Pt colloid-added hydrogen-dissolved water MB) and FIG. 12 (Examples 9 and 10; MB reduction activity of colloid-added hydrogen-dissolved water of noble metals (Pt + Pd)) are compared. Both show excellent MB reduction activity. Comparing the molar concentration (μM) of both, it is 0.98 μM for the Pt colloid, and 1.07 μM for the noble metal mixed (Pt + Pd) colloid, which are almost equal. From this, it can be said that the Pt colloid and the noble metal mixed (Pt + Pd) colloid are substantially equivalent in terms of catalytic activity with respect to the MB reduction activity expected for the noble metal catalyst according to the present invention.

(3) Reducing activity evaluation of Pt colloid catalyst-containing electrolytically treated water (added before electrolytic treatment / added after electrolytic treatment) by color change of methylene blue (3-A); reducing power evaluation test procedure Prepared by (1-A) above Prepare 2000 mL of basic water 6.86 similar to the above, add 4 mL of Pt standard solution to 1000 mL, and prepare approximately 1 liter of Pt colloid-containing basic water 6.86. Do not add Pt colloid to the remaining 1000 mL. In this way, about 1 liter of basic water 6.86 without Pt colloid and about 1 liter of basic water 6.86 with Pt colloid are prepared.

  Next, 2.86 mL of electrolyzed water (hydrogen-dissolved water) obtained by subjecting both samples to electrolysis is collected and put into a sealed quartz cell in which hydrogen gas is substituted in advance.

  Furthermore, 0.14 mL of a 1 g / L methylene blue aqueous solution degassed and sealed with hydrogen gas is added to the cell without Pt colloid. Here, both cells are set in the spectrophotometer and waited.

  Next, 12 μL of a 48 mg / L concentration Pt colloid solution is added to a cell without Pt colloid, while a 1 g / L concentration methylene blue aqueous solution previously degassed and filled with hydrogen gas is added to a cell containing Pt colloid. 0.14 mL is added, and the measurement with the spectrophotometer of both cell solutions is started. The Pt colloid concentration added in both cells is adjusted to about 182 μg / L.

(3-B); Disclosure of Examples (Example 12)
Example 12 shows the minimum value of methylene blue absorbance (A572; absorbance at a wavelength of 572 nm) from the start of measurement to 30 minutes after the start of measurement of the catalyst-prepared electrolytically treated water (MB-added basic water 6.86 + Pt colloidal electrolysis pre-addition). Is shown in FIG.

(Example 13)
The minimum value of the methylene blue absorbance (A572) of the post-catalyst-added electrolytically treated water (MB-added basic water 6.86 + Pt after colloidal electrolysis added) for 30 minutes from the start of measurement is taken as Example 13, and the results are shown in Example 12. The comparison is shown in FIG.

(3-C); Consideration of Examples FIG. 14 comparing Examples 12 and 13 shows the MB reduction activity of electrolyzed water when the addition time of Pt colloid (before or after electrolysis) is varied. Indicates. According to the figure, it is understood that higher MB reduction activity can be obtained when Pt colloid is added before electrolytic treatment. The reason for this is currently under follow-up, but it is assumed that the activated hydrogen, which is the basis for MB reduction activity, is derived from the invalidation of the oxidizing power of oxidizing substances such as oxygen in the electrolyzed water. Is done. This is because the dissolved oxygen concentration of the electrolyzed water subjected to the electrolysis treatment using the activated carbon treated water containing Pt colloid as raw water was measured immediately after the electrolysis treatment, and the dissolved oxygen concentration of the electrolyzed water was almost zero. This is an inference derived from the fact that Then, not only in the example of the electrolytic treatment, but also in the hydrogen filling treatment and the hydrogen gas bubbling treatment, the addition of the catalyst (Pt colloid) before the treatment obtains higher MB reduction activity (the oxidizing power of the oxidizing substance such as oxygen) It is considered preferable from the viewpoint of (invalidation of the invalidation). Further, for example, in the case of obtaining dissolved hydrogen water by adding a reducing agent to raw water, it is preferable from the viewpoint of obtaining higher MB reduction activity in the same manner as described above to add Pt colloid to raw water in advance. it is conceivable that. In addition, the catalyst is not limited to Pt colloid, but also in the case of Pd colloid or a mixed colloid of Pt colloid and Pd colloid, the addition of the catalyst before the treatment is performed from the viewpoint of obtaining higher MB reduction activity (catalytic activity). preferable. This is because when noble metal colloidal catalyst is added before electrolytic treatment, hydrogen can be efficiently occluded in the noble metal colloidal catalyst in the course of electrolytic treatment, and thus the hydrogen stored in the noble metal colloidal catalyst is It is considered that higher MB reduction activity (catalytic activity) is brought about.

(4) Evaluation of antioxidant activity of electrolyzed water containing Pt colloid catalyst by color change of DPPH (1,1-diphenyl-2-picrylhydrazyl) radical Free radical DPPH is an antioxidant Is deactivated as a non-radical substance by the reaction with, and the absorbance in the vicinity of a wavelength of 520 nm decreases. By measuring this decrease, the radical scavenging activity of the antioxidant can be measured.

(4-A): Antioxidant activity evaluation test procedure The antioxidant activity of each of the eight sample aqueous solutions of samples i to viii shown in Table 2 is the same as that prepared in (1-A) above. In order to investigate, 4 mL of DPPH (0.16 g / L concentration) solution was added to 16 mL of each aqueous solution, the DPPH molar concentration was adjusted to 81.15 (μM), and each sample 3 minutes after adding DPPH. The DPPH absorbance change (ΔA540; absorbance change at a wavelength of 540 nm) of the aqueous solution was measured with a spectrophotometer.

(4-B); Disclosure of Reference Examples and Examples (Reference Example 7)
The DPPH absorbance difference (ΔA540) of the aqueous solution obtained by adding DPPH to the catalyst-free aqueous solution which is the basic water 6.86 of sample i is referred to as Reference Example 7, and the results are shown in FIG. The DPPH absorbance change (ΔA540) in the figure shows the difference (ΔA540) between the absorbance of samples i to iv and the absorbance of sample i (blank). Therefore, the DPPH absorbance change (ΔA540) of Reference Example 7 is zero.

(Reference Example 8)
A change in DPPH absorbance (ΔA540) of an aqueous solution obtained by adding DPPH to a catalyst-containing aqueous solution (basic water 6.86 + Pt reference solution) of sample ii is referred to as Reference Example 8, and the result is shown in FIG.

(Reference Example 9)
The change in DPPH absorbance (ΔA540) of an aqueous solution obtained by adding DPPH to the catalyst-free electrolytically treated water (basic water 6.86 + electrolytic treatment) of Sample iii is referred to as Reference Example 9, and the results are shown in FIG.

(Example 14)
The change in DPPH absorbance (ΔA540) of an aqueous solution of sample iv (basic water 6.86 + electrolytic treatment + Pt reference solution) in which DPPH was added to the catalyst-containing electrolytically treated water was taken as Example 14, and the results were referred to as Reference Examples 7-9. FIG. 15 shows the comparison.

(Reference Example 10)
The change in DPPH absorbance (ΔA540) of an aqueous solution obtained by adding DPPH to the catalyst-free aqueous solution which is the basic water 9.18 of sample v is referred to as Reference Example 10, and the results are shown in FIG. The DPPH absorbance change (ΔA540) in the figure shows the difference (ΔA540) between the absorbance of samples v to viii and the absorbance of sample v (blank). Therefore, the DPPH absorbance change (ΔA540) of Reference Example 10 is zero.

(Reference Example 11)
The change in DPPH absorbance (ΔA540) of an aqueous solution obtained by adding DPPH to the catalyst-containing aqueous solution (basic water 9.18 + Pt reference solution) of sample vi is referred to as Reference Example 11, and the results are shown in FIG.

(Reference Example 12)
The change in DPPH absorbance (ΔA540) of an aqueous solution obtained by adding DPPH to the catalyst-free electrolytically treated water (basic water 9.18 + electrolyzed) of sample vii is referred to as Reference Example 12, and the results are shown in FIG.

(Example 15)
The change in DPPH absorbance (ΔA540) of the aqueous solution obtained by adding DPPH to the catalyst-containing electrolytically treated water (basic water 9.18 + electrolytic treatment + Pt reference solution) of sample viii is referred to as Example 15, and the results are referred to as Reference Examples 10-12. FIG. 16 shows the comparison.

(4-C); Consideration of Examples Considering the results of Examples 14 and 15 in comparison with Reference Examples 7 to 12, the catalyst contained in Examples 14 and 15 in both basic water 6.86 and 9.18. Compared with Reference Examples 7 to 12, the electrolytically treated water specifically eliminates DPPH radicals and exhibits a large antioxidant activity or radical scavenging activity. Incidentally, the Pt colloid catalyst is added before the electrolytic treatment. In addition, as shown in FIG. 15, in Reference Example 9, DPPH radical scavenging activity is observed even though it is a catalyst-free electrolytically treated water. This is because, for example, in high-concentration hydrogen-dissolved water such as the electrolytically treated water disclosed in this specification, when the oxidizing substance to be reduced is a radical having a strong oxidizing power, the radical is forced from molecular hydrogen by the radical. This suggests that the hydrogen abstraction reaction may exhibit radical scavenging activity without the aid of a catalyst.

(5) Antioxidant activity evaluation of catalyst-containing hydrogen-dissolved water (degassing treatment + hydrogen gas sealing treatment) by color change of DPPH radical (5-A); Antioxidant activity evaluation test procedure Same as (2-A) above Next, prepare “basic water 7.4” and “basic water 9.0”. Next, collect 50 mL each of 406 μM DPPH solution, basic water 7.4 and basic water 9.0, and put them in a vacuum pump. Then, after degassing for 10 minutes, the operation of filling hydrogen gas for 10 minutes is repeated three times. This operation is aimed at removing gaseous components other than hydrogen in hydrogen-dissolved water.

  Quartz obtained by taking 0.3 mL of the DPPH solution filled with hydrogen gas and 2.7 mL of basic water 7.4 and basic water 9.0 each obtained in this way, and replacing them with hydrogen gas in a closed system in advance. The change in absorbance of DPPH (ΔA540; change in absorbance at a wavelength of 540 nm) was measured with a spectrophotometer for 30 minutes for both the quartz cell with and without the addition of the Pt reference solution.

(5-B); Disclosure of Reference Examples and Examples (Reference Example 13)
Reference Example 13 shows the change in DPPH absorbance (ΔA540) of an aqueous solution in which Pt reference solution is not added to hydrogen-dissolved water (basic water 7.4 + degassing treatment + hydrogen gas sealing treatment), and the results are shown in FIG.

(Example 16)
Example 16 shows change in DPPH absorbance (ΔA540) of an aqueous solution obtained by adding a Pt reference solution to hydrogen-dissolved water (basic water 7.4 + degassing process + hydrogen gas sealing process) in an amount such that the Pt colloid concentration is 190 μg / L. The result is shown in FIG. The difference between Reference Example 13 and Example 16 is the presence or absence of the addition of Pt colloid.

(Reference Example 14)
Reference Example 14 shows the change in DPPH absorbance (ΔA540) of an aqueous solution in which Pt reference solution is not added to hydrogen-dissolved water (basic water 9.0 + degassing treatment + hydrogen gas sealing treatment), and the results are shown in FIG.

(Example 17)
Example 17 shows a change in DPPH absorbance (ΔA540) of an aqueous solution obtained by adding a Pt reference solution to hydrogen-dissolved water (basic water 9.0 + degassing treatment + hydrogen gas sealing treatment) in an amount such that the Pt colloid concentration becomes 190 μg / L. The results are shown in FIG. 18 in comparison with Reference Example 14. The difference between Reference Example 14 and Example 17 is the presence or absence of the addition of Pt colloid.

(5-C); Consideration of Examples FIG. 17 comparing Reference Example 13 and Example 16 shows DPPH radical scavenging activity of hydrogen-dissolved water at pH 7.4 with the difference of Pt colloid addition or not. . FIG. 18 comparing Reference Example 14 and Example 17 shows the DPPH radical scavenging activity of hydrogen-dissolved water at pH 9.0 with the difference in whether or not Pt colloid is added. According to the figure, in Reference Examples 13 and 14 without Pt colloid, while the absorbance change was found only by the amount considered to have spontaneously faded within the measurement time (30 minutes), Examples 16 and 17 with Pt colloid were included. Then, the manifestation of clear DPPH radical scavenging activity exceeding natural fading was observed. In addition, the level difference of DPPH radical scavenging activity by the difference in pH was not seen.

<Evaluation test for reducing activity of hydrogen-dissolved water containing enzyme hydrogenase catalyst>
Next, when an enzyme hydrogenase catalyst is contained in the hydrogen-dissolved water according to the present invention, the evaluation of the reduction activity expressed by the activation of chemically inactive molecular hydrogen contained in the hydrogen-dissolved water is as follows. Examples and reference examples are shown respectively. In this reduction activity evaluation test, the redox dye methylene blue is used as an antioxidant target, as in the reduction activity evaluation test of hydrogen-dissolved water containing a noble metal colloid catalyst. In this case, the reduction activity evaluation principle is the same as that described for the noble metal colloid catalyst described above, and therefore, redundant description thereof is omitted.

(6) Reducing activity evaluation of enzyme hydrogenase catalyst-containing hydrogen-dissolved water (degassing treatment + hydrogen gas sealing treatment) by methylene blue color change (6-A); Reducing activity evaluation test procedure Prepared by (2-A) above “Basic water 7.4” and “Basic water 9.0” are prepared in the same manner as above, and 84 mL of each of these basic water 7.4 and basic water 9.0 is collected, and a 1 g / L MB aqueous solution is obtained. Is added to each 4 mL of basic water 7.4 and basic water 9.0 with a concentration of 121.7 μM. Further, 50 mL of each of the MB-containing basic waters 7.4 and 9.0 is sampled, degassed with a vacuum pump for 10 minutes, and then charged with hydrogen gas for 10 minutes is repeated three times. This operation is aimed at removing gaseous components other than hydrogen in hydrogen-dissolved water. On the other hand, a 125 μM hydrogenase solution diluted 4-fold with distilled water is put into a 1 mL microcapsule, and nitrogen gas (inert gas) is sealed in the capsule to remove oxygen.

  3 mL each of MB-containing basic water 7.4 and basic water 9.0 obtained in this way was collected, and these were put into a quartz cell that was previously replaced with hydrogen gas in a closed system. When the hydrogenase solution prepared as described above was added to the quartz cell, the change in absorbance (ΔA572) of methylene blue was measured.

(6-B); Disclosure of Reference Examples and Examples (Example 18)
Example 18 shows the change in methylene blue absorbance (ΔA572) of an aqueous solution obtained by adding 10 μL of the hydrogenase solution prepared as described above to MB-containing hydrogen-dissolved water (MB-containing basic water 7.4 + degassing treatment + hydrogen gas sealing treatment). The results are shown in FIG.

(Reference Example 15)
The change in methylene blue absorbance (ΔA572) of an aqueous solution containing no hydrogenase solution added to MB-containing hydrogen-dissolved water (MB-containing basic water 7.4 + degassing treatment + hydrogen gas sealing treatment) is referred to as Reference Example 15, and the results are shown in Example 18. FIG. 19 shows the contrast. The difference between each sample water in Example 18 and Reference Example 15 is the presence or absence of the enzyme hydrogenase.

(Example 19)
Example 19 shows the change in methylene blue absorbance (ΔA572) of an aqueous solution obtained by adding 10 μL of the hydrogenase solution prepared as described above to MB-containing hydrogen-dissolved water (MB-containing basic water 9.0 + degassing treatment + hydrogen gas sealing treatment). The results are shown in FIG.

(Reference Example 16)
The change in methylene blue absorbance (ΔA572) of an aqueous solution in which hydrogenase solution was not added to MB-containing hydrogen-dissolved water (MB-containing basic water 9.0 + degassing treatment + hydrogen gas sealing treatment) was referred to as Reference Example 16, and the results were obtained in Example 19. It shows in FIG. The difference between each sample water of Example 19 and Reference Example 16 is the presence or absence of enzyme hydrogenase.

(6-C); Consideration of Examples When the results of Examples 18 and 19 are compared with Reference Examples 15 and 16, the catalyst-containing hydrogen-dissolved water of Examples 18 and 19 is compared with Reference Examples 15 and 16. Thus, it can be said that methylene blue is specifically reduced regardless of the pH difference, and only the catalyst-containing hydrogen-dissolved water exhibits a large reduction activity. In addition, when the presence or absence of blue coloration of the methylene blue aqueous solution was visually confirmed, only the catalyst-containing hydrogen-dissolved water of Examples 18 and 19 was colorless and transparent, and the disappearance of the blue color of methylene blue was visually recognized. In Reference Examples 15 and 16, the disappearance of methylene blue was not visible. In addition, in the catalyst-containing hydrogen-dissolved water of Examples 18 and 19, a large amount of white precipitate (reduced methylene blue) could be visually confirmed.

<< Method for quantitative analysis of dissolved hydrogen concentration by oxidation-reduction titration of redox dye >>
(A) Background of the idea In the electrolytically treated water (electrolytically reduced water) subjected to electrolytic treatment by the reduction potential water generator 11 developed by the applicant of the present application, hydrogen produced by the cathode reaction during the electrolytic treatment is surely dissolved. Yes. The concentration of hydrogen dissolved in the electrolytically treated water can be temporarily measured using a dissolved hydrogen meter. In this case, the dissolved hydrogen meter generally uses the measurement principle that the electrochemical physical quantity in the electrode reaction is replaced with the dissolved hydrogen concentration by a table lookup method. This is because the measured value tends to fluctuate relatively greatly depending on external factors such as.

  By the way, as already explained based on the above-described examples, in the non-catalyst-containing electrolytically treated water, even when an oxidation-reduction pigment (antioxidation target) such as oxidized methylene blue is added, the pigment exhibits a color change characteristic of the reduction reaction. On the other hand, in the catalyst-containing electrolytically treated water, when such a dye was added, the dye showed a color change specific to the reduction reaction. That is, the oxidation-reduction reaction of the oxidation-reduction dye was visually recognized through observing the color change of the (catalyst-containing electrolytically treated water + oxidation-reduction dye) solution.

  While repeating such experiments through trial and error, the present inventors have developed a color change reaction from blue to transparent of the redox dye methylene blue as the reducing power held by the catalyst-containing electrolytically treated water increases. Noticed that there is a tendency to take place quickly. In other words, when comparing the reducing power retained in the catalyst-containing electrolytically treated water and the reducing power consumed to reduce the total amount of the added redox dye methylene blue, the former exceeds the latter It was found that there is some correlation between the magnitude of the remaining power of the reducing power, which is the difference between the two, and the color change reaction rate of the redox dye methylene blue.

  Based on these findings, the present inventors have conducted earnest research on the industrial applicability of such correlations. As a result, the present inventors have demonstrated that the antioxidant power of the catalyst-containing electrolytically treated water (through the redox reaction of the redox dye methylene blue) ( He came up with the idea that the dissolved hydrogen concentration could be quantitatively analyzed.

  As a means to embody such an idea, when a redox dye solution is dropped into a predetermined amount of test water containing a noble metal colloid catalyst by a titration operation performed in isolation from the external environment, The amount of dissolved hydrogen in the test water is determined from the amount of dripping up to the end of the color change of the dye due to the reduction reaction of the redox dye via a colloid catalyst, and the test water is determined based on the predetermined amount and the amount of dripping. It is found that a method for quantitative analysis of dissolved hydrogen concentration can be provided for quantitative analysis of dissolved hydrogen concentration, and as an apparatus for the analysis, a cylindrical container having one end closed and the other end opened, and from the open end A gas impervious tester isolated from the external environment, comprising a pusher that is movably inserted in a piston manner into the cylindrical container, and capable of operating a stirrer for a stirrer, The closed end and the side wall of the cylindrical container so that the liquid can be injected into the test water storage chamber defined by the closed end, the inner side wall, and the pusher of the cylindrical container while being isolated from the external environment. It was found that a quantitative analysis apparatus for the dissolved hydrogen concentration provided with a liquid injection part in either the pusher or the pusher is suitable. As a modification of the quantitative analysis method, instead of quantitative analysis based on the amount of dripping up to the end of the color change of the dye due to the reduction reaction of the redox dye, a predetermined amount of test in which a precious metal colloid catalyst was present was used. Based on the color change rate of the redox dye due to the reduction reaction of the redox dye via a noble metal colloid catalyst when a predetermined amount of a redox dye solution is dropped into water, dissolved hydrogen in the test water You may employ | adopt the quantitative analysis method of the dissolved hydrogen concentration which quantitatively analyzes a density | concentration.

(B) Experimental purpose When a predetermined concentration solution of the oxidation-reduction dye methylene blue is dropped into hydrogen-dissolved water containing catalyst-containing electrolytically treated water, until the solution after the dropping no longer exhibits a reduction color reaction. It is confirmed through the following experiment that the total amount of added methylene blue added to (hereinafter may be referred to as “end point”) is a measure for quantitative analysis of dissolved hydrogen concentration (apparent antioxidant power).

(C) Outline of effective dissolved hydrogen concentration quantitative analysis method When a catalyst is contained in hydrogen-dissolved water according to the present invention, chemically inactive molecular hydrogen contained in the hydrogen-dissolved water is activated. In order to quantitatively analyze the effective amount of the reducing power (antioxidant power) expressed in, that is, the effective dissolved hydrogen concentration DH (mg / L), Pt colloid as a catalyst and methylene blue as a redox dye Was used for redox titration of methylene blue against hydrogen water dissolved with catalyst (Pt colloid).

(D) Experimental procedure The basic experimental procedure is to prepare several sample water (measured characteristic values such as dissolved hydrogen concentration) in advance and add catalyst (Pt colloid) to these sample waters. At the same time, methylene blue is dripped. Then, the presence / absence of a correlation between the effective value of the dissolved hydrogen concentration obtained from each methylene blue total dripping amount or the like and the actually measured value with the dissolved hydrogen meter is compared and evaluated.

  If there is a correlation between the two, the validity of the quantitative analysis of dissolved hydrogen concentration by methylene blue oxidation-reduction titration and the fact that the key substance that expresses the obvious antioxidant function is dissolved hydrogen is objective. It is thought that it can also be verified.

  Based on such a basic concept, first, a 40-fold concentration Pt reference solution prepared from the above-described Pt reference solution to a 40-fold concentration is prepared. The concentration C (Pt) of the platinum component in the 40-fold concentration Pt standard solution is calculated from C (Pt) = 24 g × 0.04 / 500 mL to 192 mg / L.

  Next, a 1 g / L concentration (volume molar concentration; 2677.4 μM) methylene blue aqueous solution and a 10 g / L concentration (volume molar concentration: 26773.8 μM) methylene blue aqueous solution are prepared. Here, two types of methylene blue aqueous solutions with different concentrations were prepared because the amount of added methylene blue solution was changed by changing the concentration of the methylene blue solution added according to the hydrogen concentration that would be dissolved in the test water. This is because the accuracy of the experiment can be improved. However, the Pt concentration of the Pt reference solution and the MB concentration of the methylene blue aqueous solution are not limited to these, and may be appropriately adjusted according to various conditions such as the amount of hydrogen that will be dissolved in the test water.

  Next, 50 mL of the 40-fold concentration Pt reference solution prepared as described above and 50 mL of each of two types of methylene blue aqueous solutions having different concentrations were collected in separate deaeration bottles and degassed with a vacuum pump for 10 minutes. The operation of sealing nitrogen gas for 10 minutes is repeated three times to prepare a 40-fold concentration Pt reference solution and a methylene blue aqueous solution substituted with nitrogen gas. Such an operation is aimed at removing gaseous components other than nitrogen (inert gas) in each solution.

  Next, 200 mL of test water is put into an acrylic gas impermeability tester together with a magnetic stirrer. This tester was created for this experiment.It forms the bottom by bonding an acrylic circular plate to one end in the longitudinal direction of an acrylic cylindrical hollow tube, and its open side is The piston is sealed in a longitudinally movable manner with a pusher made of a circular plate having a diameter slightly smaller than the inner diameter of the tube. A seal ring made of a material such as silicon rubber is attached to the pusher so as to cover the entire periphery thereof. A 40-fold concentration Pt reference solution or MB solution can be injected into the test device side wall in a state where it is isolated from the external environment into the test water storage chamber defined by the bottom surface, the inner side wall, and the pusher of the test device. Thus, the solution injection part which consists of an acrylic cylindrical hollow tube is provided toward the radial direction outer side in the tester. The solution injection part is detachably provided with a rubber stopper for inserting a syringe needle. When the test water is introduced into the test water storage chamber of the test device constructed in this way, the test water is poured gently with the pusher removed from the test device, and then the test water is stored in the test water storage chamber. Attach the pusher so that no phase occurs. As a result, the test water can be confined in the test water storage chamber of the test device while being isolated from the external environment. In addition, when introducing the 40-fold concentration Pt reference solution or MB solution into the test water storage chamber of the tester, the solution is sucked and collected so that no gas phase is generated in the syringe, and the needle of the syringe is After inserting into the rubber stopper attached to the injection part, the solution is gently injected by pushing the piston of the syringe. Note that the tester disclosed here is merely an example, and the material of the tester is gas-impermeable and does not occlude hydrogen (for example, stainless steel is gas-impermeable but is the object of measurement. It is not suitable as a test material because it absorbs hydrogen.), The test water storage chamber can be isolated from the external environment, the test water storage chamber volume is variable, and the test water storage chamber is airtight. It can be kept liquid-tight, 40-fold concentration Pt reference solution, MB solution, etc. can be added while the test water storage chamber is isolated from the external environment, and the stirrer for the stirrer can be operated. If the conditions are satisfied, other containers can be appropriately employed.

  Next, the test water-containing test device is placed on a magnetic stirrer base with the bottom face down, and stirring with a stirrer is started.

  Next, 1 mL of the 40-fold concentration Pt reference solution substituted with nitrogen gas is injected into the test water storage chamber using a syringe, and sufficiently stirred and mixed.

  Next, the above-described methylene blue aqueous solution with a predetermined concentration substituted with nitrogen gas is injected little by little using a syringe while visually observing the color change of the test water. Here, if the dissolved hydrogen concentration in the test water is higher than the amount of methylene blue added, the methylene blue is reduced to become colorless. However, if the amount of methylene blue aqueous solution added is gradually increased, The dissolved hydrogen in the test water cancels each other, and the color change of methylene blue from blue to colorless can no longer be observed. If this time is taken as the end point, the dissolved hydrogen concentration DH of the test water can be determined from the methylene blue concentration of the methylene blue aqueous solution and the total amount of the added methylene blue aqueous solution.

(E) How to determine the effective dissolved hydrogen concentration Below, the formula for calculating the effective dissolved hydrogen concentration DH in the test water from the concentration of the methylene blue aqueous solution added to the test water and the total amount added, and the formula The meaning of the effective dissolved hydrogen concentration DH will be described with reference to the derivation process.

First, in the following description, the volume of test water is 200 mL, and the methylene blue volume molar concentration of the methylene blue aqueous solution added to the test water is N (μmol / L). Furthermore, when the total amount of methylene blue aqueous solution added until reaching the end point is A (mL), the total amount B (mol) of added methylene blue molecules is
B = N · A (μmol / L × mL)
= N · A (mμmol) (Formula 1)
It becomes. Here, when the chemical formula of the methylene blue molecule is MBCl and the chemical formula of the hydrogen molecule is H ₂ , the reaction between the hydrogen molecule activated by the Pt colloid and the methylene blue molecule in the aqueous solution is expressed by the following reaction formula 1. The

H ₂ + MBCl → HCl + MBH (Reaction Formula 1)
Here, HCl is hydrochloric acid and MBH is reduced methylene blue. According to Reaction Formula 1, 1 mol of hydrogen molecules and 1 mol of methylene blue molecules react to form 1 mol of reduced methylene blue molecules. In order to explain with the exchange of electrons, the reaction equation is divided into two half-reaction equations as follows.

H ₂ → H ⁺ + (H ⁺ + 2e ⁻ ) (half reaction formula 1)
MB ⁺ + (H ⁺ + 2e ⁻ ) → MBH (half reaction formula 2)
Half-reaction formula 1 means that one mole of hydrogen molecule emits two moles of electrons, while half-reaction formula 2 means that one mole of methylene blue cation, that is, one mole of methylene blue molecule accepts two moles of electrons. Means. Here, one mole of hydrogen molecule is equivalent to 2 grams because it emits two moles of electrons, whereas one mole of methylene blue cation, ie, one mole of methylene blue molecule, is equivalent to 2 grams because it accepts two moles of electrons. As a result, the number of gram equivalents of a hydrogen molecule and a methylene blue cation, that is, a methylene blue molecule, are both the same, so the hydrogen molecule and the methylene blue molecule are in a one-to-one relationship in terms of molar ratio. Will react.

  Considering this, the total amount B of methylene blue added to the test water is also the total amount of consumed hydrogen molecules.

Therefore, when the total amount of hydrogen molecules to be measured is C (mμmol), from the above equation 1,
C = B = N · A (mμmol) (Formula 2)
It becomes. Furthermore, the volume of the test water is 200 mL, and the effective molar concentration H ₂ (mol / L) of hydrogen molecules in the test water is a value obtained by dividing the number of moles C (mol) by the volume (mL). because there is,
H ₂ (mol / L) = C / 200 (mμmol / mL)
= C / 200 (μmol / L) (Formula 3)
It becomes. Furthermore, when this unit is converted into mass concentration (g / L), if the mass concentration of the corresponding hydrogen molecule is D, the following proportional expression for the hydrogen molecule H ₂ :
1 mol / 2g = H ₂ (μmol / L) / D (Formula 4)
From this, substituting equation 3 into equation 4,
D = 2 · C / 200 (μg / L)
= C / 100 (μg / L) (Formula 5)
It becomes. This is the effective mass concentration of hydrogen molecules contained in 200 mL of test water. The effective hydrogen molecule mass concentration D is in the order of micrograms. To convert to the milligram order, multiply the numerator and denominator by 1000,
D = C · 1000/100 · 1000 (μg / L)
= C · 10 ⁻⁵ (mg / L) (Formula 6)
And it is sufficient.

Then, from the relationship of Formula 2, the number of moles C of hydrogen molecules in Formula 6 can be replaced with the total amount B of methylene blue.
D = N · A (mμmol) · 10 ⁻⁵ (mg / L) (Formula 7)
Is established.

  From Equation 7, the total amount of methylene blue aqueous solution added by adding the effective hydrogen molecule mass concentration D (mg / L) contained in the test water to the methylene blue volume molar concentration N (μmol / L) until reaching the end point. It can be seen that it can be obtained by multiplying (mL).

  By the way, not only the hydrogen molecule (hydrogen gas) which is trying the quantitative analysis here, but also various ions, oxygen molecule (oxygen gas), carbon dioxide (carbon dioxide gas), etc. are dissolved in the test water. Among these, examples of the substances involved in the oxidation-reduction reaction in the test water include oxygen molecules, hypochlorite and hypochlorous acid in addition to hydrogen molecules. Such oxygen molecules usually act mainly as an oxidizing agent in the oxidation-reduction reaction, and do not act as a reducing agent except in some special cases. In particular, in the test for reducing methylene blue as described here, oxygen molecules and the like act as an oxidizing agent and do not reduce methylene blue. Conversely, oxidized methylene blue is converted to oxidized methylene blue. End up. In other words, even if the methylene blue reduced by the activation of molecular hydrogen remains colorless as a reduced methylene blue or exists as a white precipitate, if such oxygen molecules coexist, it is reduced again. Methylene blue is oxidized and returned to the original oxidized methylene blue. In addition, even if not through methylene blue, activated hydrogen molecules and oxygen molecules react directly to deprive the reducing power of a considerable amount of hydrogen molecules. become unable. That is, as shown in FIGS. 21 and 22, for example, when oxides such as oxygen molecules coexist in hydrogen-dissolved water, the amount of hydrogen molecules corresponding to these amounts is consumed and added to the end point. The total amount of is also reduced according to the amount of oxide.

  Considering this, the dissolved hydrogen concentration measured by the quantitative analysis method using methylene blue can be said to be an effective dissolved hydrogen concentration obtained by subtracting the hydrogen concentration consumed by the oxidizing agent such as dissolved oxygen. .

(F) Disclosure of Reference Examples and Examples (Reference Example 17)
Alkaline electrolyzed water that has been subjected to continuous electrolysis treatment using electrolysis conditions of electrolysis range “4” with standard water volume in an electrolyzed water generator “Mini Water” (equipped with activated carbon filter) manufactured by Miz Co., Ltd. is used as the test water. After injecting 1 mL of 40-fold concentration Pt standard solution substituted with nitrogen gas into the test water storage chamber using a syringe, and sufficiently stirring and mixing, 1 g / L concentration (volume molar concentration; 2679. 4 μM) of the methylene blue aqueous solution was injected little by little using a syringe while visually observing the color change of the test water. The total injection amount of the methylene blue aqueous solution up to the end point was 1 mL, and the effective value of the dissolved hydrogen concentration DH determined by substituting each value in the above equation 7 was 0.03 (mg / L). PH, oxidation-reduction potential ORP (mV), electrical conductivity EC (mS / m), water temperature T (° C), dissolved oxygen concentration DO (mg / L), dissolved hydrogen in the test water according to Reference Example 17 The measured value (mg / L) of the concentration DH and the effective value (mg / L) of the dissolved hydrogen concentration DH obtained by substituting each value in the above equation 7 are shown in Table 3, and the measured value and effective value of DH are shown in Table 3. It shows in FIG. In addition, as various instruments used for measuring various physical property values, the same ones as described above were used.

(Reference Example 18)
After boiling purified water treated with Fujisawa city tap water through an ion exchange column manufactured by Organo Corporation, water was boiled with hydrogen gas and the temperature was cooled to 20 ° C. After injecting 200 mL of test water into 1 mL of the 40-fold concentration Pt standard solution substituted with nitrogen gas into the test water storage chamber using a syringe and thoroughly stirring the mixture, 10 g / L is added to the test water. A methylene blue aqueous solution having a concentration (volume molar concentration: 26773.8 μM) was injected little by little using a syringe while visually observing the color change of the test water. The total injection amount of the methylene blue aqueous solution up to the end point was 6.2 mL, and the effective value of the dissolved hydrogen concentration DH obtained by substituting each value in Equation 7 was 1.66 (mg / L). . Various physical property values of the test water according to Reference Example 18 are shown in Table 3, and the actual measured value and effective value of the dissolved hydrogen concentration DH are shown in FIG.

(Example 20)
Electrolytically treated water obtained by electrolyzing the basic water 6.86 of the sample i described above in a continuous water-flowing type at a flow rate of 1 liter per minute under 5 A constant current electrolysis conditions is used as test water, and 200 mL of the test water is used. After injecting 1 mL of the above 40-fold concentration Pt reference solution substituted with nitrogen gas into the test water storage chamber using a syringe and stirring sufficiently, the mixture was mixed with 10 g / L concentration (volume molar concentration; 26773.8 μM) methylene blue aqueous solution was injected little by little using a syringe while visually observing the color change of the test water. The total amount of methylene blue solution injected up to the end point was 5.9 mL, and the effective value of the dissolved hydrogen concentration DH determined by substituting each value into the above equation 7 was 1.58 (mg / L). . Various physical property values of the test water according to this Working Example 20 are shown in Table 3, and the actual measured value and effective value of the dissolved hydrogen concentration DH are shown in FIG.

(Example 21)
Electrolyzed water obtained by electrolyzing the above-mentioned basic water 9.18 of sample v at a flow rate of 1 liter per minute under electrolysis conditions of 5 A constant current at a flow rate of 5 A is used as test water. After injecting 1 mL of the above 40-fold concentration Pt reference solution substituted with nitrogen gas into the test water storage chamber using a syringe and stirring sufficiently, the mixture was mixed with 10 g / L concentration (volume molar concentration; 26773.8 μM) methylene blue aqueous solution was injected little by little using a syringe while visually observing the color change of the test water. The total amount of methylene blue solution injected until reaching the end point was 5.0 mL, and the effective value of the dissolved hydrogen concentration DH determined by substituting each value in the above equation 7 was 1.34 (mg / L). . Various physical property values of the test water according to Example 21 are shown in Table 3, and the actual measured value and effective value of the dissolved hydrogen concentration DH are shown in FIG.

(Example 22)
A pH buffer aqueous solution obtained by diluting standard buffer solution 4.01 (phthalate aqueous solution) manufactured by Wako Pure Chemical Industries, Ltd. 10-fold with purified water was continuously passed under electrolysis conditions of 5 A constant current at a flow rate of 1 liter per minute. Electrolyzed electrolyzed water is used as test water, and 200 mL of the test water is injected with 1 mL of the 40-fold concentration Pt reference solution substituted with nitrogen gas as described above, using a syringe. After thoroughly stirring and mixing, a 10 g / L concentration (volume molar concentration: 26773.8 μM) of methylene blue aqueous solution was added to the test water using a syringe while observing the color change of the test water visually. Injected. The total amount of methylene blue solution injected until reaching the end point was 6.3 mL, and the effective value of the dissolved hydrogen concentration DH determined by substituting each value into the above formula 7 was 1.69 (mg / L). . Various physical property values of the test water according to Example 22 are shown in Table 3, and the actual measured value and effective value of the dissolved hydrogen concentration DH are shown in FIG.

(Example 23)
Circulating electrolyzed water obtained by electrolytically treating the basic water 6.86 of sample i described above in a continuous water circulation system (circulating water amount is 0.8 liters) at a flow rate of 1 liter per minute and 5 A constant current for 3 minutes. 1 mL of the above 40-fold concentrated Pt reference solution substituted with nitrogen gas is poured into the test water storage chamber using a syringe and mixed thoroughly with 200 mL of the test water. A methylene blue aqueous solution having a concentration of 10 g / L (volume molar concentration: 26773.8 μM) was injected into the test water little by little using a syringe while visually observing the color change of the test water. The total injection amount of the same methylene blue aqueous solution up to the end point was 9.6 mL, and the effective value of the dissolved hydrogen concentration DH obtained by substituting each value into the above formula 7 was 2.57 (mg / L). . Various physical property values of the test water according to this working example 23 are shown in Table 3, and the actual measured value and effective value of the dissolved hydrogen concentration DH are shown in FIG.

(Example 24)
Circulating electrolyzed water obtained by electrolytically treating the above-mentioned basic water 9.18 of sample v at a flow rate of 1 liter per minute in an electrolysis condition of 5 A constant current in a continuous water circulation type (circulating water amount is 0.8 liter) for 3 minutes. 1 mL of the above 40-fold concentrated Pt reference solution substituted with nitrogen gas is poured into the test water storage chamber using a syringe and mixed thoroughly with 200 mL of the test water. A methylene blue aqueous solution having a concentration of 10 g / L (volume molar concentration: 26773.8 μM) was injected into the test water little by little using a syringe while visually observing the color change of the test water. The total injection amount of the methylene blue aqueous solution up to the end point was 12.3 mL, and the effective value of the dissolved hydrogen concentration DH obtained by substituting each value into Equation 7 was 3.29 (mg / L). . Various physical property values of the test water according to this Working Example 24 are shown in Table 3, and the actual measured value and effective value of the dissolved hydrogen concentration DH are shown in FIG.

(Example 25)
Circulating electrolytically treated water obtained by electrolytically treating the same pH buffered aqueous solution as in Example 22 in a continuous water circulation type (circulating water amount 0.8 liters) at a flow rate of 1 liter per minute for 5 minutes under a constant current electrolysis condition. The test water is 200 mL of the test water, and 1 mL of the 40-fold concentration Pt standard solution substituted with nitrogen gas is injected into the test water storage chamber using a syringe and sufficiently stirred and mixed. A methylene blue aqueous solution having a concentration of 10 g / L (volume molar concentration: 26773.8 μM) was injected into the test water little by little using a syringe while visually observing the color change of the test water. The total injection amount of the same methylene blue aqueous solution up to the end point was 12.4 mL, and the effective value of the dissolved hydrogen concentration DH obtained by substituting each value into Equation 7 was 3.32 (mg / L). . Various physical property values of the test water according to this Working Example 25 are shown in Table 3, and the actual measured value and effective value of the dissolved hydrogen concentration DH are shown in FIG.

（Ｇ） 実施例の考察
表３および図２３によれば、溶存水素濃度ＤＨの実測値と実効値のあいだには、実測値が高いときにはそれに応じて実効値も高くなることから、相応の相関性があることがわかる。また、参考例１８、および、実施例２０〜２５の溶存水素濃度ＤＨの実効値は、参考例１７のＤＨ実効値と比較して、いずれも１．３（ｍｇ／Ｌ）を超えるという高い濃度を示した。特に、実施例２０〜２５のＤＨ実効値は、常温（２０°Ｃ）かつ大気圧下での分子状水素の水への飽和溶解濃度がおよそ１．６（ｍｇ／Ｌ）であるのに対して、およそ２．５〜３．３（ｍｇ／Ｌ）というきわめて高い濃度を示した。

(G) Consideration of Examples According to Table 3 and FIG. 23, when the measured value is high, the effective value increases correspondingly between the measured value and the effective value of the dissolved hydrogen concentration DH. It turns out that there is sex. Further, the effective value of the dissolved hydrogen concentration DH in Reference Example 18 and Examples 20 to 25 is higher than that in Reference Example 17 in any case exceeding 1.3 (mg / L). showed that. In particular, the effective DH values of Examples 20 to 25 are that the saturated dissolution concentration of molecular hydrogen in water at room temperature (20 ° C) and atmospheric pressure is approximately 1.6 (mg / L). Thus, a very high concentration of about 2.5 to 3.3 (mg / L) was exhibited.

  In the quantitative analysis tests of dissolved hydrogen concentration conducted here, activated carbon-treated water (without adding a reducing agent) is used in all cases, and chlorine-based oxidizing substances such as hypochlorous acid are removed beforehand. Therefore, oxygen molecules are thought to be the main oxidants remaining in the test water. In addition, even if oxygen molecules are once removed with activated carbon, the test water dissolves into the water as soon as it comes into contact with the atmosphere. Therefore, it is difficult to remove only with activated carbon unless some reducing agent is used. .

  However, on the premise of applying the antioxidant method proposed in the present invention, the concentration of dissolved substances such as dissolved oxygen is increased while the dissolved hydrogen concentration is made as high as possible, as in the reduction potential water generator developed by the present applicant. Is as low as possible in order to expect the reduction activity and the antioxidant activity derived from the antioxidant functional water according to the combination of the hydrogen-dissolved water and the catalyst according to the present invention.

  Therefore, when the dissolved hydrogen water according to the present invention is defined from the viewpoint of the effective value of the dissolved hydrogen concentration DH obtained using the dissolved hydrogen concentration quantitative analysis method using the redox dye according to the present invention, the present invention As the dissolved hydrogen water according to the above, DH having a saturation concentration or higher under atmospheric pressure (eg, 1.6 or higher at 1 atm, 3.2 or higher at 2 atm, 4.8 or higher at 3 atm,...). What shows an effective value is preferable. Further, when the atmospheric pressure is 1 atm, the dissolved hydrogen concentration DH effective value is 1.7 or more, 1.8 or more, 1.9 or more, 2.0 or more, 2.1 or more, 2.2 or more, 2 .3 or more, 2.4 or more, 2.5 or more, 2.6 or more, 2.7 or more, 2.8 or more, 2.9 or more, 3.0 or more, 3.1 or more, 3.2 or more, 3 .3 or higher (both units are in mg / L), the higher the better. This is because the expression of the reduction activity and the antioxidant activity derived from the antioxidant functional water related to the combination of the hydrogen-dissolved water and the catalyst according to the present invention can be expected at a high level.

  This knowledge newly proposes a method for quantitative analysis of hydrogen concentration in hydrogen-dissolved water including electrolyzed water and a measure of the apparent antioxidant power of the hydrogen-dissolved water. In addition, the measurement of dissolved hydrogen concentration using an existing dissolved hydrogen meter is complicated in its measurement procedure and handling, is not fully satisfactory in terms of measurement accuracy, and its cost is very high. On the other hand, in the dissolved hydrogen concentration quantification method using the redox dye according to the present invention, the measurement procedure and handling are relatively simple, and the measurement accuracy can be improved by removing the oxidant contained in the test water. In this respect as well, the principle is that the number of molecular hydrogen particles is directly quantitatively analyzed through a chemical reaction with a redox dye, so that the accuracy is high and the cost is very low.

<< Radical scavenging activity evaluation test using epinephrine oxidation method in XOD experimental system >>
Next, the radical scavenging activity evaluation test method using the epinephrine oxidation method in the XOD experimental system will be described in the following (A). Moreover, anti-oxidation function water according to the present invention when using the same test method; for the radical scavenging activity (A nti O xidant- functioning W ater . Hereinafter sometimes referred to as "AOW") or the like is expressed, AOW As an example in which a noble metal colloid catalyst (Pt colloid / Pd colloid / Pt / Pd mixed colloid) is added to hydrogen-dissolved water, examples and reference examples are shown in the following (B). Note that the XOD experimental system is a superoxide anion obtained by reducing one electron of oxygen by electrons released by oxidation of xanthine through a process in which xanthine oxidase (XOD), which is a biological enzyme, acts on xanthine in an oxygen-dissolved solution system. An experimental system (hereinafter, referred to as “XOD experimental system”) that generates radicals (hereinafter, may be simply referred to as “(· O ₂ ⁻ )”).

(A) Radical scavenging activity evaluation test method using epinephrine oxidation method in XOD experimental system (A-1) Background of idea As a conventional method for measuring free radicals, for example, “free radical and medicine” (publishing company Yodogawa Co., Ltd.) As described in p133-141 of the bookstore ISBN 4-567-49380-X), a cytochrome c reduction method is known.

This cytochrome c reduction method (see FIG. 24) is based on an oxidized cytochrome c (ferrocytochrome c) of oxidized cytochrome c (ferricytochrome c (Fe ³⁺ )) by superoxide anion radical (.O ₂ ⁻ ) in the XOD experimental system. The reduction reaction to (Fe ²⁺ )) is inhibited by analytes such as SOD and antioxidants through the time course of the absorption maximum (wavelength: 550 nm) of oxidized cytochrome c by a spectrophotometer. Yes, it utilizes the reactivity of (.O ₂ ⁻ ) as a one-electron reducing agent.

The measurement principle will be described in detail. In the cytochrome c reduction method, an analyte such as an antioxidant is (· O ₂ ⁻ ) in preference to (or simultaneously with) the reduction reaction of oxidized cytochrome c by (· O ₂ ⁻ ). ) Is reduced, the reduced amount of oxidized cytochrome c, that is, the amount of reduced cytochrome c produced is suppressed (suppresses an upward trend or begins to show a downward trend). Then, the absorption maximum (A550) of reduced cytochrome c is also reduced. When this is considered including the time factor, the absorption maximum (A550) of reduced cytochrome c per unit time decreases with the amount of (.O ₂ ⁻ ) erased. By observing the transition of the absorption maximum (A550) over time, the SOD-like activity of the subject can be measured.

However, in the SOD-like activity measurement system using the above conventional cytochrome c reduction method, when a substance having a remarkable reducing power such as antioxidant functional water or ascorbic acid according to the present invention is used as the analyte, high accuracy is obtained. In addition to being unable to obtain the measurement result, there is a problem that the measurement result opposite to the original is derived. This is because (· O ₂ ⁻ ) is used as a reducing agent. That is, the AOW and ascorbic acid of the present invention reduce (.O ₂ ⁻ ) by reduction and simultaneously reduce oxidized cytochrome c. As a result, it is conceivable that, for example, (· O ₂ ⁻ ) is all reduced and eliminated, and at the same time, oxidized cytochrome c is also reduced by the remaining power. In this case, there is a possibility that not only a highly accurate measurement result can be obtained but also a measurement result opposite to the original one such that the apparent SOD-like activity is low may be derived.

  Therefore, as a result of earnest search for free radical reaction reagents suitable for the radical scavenging activity evaluation test of antioxidant functional water according to the present invention, the present inventors cannot use oxidation of reduced epinephrine. I came to get the knowledge that.

When reduced epinephrine is oxidized to a superoxide anion radical (.O ₂ ⁻ ), it changes to red adrenochrome (oxidized epinephrine), and its absorption maximum (A480) increases. At this time, (.O ₂ ⁻ ) acts as an oxidizing agent. Incidentally, reduced epinephrine is not easily oxidized by normal oxygen molecules, and does not show a color reaction to red even if it is oxidized. In other words, it has been experimentally confirmed that reduced epinephrine does not increase its absorption maximum (A480) even in an oxygen-dissolved solution system. This means that reduced epinephrine is suitable as a free radical reaction reagent for distinguishing between normal oxygen molecules (O ₂ ) and superoxide anion radicals (.O ₂ ⁻ ).

In the epinephrine oxidation method (see FIG. 25), it is assumed that an appropriate amount of (.O ₂ ⁻ ) has been generated in advance in the XOD experimental system. The (.O ₂ ⁻ ) thus generated changes the reduced epinephrine into an oxidized form according to the following chain reaction.

RH ₃ ⁻ + • O ₂ ⁻ + 2H ⁺ ⇒ • RH ₃ + H ₂ O ₂
・ RH ₃ + O ₂ ⇒ RH ₂ + • O ₂ ⁻ + H ⁺
RH ₂ + • O ₂ ⁻ + H ⁺ ⇒ • RH + H ₂ O ₂
・ RH + O ₂ ⇒ R + ・ O ₂ ⁻ + H ⁺
However, (RH ₃ ⁻ ) is reduced epinephrine, and (R) is oxidized epinephrine (adrenochrome). In the vicinity of physiological pH, reduction and epinephrine ^- but low reactivity with, if large doses of reduced epinephrine, reduced and epinephrine (· O ₂₎ ^- is the second-order rate of (· O ₂₎ Speed up. Therefore, in the present epinephrine oxidation method, the molar concentration of reduced epinephrine is preferably set to a high concentration of, for example, about 1 mM. Furthermore, reduced epinephrine tends to be easily oxidized by a small amount of transition metal such as iron ions. In order to eliminate the influence of such disturbance, it is necessary that a chelating agent such as EDTA coexists in the test solution.

Well this time, (· O ₂ ^-) in preference to oxidation of reduced epinephrine by (or simultaneously), the subject, such as antioxidants (· O ₂ ^-) As you reduced erased, reduced The oxidation amount of epinephrine, that is, the production amount of oxidized epinephrine is gradually suppressed. Then, the upward trend of the absorption maximum of oxidized epinephrine (A480) becomes moderate. When this is considered including the time factor, the upward trend of the absorption maximum (A480) of oxidized epinephrine per unit time becomes moderate with the amount of (.O ₂ ⁻ ) erased. Therefore, the SOD-like activity (radical scavenging activity) of the specimen can be measured by observing the transition of the absorption maximum (A480) over time.

  Specifically, considering a graph with elapsed time on the horizontal axis and absorbance (A480) on the vertical axis, SOD-like activity is expressed as the amount of change (ΔA480) in absorbance (A480) per unit time (ΔT). I can express. That is, the slope of the tangent line (ΔA / ΔT) in the graph represents the SOD-like activity. Therefore, regarding the SOD-like activity graph in the subject, it can be determined that the SOD-like activity is small when the positive slope (rising upward characteristic) is large, and conversely, when it is small, it is large. In addition, it can be determined that the SOD-like activity is large when the negative slope (characteristic of descending to the right) is large, and conversely when it is small. However, when the case where the positive slope is small and the case where the negative slope is small are compared in terms of the level of radical scavenging activity, it can be said that the latter has higher radical scavenging activity than the former.

  The above is the measurement principle of radical scavenging activity (SOD-like activity) using the epinephrine oxidation method.

(A-2) Reagents used Reagents used for the radical scavenging activity (SOD-like activity) test using the epinephrine oxidation method are listed below.

(1) Dulbecco's phosphate buffered saline powder (PBS): Wako Pure Chemical Industries
(2) Xanthine (2,6-dioxopurine): Wako Pure Chemical Industries
(3) Xanthine oxidase suspension (derived from buttermilk): Wako Pure Chemical Industries
(4) EDTA-2Na dihydrate: Dojindo Laboratories, Wako Pure Chemical Industries Sales
(5) 1 mol / L sodium hydroxide solution ... Wako Pure Chemical Industries
(6) L (+)-ascorbic acid ... Wako Pure Chemical Industries
(7) (±) epinephrine (dl-epinephrine) (dl-adrenaline) ... manufactured by Wako Pure Chemical Industries, Ltd. (A-3) Reagent preparation methods The reagent preparation methods listed in (A-2) above are as follows. Street.

(1) Preparation of PBS buffer stock solution containing EDTA 2 bags for 500 mL of Dulbecco's phosphate buffered saline powder (hereinafter referred to as “PBS”) are dissolved in 100 mL of distilled water and divided into two equal parts. 0.19 g of EDTA-2Na is dissolved in 50 mL of one. This is used as an EDTA stock solution. Take 0.5 mL of this EDTA stock solution and 49.5 mL of the solution without EDTA, and mix them.

  The mixed solution obtained at this time is a PBS buffer stock solution containing EDTA (1.9 mg). In terms of PBS concentration, this is diluted 10 times. If there are many metal ion species in the test water, the EDTA stock solution may be directly diluted 10 times, for example. In this case, since the concentration of EDTA is high, metal ions that are a cause of a decrease in measurement accuracy can be removed sufficiently. The EDTA-containing PBS buffer stock solution is prepared for the purpose of fixing the pH of the solution to about 7.4, which is a physiological liquid, and preventing a decrease in measurement accuracy due to metal ions.

(2) Preparation of 1.5 mM xanthine solution Xanthine is dissolved in 350 mL of distilled water by adding xanthine = 0.228≈0.23 g and 80 drops of 1 (mol / L) sodium hydroxide aqueous solution. Take 35 mL of this, and add PBS buffer stock solution containing EDTA to make 100 mL.

(3) Preparation of xanthine oxidase solution The xanthine oxidase suspension is diluted 100 times with a PBS buffer stock solution containing EDTA. This is prepared for each experimental run.

(4) Preparation of epinephrine solution With a stirrer for a stirrer, 100 mL of distilled water is put into a vial bottle and sealed with a rubber stopper. The rubber stopper is pierced with an injection needle for exhaustion and a needle connected to a nitrogen gas cylinder. . In this state, a vial bottle containing distilled water is placed on a stirrer base, and nitrogen gas is sealed in distilled water while stirring vigorously, and the inside of distilled water is completely replaced with nitrogen gas. This nitrogen gas replacement treatment is performed for 30 minutes. Thereafter, 0.15 g of epinephrine is added, stoppered, stirred gently with a stirrer, and filled with nitrogen gas. This nitrogen gas replacement process continues until the end of the experiment. This is the preparation of the epinephrine solution. The point in such preparation is to increase the stirring before the addition of epinephrine and to gently the stirring after the addition of epinephrine.

(A-4) Test procedure In the conventional XOD experimental system, all reagents and aqueous solution to be tested are added to the cell sequentially, and finally xanthine oxidase (XOD) is added, and the reaction is started by the addition of this XOD. At the same time, measurement with a spectrophotometer was started.

However, in this conventional method, when the test aqueous solution is added, (.O ₂ ⁻ ) is not yet fully formed, and at this point, the oxygen molecules that are the production raw material of (• O ₂ ⁻ ) remain as they are. It exists in the state. In other words, oxygen molecules change from time of addition of XOD to (• O ₂ ⁻ ) over time, and as a result, the amount of (• O ₂ ⁻ ) increases, so immediately after the addition of the test solution. An appropriate amount of (• O ₂ ⁻ ) has not been obtained. Further, in the conventional method, (· O ₂ ^-) since the amount of dissolved oxygen which is yielding feedstock of not clearly perceived, each time the same amount ^- clear whether is generated (· O ₂₎ It wasn't.

In consideration of these, first, a PBS buffer stock solution containing EDTA, a xanthine solution, a xanthine oxidase solution, and distilled water for supplying oxygen are first added to the cell and mixed. After generating (.O ₂ ⁻ ), it was considered that it would be desirable to start the measurement by adding test water and an epinephrine solution.

  Therefore, in this epinephrine oxidation method, each reagent solution or test water is sequentially introduced into the cell according to the following procedure. In addition, a waiting time is set as necessary. The volume of the cell is 3 mL, about 1/3 of which is occupied by the test water and distilled water for supplying oxygen, and the remaining about 1/3 is the xanthine solution such as pH buffer containing EDTA. , Xanthine oxidase solution, and epinephrine solution.

 (1) Add 300 μL of PBS buffer stock solution containing EDTA.

 (2) Add 300 μL of xanthine solution.

 (3) Add 900 μL of distilled water for supplying oxygen (about 1/3 of the cell volume).

 (4) Add 100 μL of xanthine oxidase solution.

(5) Wait 5 minutes to generate an appropriate amount of (.O ₂ ⁻ ).

 (6) Add 1 mL of test water (liquid) (1/3 of the cell volume).

 (7) Add 400 μL of epinephrine solution.

 (8) Immediately thereafter, start measuring the time-dependent change in absorbance (A480) with a spectrophotometer.

 (9) Wait 140 seconds to level out the local concentration gradient difference of reagents in the cell. That is, the measurement data from the start of measurement until 140 seconds have elapsed are excluded in principle from the radical scavenging activity characteristic graph described later. The observation time for the change over time was set to 15 minutes, excluding the waiting time of 140 seconds in (9) above. This is because, for example, in about 5 minutes or 10 minutes, there is a case where a clear difference tendency regarding radical scavenging activity between platinum and palladium may not be recognized.

In addition, as it was found through experiments, the radical addition activity of each reagent was also determined by the conventional method of adding all reagents together, adding xanthine oxidase at the end, and starting the reaction / measurement. Can grasp. However, preferably, it is considered that a tendency closer to the actual radical scavenging activity can be grasped if an assay solution is added after an appropriate amount of (.O ₂ ⁻ ) has been generated in advance in the XOD experimental system. In addition, in the conventional method, although it depends on the production lot of xanthine oxidase, it tends to take a relatively long time to produce an appropriate amount of (.O ₂ ⁻ ), so radicals such as test water can be eliminated in a short time. It is difficult to grasp the activity. In particular, the accuracy of the conventional method is poor for the purpose of grasping the difference in catalytic activity between platinum and palladium. Including such practical elements, the addition timing or standby timing of each reagent is performed as described above.

(B) Disclosure of Examples and Reference Examples by Radical Scavenging Activity Evaluation Test Method Using Epinephrine Oxidation Method in XOD Experimental System (Reference Example 19)
The radical scavenging activity measurement data according to the test procedure described in (A-4) when distilled water (manufactured by Wako Pure Chemical Industries) is adopted as the test water is referred to as Reference Example 19. It should be noted that the radical scavenging activity measurement data of the present Reference Example 19 may have slightly different radical scavenging activity characteristics between production lots under test conditions using xanthine oxidase from different production lots.

(Reference Example 20)
The measurement data for radical scavenging activity according to the same test procedure as in Reference Example 19 when hydrogen gas-substituted distilled water (manufactured by Wako Pure Chemical Industries, Ltd.) is adopted as test water is referred to as Reference Example 20. Regarding the radical scavenging activity measurement data of Reference Example 20, as in Reference Example 19, the radical scavenging activity characteristics may differ slightly between production lots under the test conditions using xanthine oxidase from different production lots. I will add that.

(Example 26)
As test water, after adding the Pt standard solution described in Examples 3 to 5 to distilled water (manufactured by Wako Pure Chemical Industries, Ltd., the same applies below) in an amount such that the Pt colloid concentration is 48 μg / L, Example 26 shows radical scavenging activity measurement data according to the same test procedure as in Reference Example 19 when hydrogen-substituted antioxidant functional water (AOW) is employed.

(Example 27)
Example 26 when AOW in which a Pt standard solution similar to that in Example 26 was added to distilled water in such an amount that the Pt colloid concentration was 96 μg / L and then replaced with hydrogen gas was used as test water. Radical scavenging activity measurement data according to the same test procedure as in Example 27 is taken as Example 27.

(Example 28)
Example 26 when AOW in which a Pt colloid solution similar to that in Example 26 was added to distilled water in such an amount that the Pt colloid concentration was 192 μg / L and then replaced with hydrogen gas was used as test water. Radical scavenging activity measurement data according to the same test procedure as in Example 28 is taken as Example 28.

(Example 29)
Example 26 when AOW in which a Pt colloid solution similar to that in Example 26 was added to distilled water in such an amount that the Pt colloid concentration was 384 μg / L and then replaced with hydrogen gas was used as test water. Radical scavenging activity measurement data according to the same test procedure as in Example 28 is taken as Example 28.

(Example 30)
Example 26 in which AOW in which a Pt colloid solution similar to that in Example 26 was added to distilled water in such an amount that the Pt colloid concentration was 768 μg / L and then replaced with hydrogen gas was used as test water. Radical scavenging activity measurement data according to the same test procedure as in Example 30 is referred to as Example 30.

(Example 31)
As test water, after adding the Pd standard solution described in Examples 6 to 8 to the test water in such an amount that the Pd colloid concentration is 48 μg / L, anti-oxidation functional water (AOW) in which this was replaced with hydrogen gas was added. Example 31 shows radical scavenging activity measurement data according to the same test procedure as in Reference Example 19 when employed.

(Example 32)
Example 31 when AOW in which a Pd standard solution similar to Example 31 was added to distilled water in an amount such that the Pd colloid concentration was 96 μg / L and then replaced with hydrogen gas was used as test water. Radical scavenging activity measurement data according to the same test procedure as in Example 27 is taken as Example 27.

(Example 33)
Example 31 when AOW in which a Pd colloid solution similar to that in Example 31 was added to distilled water in such an amount that the Pd colloid concentration was 192 μg / L and then replaced with hydrogen gas was used as test water. Radical scavenging activity measurement data according to the same test procedure as in Example 33 is taken as Example 33.

(Example 34)
Example 31 when AOW in which a Pd colloid solution similar to that in Example 31 was added to distilled water in such an amount that the Pd colloid concentration was 384 μg / L and then replaced with hydrogen gas was used as test water. Radical scavenging activity measurement data according to the same test procedure as Example 34 is taken as Example 34.

(Example 35)
Example 31 when AOW in which a Pd colloid solution similar to that in Example 31 was added to distilled water in such an amount that the Pd colloid concentration was 768 μg / L and then replaced with hydrogen gas was used as test water. Radical scavenging activity measurement data according to the same test procedure as in Example 35 is taken as Example 35.

(Example 36)
As test water, a platinum colloid solution having a particle size distribution of about 1 to 2 nm manufactured by the present applicant based on the above-mentioned paper “How to make and use Pt colloid” by Namba et al. Example 36 shows radical scavenging activity measurement data in accordance with the same test procedure as in Reference Example 19 when AOW in which the Pt colloid concentration is added in an amount of 66 μg / L and then replaced with hydrogen gas is employed.

(Example 37)
Example 36 when AOW in which a platinum colloid solution similar to Example 36 was added to distilled water in such an amount that the Pt colloid concentration was 96 μg / L and then replaced with hydrogen gas was used as test water. Radical scavenging activity measurement data according to the same test procedure as Example 37 is taken as Example 37.

(Example 38)
Example 36 when AOW in which a platinum colloid solution similar to Example 36 was added to distilled water in such an amount that the Pt colloid concentration was 144 μg / L and then replaced with hydrogen gas was used as test water. Radical scavenging activity measurement data according to the same test procedure as Example 38 is taken as Example 38.

(Example 39)
Example 36 when AOW in which a platinum colloid solution similar to that in Example 36 was added to distilled water in such an amount that the Pt colloid concentration was 192 μg / L and then replaced with hydrogen gas was used as test water. Radical scavenging activity measurement data according to the same test procedure as in Example 39 is taken as Example 39.

(Example 40)
Example 36 when AOW in which a platinum colloid solution similar to that in Example 36 was added to distilled water in such an amount that the Pt colloid concentration was 384 μg / L and then replaced with hydrogen gas was used as test water. Radical scavenging activity measurement data according to the same test procedure as in Example 40 is taken as Example 40.

(Example 41)
Example 36 when AOW in which a platinum colloid solution similar to Example 36 was added to distilled water in such an amount that the Pt colloid concentration was 768 μg / L and then replaced with hydrogen gas was used as test water. Radical scavenging activity measurement data according to the same test procedure as in Example 41 is taken as Example 41.

(Example 42)
As test water, (Pt + Pd) mixed colloid prepared by mixing a distilled water with a Pt standard solution similar to Example 26 and a Pd standard solution similar to Example 31 so that the molar ratio is 1: 2. Example 42 shows radical scavenging activity measurement data according to the same test procedure as in Reference Example 19 when AOW in which the concentration is 96 μg / L and then replaced with hydrogen gas is employed.

(Example 43)
As test water, the same (Pt + Pd) mixed colloid as in Example 42 was added to distilled water in such an amount that the concentration was 192 μg / L, and then AOW was used in which this was replaced with hydrogen gas. Radical scavenging activity measurement data according to the same test procedure as in Example 42 is referred to as Example 43.

(Example 44)
As test water, the same (Pt + Pd) mixed colloid as in Example 42 was added to distilled water in such an amount that the concentration was 384 μg / L, and then AOW was used in which this was replaced with hydrogen gas. Radical scavenging activity measurement data according to the same test procedure as in Example 42 is referred to as Example 44.

(Example 45)
As test water, the same (Pt + Pd) mixed colloid as in Example 42 was added to distilled water in such an amount that the concentration was 768 μg / L, and then AOW substituted with hydrogen gas was used. Radical scavenging activity measurement data according to the same test procedure as in Example 42 is referred to as Example 45.

(Example 46)
As test water, (Pt + Pd) mixed colloid prepared by mixing a distilled water with a Pt standard solution similar to Example 26 and a Pd standard solution similar to Example 31 so that the molar ratio is 1: 5. Example 46 shows radical scavenging activity measurement data according to a test procedure similar to that of Reference Example 19 when AOW in which the concentration is 144 μg / L and then hydrogen gas replacement is employed.

(Example 47)
As test water, (Pt + Pd) mixed colloid prepared by mixing a distilled water with a Pt reference solution similar to Example 26 and a Pd reference solution similar to Example 31 so that the molar ratio is 1:10. Example 47 shows radical scavenging activity measurement data according to the same test procedure as Example 46 when AOW in which the concentration is 240 μg / L and then hydrogen gas replacement is adopted.

(Example 48)
As test water, (Pt + Pd) mixed colloid prepared by mixing a distilled water with a Pt standard solution similar to Example 26 and a Pd standard solution similar to Example 31 so that the molar ratio is 1:15. Example 48 shows radical scavenging activity measurement data according to the same test procedure as Example 46 when AOW in which the concentration is 336 μg / L and then hydrogen gas replacement is used is added.

(Example 49)
As test water, a (Pt + Pd) mixed colloid prepared by mixing and mixing distilled water with a Pt standard solution similar to Example 26 and a Pd standard solution similar to Example 31 at a molar ratio of 1:20. Example 49 shows radical scavenging activity measurement data according to the same test procedure as in Example 46 when AOW in which the concentration is 432 μg / L and then hydrogen gas replacement is used is added.

(Example 50)
As test water, (Pt + Pd) mixed colloid prepared by mixing and mixing distilled water with a Pt standard solution similar to Example 26 and a Pd standard solution similar to Example 31 to a molar ratio of 1:25. Example 50 shows radical scavenging activity measurement data according to the same test procedure as Example 46 when AOW in which the concentration is 528 μg / L and then hydrogen gas replacement is used is added.

(Reference Example 21)
The radical scavenging activity measurement data according to a test procedure in which a part of the procedure described in (A-4) is modified when distilled water substituted with hydrogen gas is adopted as test water is referred to as Reference Example 21. The modified part of the above test procedure is for oxygen supply instead of adding 300 μL of xanthine solution and 100 μL of xanthine oxidase solution into the test cell, that is, instead of removing the (.O ₂ ⁻ ) production system. The amount of distilled water was increased from 900 μL to 1300 μL.

(Example 51)
As test water, (Pt + Pd) mixed colloid prepared by mixing a distilled water with a Pt standard solution similar to Example 26 and a Pd standard solution similar to Example 31 so that the molar ratio is 1: 5. Radical scavenging activity according to a test procedure in which a part of the procedure described in (A-4) is modified, when AOW in which the concentration is 144 μg / L and then hydrogen gas replacement is adopted is used. The measurement data is referred to Reference Example 51. The modified part of the test procedure is the same as in Reference Example 21.

(Example 52)
As test water, (Pt + Pd) mixed colloid prepared by mixing a distilled water with a Pt reference solution similar to Example 26 and a Pd reference solution similar to Example 31 so that the molar ratio is 1:10. Example 52 shows radical scavenging activity measurement data according to the same test procedure as in Example 51 when AOW in which the concentration is 240 μg / L and then hydrogen gas replacement is used is used.

(Example 53)
As test water, (Pt + Pd) mixed colloid prepared by mixing a distilled water with a Pt standard solution similar to Example 26 and a Pd standard solution similar to Example 31 so that the molar ratio is 1:15. Example 53 shows radical scavenging activity measurement data according to the same test procedure as Example 51 when AOW in which the concentration is 336 μg / L and then hydrogen gas replacement is employed is added.

(Example 54)
As test water, a (Pt + Pd) mixed colloid prepared by mixing and mixing distilled water with a Pt standard solution similar to Example 26 and a Pd standard solution similar to Example 31 at a molar ratio of 1:20. Example 54 shows radical scavenging activity measurement data according to the same test procedure as Example 51 when AOW in which the concentration is 432 μg / L and then hydrogen gas replacement is used is added.

(Example 55)
As test water, (Pt + Pd) mixed colloid prepared by mixing and mixing distilled water with a Pt standard solution similar to Example 26 and a Pd standard solution similar to Example 31 to a molar ratio of 1:25. Example 55 shows radical scavenging activity measurement data according to the same test procedure as in Example 51 when AOW in which the concentration is 528 μg / L and then hydrogen gas replacement is used is used.

(Reference Example 22)
A pH buffer aqueous solution (basic water 6.86) obtained by diluting a standard buffer solution 6.86 (phosphate aqueous solution) manufactured by Wako Pure Chemical Industries, Ltd. 10 times with purified water is used as test water. The radical scavenging activity measurement data according to the test procedure described in (A-4) is referred to as Reference Example 22.

(Reference Example 23)
The catalyst-free electrolyzed water obtained by electrolyzing the same basic water 6.86 as in Reference Example 22 at a flow rate of 1.5 liters per minute and under a 5 A constant current electrolysis condition was used as test water. The radical scavenging activity measurement data according to the same test procedure as in Reference Example 22 for this test water is referred to as Reference Example 23.

(Example 56)
1 liter of basic water 6.86 similar to Reference Example 22 was taken, and Pt colloid-containing basic water 6.86 to which a Pt standard solution similar to Example 26 was added in an amount of 48 μg / L was added thereto. Prepare. The pre-catalyst-added 1-pass electrolyzed water obtained by electrolytically treating the basic water 6.86 containing Pt colloid thus prepared under the same electrolysis conditions as in Reference Example 23 as test water (AOW). The radical scavenging activity measurement data of test water (AOW) according to the same test procedure as in Reference Example 22 is referred to as Example 56.

(Example 57)
1 liter of basic water 6.86 similar to Reference Example 22 was taken, and Pt colloid-containing basic water 6.86 added with an amount of 96 μg / L of the same Pt standard solution as in Example 26 was added thereto. Prepare. The pre-catalyst-added 1-pass electrolyzed water obtained by electrolytically treating the basic water 6.86 containing Pt colloid thus prepared under the same electrolysis conditions as in Reference Example 23 as test water (AOW). Example 57 is the radical scavenging activity measurement data of test water (AOW) according to the same test procedure as in Example 56.

(Example 58)
1 liter of basic water 6.86 similar to Reference Example 22 was taken, and Pt colloid-containing basic water 6.86 added with an amount of Pt standard solution similar to that of Example 26 in an amount of 192 μg / L. Prepare. The pre-catalyst-added 1-pass electrolyzed water obtained by electrolytically treating the basic water 6.86 containing Pt colloid thus prepared under the same electrolysis conditions as in Reference Example 23 as test water (AOW). Example 58 shows radical scavenging activity measurement data of test water (AOW) according to the same test procedure as in Example 56.

(Example 59)
1 liter of basic water 6.86 similar to Reference Example 22 was taken, and Pt colloid-containing basic water 6.86 added with an amount of Pt standard solution similar to Example 26 in an amount of 384 μg / L. Prepare. The pre-catalyst-added 1-pass electrolyzed water obtained by electrolytically treating the basic water 6.86 containing Pt colloid thus prepared under the same electrolysis conditions as in Reference Example 23 as test water (AOW). Example 59 is the radical scavenging activity measurement data of test water (AOW) according to the same test procedure as in Example 56.

(Example 60)
1 liter of basic water 6.86 similar to Reference Example 22 was taken, and Pt colloid-containing basic water 6.86 added with an amount of Pt standard solution similar to Example 26 in an amount of 768 μg / L. Prepare. The pre-catalyst-added 1-pass electrolyzed water obtained by electrolytically treating the basic water 6.86 containing Pt colloid thus prepared under the same electrolysis conditions as in Reference Example 23 as test water (AOW). Example 60 is the radical scavenging activity measurement data of test water (AOW) according to the same test procedure as in Example 56.

(Example 61)
Take 1 liter of basic water 6.86 similar to Reference Example 22, and add Pd colloid-containing basic water 6.86 to which Pd standard solution similar to Example 31 was added in an amount of 48 μg / L. Prepare. The pre-catalyst-added 1-pass electrolyzed water obtained by electrolytically treating the basic water containing Pd colloid 6.86 prepared in this way under the same electrolysis conditions as in Reference Example 23 was used as test water (AOW). Example 61 is the radical scavenging activity measurement data of test water (AOW) according to the same test procedure as in Reference Example 22.

(Example 62)
1 liter of basic water 6.86 similar to that of Reference Example 22 was taken, and Pd colloid-containing basic water 6.86 to which a Pd standard solution similar to that of Example 31 was added in such an amount that the concentration was 96 μg / L was added thereto. Prepare. The pre-catalyst-added 1-pass electrolyzed water obtained by electrolytically treating the basic water containing Pd colloid 6.86 prepared in this way under the same electrolysis conditions as in Reference Example 23 was used as test water (AOW). Example 62 shows radical scavenging activity measurement data of test water (AOW) according to the same test procedure as in Example 61.

(Example 63)
1 liter of basic water 6.86 similar to Reference Example 22 was taken, and Pd colloid-containing basic water 6.86 to which a concentration of 192 μg / L of the same Pd standard solution as in Example 31 was added. Prepare. The pre-catalyst-added 1-pass electrolyzed water obtained by electrolytically treating the basic water containing Pd colloid 6.86 prepared in this way under the same electrolysis conditions as in Reference Example 23 was used as test water (AOW). The radical scavenging activity measurement data of test water (AOW) according to the same test procedure as in Example 61 is referred to as Example 63.

(Example 64)
1 liter of basic water 6.86 similar to Reference Example 22 was taken, and Pd colloid-containing basic water 6.86 added with an amount of Pd standard solution similar to Example 31 in an amount of 384 μg / L was added thereto. Prepare. The pre-catalyst-added 1-pass electrolyzed water obtained by electrolytically treating the basic water containing Pd colloid 6.86 prepared in this way under the same electrolysis conditions as in Reference Example 23 was used as test water (AOW). The radical scavenging activity measurement data of test water (AOW) according to the same test procedure as in Example 61 is referred to as Example 64.

(Example 65)
1 liter of basic water 6.86 similar to Reference Example 22 was taken, and Pd colloid-containing basic water 6.86 to which a concentration of 768 μg / L of the same Pd standard solution as in Example 31 was added. Prepare. The pre-catalyst-added 1-pass electrolyzed water obtained by electrolytically treating the basic water containing Pd colloid 6.86 prepared in this way under the same electrolysis conditions as in Reference Example 23 was used as test water (AOW). Example 65 is the radical scavenging activity measurement data of test water (AOW) according to the same test procedure as in Example 61.

Example 66
1 liter of basic water 6.86 similar to Reference Example 22 was taken, and Pt colloid-containing basic water 6.86 to which a Pt standard solution similar to Example 26 was added in an amount of 48 μg / L was added thereto. Prepare. 6.86 basic water containing Pt colloid prepared in this manner was subjected to electrolytic treatment for 3 minutes in a continuous water circulation type (circulation water amount is 0.8 liter) at a flow rate of 1.5 liters per minute and under a 5 A constant current electrolysis condition. The pre-catalyst-added circulating electrolyzed water is the test water (AOW), and the radical scavenging activity measurement data of this test water (AOW) according to the same test procedure as in Reference Example 22 is referred to as Example 66.

(Example 67)
1 liter of basic water 6.86 similar to Reference Example 22 was taken, and Pt colloid-containing basic water 6.86 added with an amount of 96 μg / L of the same Pt standard solution as in Example 26 was added thereto. Prepare. The pre-catalyst-added circulating electrolyzed water prepared by electrolyzing the thus prepared basic water 6.86 containing Pt colloid for 3 minutes under the same electrolysis conditions as in Example 66 in a continuous water circulation system (circulating water amount is 0.8 liter). Is the test water (AOW), and the radical scavenging activity measurement data of this test water (AOW) according to the same test procedure as in Example 66 is referred to as Example 67.

Example 68
1 liter of basic water 6.86 similar to Reference Example 22 was taken, and Pt colloid-containing basic water 6.86 added with an amount of Pt standard solution similar to that of Example 26 in an amount of 192 μg / L. Prepare. The pre-catalyst-added circulating electrolyzed water prepared by electrolyzing the thus prepared basic water 6.86 containing Pt colloid for 3 minutes under the same electrolysis conditions as in Example 66 in a continuous water circulation system (circulating water amount is 0.8 liter). Is the test water (AOW), and the radical scavenging activity measurement data of this test water (AOW) according to the same test procedure as in Example 66 is referred to as Example 68.

(Example 69)
1 liter of basic water 6.86 similar to Reference Example 22 was taken, and Pt colloid-containing basic water 6.86 added with an amount of Pt standard solution similar to Example 26 in an amount of 384 μg / L. Prepare. The pre-catalyst-added circulating electrolyzed water prepared by electrolyzing the thus prepared basic water 6.86 containing Pt colloid for 3 minutes under the same electrolysis conditions as in Example 66 in a continuous water circulation system (circulating water amount is 0.8 liter). Is the test water (AOW), and the radical scavenging activity measurement data of this test water (AOW) according to the same test procedure as in Example 66 is referred to as Example 69.

(Example 70)
1 liter of basic water 6.86 similar to Reference Example 22 was taken, and Pt colloid-containing basic water 6.86 added with an amount of Pt standard solution similar to Example 26 in an amount of 768 μg / L. Prepare. The pre-catalyst-added circulating electrolyzed water prepared by electrolyzing the thus prepared basic water 6.86 containing Pt colloid for 3 minutes under the same electrolysis conditions as in Example 66 in a continuous water circulation system (circulating water amount is 0.8 liter) Is the test water (AOW), and the radical scavenging activity measurement data of this test water (AOW) according to the same test procedure as in Example 66 is referred to as Example 70.

(Example 71)
Take 1 liter of basic water 6.86 similar to Reference Example 22, and add Pd colloid-containing basic water 6.86 to which Pd standard solution similar to Example 31 was added in an amount of 48 μg / L. Prepare. The Pd colloid-containing basic water 6.86 thus prepared was subjected to electrolytic treatment for 3 minutes in a continuous water circulation type (circulation water amount 0.8 liters) at a flow rate of 1.5 liters per minute and under a 5 A constant current electrolysis condition. The pre-catalyst-added circulating electrolyzed water is the test water (AOW), and the radical scavenging activity measurement data of this test water (AOW) according to the same test procedure as in Reference Example 22 is referred to as Example 71.

(Example 72)
1 liter of basic water 6.86 similar to that of Reference Example 22 was taken, and Pd colloid-containing basic water 6.86 to which a Pd standard solution similar to that of Example 31 was added in such an amount that the concentration was 96 μg / L was added thereto. Prepare. Pre-catalyst-added circulating electrolyzed water prepared by electrolytically treating Pd colloid-containing basic water 6.86 prepared in this manner for 3 minutes in a continuous water circulation type (circulating water amount is 0.8 liter) under the same electrolysis conditions as in Example 66. Is the test water (AOW), and the radical scavenging activity measurement data of this test water (AOW) according to the same test procedure as in Example 71 is referred to as Example 72.

(Example 73)
1 liter of basic water 6.86 similar to Reference Example 22 was taken, and Pd colloid-containing basic water 6.86 to which a concentration of 192 μg / L of the same Pd standard solution as in Example 31 was added. Prepare. Pre-catalyst-added circulating electrolyzed water prepared by electrolytically treating Pd colloid-containing basic water 6.86 prepared in this manner for 3 minutes in a continuous water circulation type (circulating water amount is 0.8 liter) under the same electrolysis conditions as in Example 66. Is the test water (AOW), and the radical scavenging activity measurement data of this test water (AOW) according to the same test procedure as in Example 71 is referred to as Example 73.

(Example 74)
1 liter of basic water 6.86 similar to Reference Example 22 was taken, and Pd colloid-containing basic water 6.86 added with an amount of Pd standard solution similar to Example 31 in an amount of 384 μg / L was added thereto. Prepare. Pre-catalyst-added circulating electrolyzed water prepared by electrolytically treating Pd colloid-containing basic water 6.86 prepared in this manner for 3 minutes in a continuous water circulation type (circulating water amount is 0.8 liter) under the same electrolysis conditions as in Example 66. Is the test water (AOW), and the radical scavenging activity measurement data of this test water (AOW) according to the same test procedure as in Example 71 is referred to as Example 74.

(Example 75)
1 liter of basic water 6.86 similar to Reference Example 22 was taken, and Pd colloid-containing basic water 6.86 to which a concentration of 768 μg / L of the same Pd standard solution as in Example 31 was added. Prepare. Pre-catalyst-added circulating electrolyzed water prepared by electrolytically treating Pd colloid-containing basic water 6.86 prepared in this manner for 3 minutes in a continuous water circulation type (circulating water amount is 0.8 liter) under the same electrolysis conditions as in Example 66. Is the test water (AOW), and the radical scavenging activity measurement data of this test water (AOW) according to the same test procedure as in Example 71 is set as Example 75.

(Example 76)
Reference Example 21 when AOW in which a Pt colloid solution similar to that in Example 26 was added to distilled water in such an amount that the Pt colloid concentration was 384 μg / L and then replaced with hydrogen gas was used as test water. Example 76 shows radical scavenging activity measurement data according to a modified test procedure in the same manner as in Example 76.

(Example 77)
Example 76 when AOW in which a Pd colloid solution similar to that in Example 31 was added to distilled water in such an amount that the Pd colloid concentration was 384 μg / L and then replaced with hydrogen gas was used as test water. Radical scavenging activity measurement data according to the same test procedure as in Example 77 is taken as Example 77.

(Reference Example 24)
As the test water, radical scavenging activity measurement data according to the same test procedure as in Reference Example 19 was adopted when an AsA aqueous solution in which ascorbic acid (AsA) was added to distilled water in such an amount that the concentration was 35.5 μM was adopted. This is referred to as Reference Example 24.

(Reference Example 25)
As the test water, radical scavenging activity measurement data according to the same test procedure as in Reference Example 19 when an AsA aqueous solution in which ascorbic acid (AsA) is added to distilled water in an amount of 71 μM is adopted as a reference water 25.

(Reference Example 26)
As the test water, radical scavenging activity measurement data according to the same test procedure as in Reference Example 19 when an AsA aqueous solution in which ascorbic acid (AsA) is added to distilled water in an amount of 142 μM is used as a reference water 26.

(Reference Example 27)
As the test water, radical scavenging activity measurement data according to the same test procedure as in Reference Example 19 when an AsA aqueous solution in which ascorbic acid (AsA) is added to distilled water in such an amount that the concentration is 284 μM is used as a reference example 27.

(C) Consideration of Examples FIG. 26 comparing Reference Examples 19 and 20 with Examples 26 to 30 is a Pt colloid catalyst having a Pt colloid (particle size distribution 2 to 4 nm) concentration as a main parameter. The time-dependent change characteristic of the radical scavenging activity which contained hydrogen dissolved water (AOW) shows is shown. Here, both Reference Examples 19 and 20 were used as comparative controls because the radical scavenging activity characteristics when oxygen was removed from the test water (liquid) occupying 1/3 of the 3 mL capacity test cell. It is the purpose to grasp the tendency of. It should be noted that, even when the hydrogen water-substituted distilled water of Reference Example 20 is used as the test water, the time-dependent change characteristics of both radical scavenging activities are completely overlapped. This has been confirmed by experiments not shown. This means that as long as the degree of oxygen removal is consistent, the type of gas as a control does not affect the time-dependent change characteristics of radical scavenging activity (the same applies hereinafter). According to the figure, when compared with the radical scavenging activity characteristics of Reference Examples 19 and 20 (hereinafter, the comparative examples are abbreviated as “control characteristics”), the absorbance (A480) of the spectrophotometer is measured. The radical scavenging activity characteristics exhibited by the AOWs of Examples 26 to 30 (hereinafter referred to as “subject characteristics”) after about 680 seconds from the start of measurement with time (hereinafter abbreviated as “measurement start time”). "Is abbreviated as"), which is significantly below the control properties at any concentration. That is, it can be seen that the AOWs of Examples 26 to 30 begin to express good radical scavenging activity in a wide concentration range after a certain amount of elapsed time. Further, when the subject characteristics of Examples 26 to 30 are well analyzed, the time required for radical scavenging is shorter as the concentration is higher, depending on the concentration of Pt colloid. That is, it can be seen that the radical scavenging activity expressed by AOW increases depending on the concentration of Pt colloid. In addition, when Pt colloid is employ | adopted as a noble metal catalyst, in the theme characteristic of Examples 26-30, the time area | region which exceeds a control | contrast characteristic significantly exists in any density | concentration. The reason for this will be described later in the section of “Palladium (Pd) colloids with low oxygen reactivity / catalytic activity / hydrogen storage capacity” and will not be discussed here (the same applies hereinafter).

FIG. 27 comparing Reference Examples 19 and 20 with Examples 31 to 35 shows the time-dependent change in radical scavenging activity expressed by Pd colloid catalyst-containing hydrogen-dissolved water (AOW) with Pd colloid concentration as a main parameter. Show properties. According to the figure, when compared with the control characteristics of Reference Examples 19 and 20, the subject characteristics of Examples 31 to 35 are of low concentration (Examples 31 to 33) in almost all time regions from the start of measurement. ) Is almost the same as the control characteristic, but it can be seen that the high concentration (Examples 34 to 35) generally tends to be significantly lower than the control characteristic. That is, it can be seen that the AOWs of Examples 31 to 35 exhibit good radical scavenging activity at high concentrations (Examples 34 to 35). Further, when the subject characteristics of Examples 34 to 35 are well analyzed, the time required for radical scavenging is shorter as the concentration is higher, depending on the concentration of Pd colloid. That is, it can be seen that the radical scavenging activity expressed by AOW increases depending on the concentration of Pd colloid. In particular, the subject characteristics of the high concentration (Examples 34 to 35) begin to show a significant decrease in absorbance after about 440 seconds and about 230 seconds from the start of measurement. Assuming this reason, in the case of the high concentration (Examples 34 to 35), the existence concentration (abundance) of (.O ₂ ⁻ ) works as if it is a switch, and starts to delete it actively. It is guessed that. In addition, when Pd colloid is employ | adopted as a noble metal catalyst, the theme characteristic of Examples 31-35 is generally lower than the control | contrast characteristic in any density | concentration. The reason for this will be mentioned later in the section of “Palladium (Pd) colloids to be difficult to react with oxygen, catalytic activity, and hydrogen storage capacity” and will not be touched on here (hereinafter the same).

  FIG. 28 comparing Reference Examples 19 and 20 with Examples 36 to 41 shows Pt colloid catalyst-containing hydrogen-dissolved water (AOW) with Pt colloid (particle size distribution is 1 to 2 nm) concentration as a main parameter. The time-dependent change characteristic of the radical scavenging activity which is expressed is shown. According to the figure, when compared with the control characteristics of Reference Examples 19 and 20, after about 920 seconds from the start of measurement, the subject characteristics of Examples 36 to 41 are significantly lower than the control characteristics at any concentration. You can see that That is, it can be seen that the AOWs of Examples 36 to 41 begin to express good radical scavenging activity in a wide concentration range after a certain amount of elapsed time. Further, when the subject characteristics of Examples 36 to 41 are well analyzed, the time required for radical scavenging is shorter as the concentration is higher, depending on the concentration of Pt colloid. That is, it can be seen that the radical scavenging activity expressed by AOW increases depending on the concentration of Pt colloid.

  Here, in order to clarify the relationship between the particle size parameter of Pt colloid (particle size distribution is 2 to 4 nm / particle size distribution is 1 to 2 nm) and radical scavenging activity, the concentration of Pt colloid having a particle size distribution of 2 to 4 nm 26 is a main parameter, and FIG. 28 is a main parameter of a Pt colloid concentration with a particle size distribution of 1 to 2 nm. In order to eliminate the influence of the concentration parameter, for example, Example 27 and Example 37 having a common Pt concentration parameter (96 μg / L) will be compared. In Example 27, the peak of absorbance reaches about 320 seconds after the start of measurement, and then the subject characteristic gradually shows a downward trend, and the absorbance is once suppressed to almost zero after about 440 seconds. . On the other hand, in Example 37, the absorbance peaked at about 760 seconds after the start of measurement, and then the subject characteristic showed a gradual downward trend. However, the absorbance decreased to almost 0 in the measurement time region. It will not be suppressed. Next, Example 29 and Example 40 having a common Pt concentration parameter (384 μg / L) will be compared. In Example 29, the subject characteristic is suppressed to almost 0 after about 170 seconds from the start of measurement, and the suppression tendency continues thereafter. On the other hand, in Example 40, the peak of absorbance reaches about 260 seconds after the start of measurement, and then the subject characteristic rapidly decreases, and the absorbance is suppressed to almost 0 after about 340 seconds. Has been. Considering these comprehensively, as the Pt colloid catalyst used for the antioxidant functional water according to the present invention, the Pt colloid catalyst having a particle size distribution of 2 to 4 nm as compared with the one having a particle size distribution of 1 to 2 nm, It can be said that it is more preferable from the viewpoint of expressing good radical scavenging activity (derived from the short time required to suppress the absorbance to almost zero).

  FIG. 29 comparing Reference Examples 19 and 20 with Examples 42 to 45 shows the (Pt + Pd) mixed colloid (particle size distribution is 2 to 4 nm, Pt: Pd mixing molar ratio is 1: 2). The time-dependent change characteristic of radical scavenging activity expressed by (Pt + Pd) mixed colloid catalyst-containing hydrogen-dissolved water (AOW) as a main parameter is shown. According to the figure, when compared with the control characteristics of Reference Examples 19 and 20, the subject characteristics of Examples 42 to 45 are significantly lower than the control characteristics at any concentration after about 900 seconds from the start of measurement. You can see that That is, it can be seen that the AOWs of Examples 42 to 45 begin to express good radical scavenging activity in a wide concentration range after a certain amount of elapsed time. Further, when the subject characteristics of Examples 42 to 45 are analyzed well, the time required for radical scavenging is shorter as the concentration is higher, depending on the concentration of the (Pt + Pd) mixed colloid. That is, it can be seen that the radical scavenging activity expressed by AOW increases depending on the concentration of the (Pt + Pd) mixed colloid.

  FIG. 30, which compares Reference Examples 19 and 20 with Examples 46 to 50, shows the (Pt + Pd) mixed colloid (particle size distribution is 2 to 4 nm) concentration as a main parameter, and the mixed molar ratio of Pt: Pd. The time-dependent change characteristic of radical scavenging activity expressed by (Pt + Pd) mixed colloid catalyst-containing hydrogen-dissolved water (AOW) as a sub main parameter is shown. According to the figure, when compared with the control characteristics of Reference Examples 19 and 20, the subject characteristics of Examples 46 to 50 are significantly lower than the control characteristics at any concentration after about 520 seconds from the start of measurement. You can see that That is, it can be seen that the AOWs of Examples 46 to 50 begin to exhibit good radical scavenging activity in a wide concentration range after a certain amount of elapsed time. Further, when the subject characteristics of Examples 46 to 50 are well analyzed, the time required for radical scavenging is shorter as the concentration is higher, depending on the concentration of the (Pt + Pd) mixed colloid. That is, it can be seen that the radical scavenging activity expressed by AOW increases depending on the concentration of the (Pt + Pd) mixed colloid.

FIG. 31, which compares Reference Example 21 with Examples 51 to 55, has a (Pt + Pd) mixed colloid (particle size distribution of 2 to 4 nm) concentration as a main parameter, and a Pt: Pd mixing molar ratio as a minor component. The time-dependent change characteristic of the radical scavenging activity expressed by the (Pt + Pd) mixed colloid catalyst-containing hydrogen-dissolved water (AOW) as a parameter is shown. In Reference Example 21 and Examples 46 to 50, the (.O ₂ ⁻ ) generation system is removed. According to the figure, when compared with the control characteristic of Reference Example 21, in the subject characteristic of Examples 51 to 55, the (.O ₂ ⁻ ) generation system is removed, but (· O ₂ ^- propensity to generate) is observed. This point will be described later in connection with FIG. 37 and the like, and will not be discussed further here. However, this (• O ₂ ⁻ ) generation tendency depends on the concentration of the (Pt + Pd) mixed colloid. The darker is the more suppressed. That is, it can be seen that the radical scavenging activity expressed by AOW increases depending on the concentration of the (Pt + Pd) mixed colloid. Further, taking into account the phenomenon aspect relating to FIG. 37, which will be described later, it can be inferred that the higher the mixing molar ratio of the Pd colloid, the more the tendency of (.O ₂ ⁻ ) generation is suppressed.

  FIG. 32 comparing Reference Examples 22 and 23 with Examples 56 to 60 shows Pt colloid catalyst pre-added 1-pass electrolyzed water with Pt colloid (particle size distribution 2 to 4 nm) concentration as a main parameter. The time-dependent change characteristic of the radical scavenging activity which (AOW) expresses is shown. According to the figure, the subject characteristics of Examples 56-60 are almost the same as the control characteristics in the low concentration (Examples 56-57), but in the high concentration (Examples 58-60), It can be seen that after about 740 seconds from the measurement start time, the concentration is significantly lower than the control characteristic at any concentration. That is, it can be seen that the AOWs of Examples 58 to 60 begin to express good radical scavenging activity in a wide concentration range after a certain amount of elapsed time. Further, when the subject characteristics of Examples 58 to 60 are well analyzed, the time required for radical scavenging is shorter as the concentration is higher, depending on the concentration of Pt colloid. That is, it can be seen that the radical scavenging activity expressed by AOW increases depending on the concentration of Pt colloid.

FIG. 33 comparing Reference Examples 22 and 23 with Examples 61 to 65 shows Pd colloid catalyst pre-added 1-pass electrolyzed water with Pd colloid (particle size distribution 2 to 4 nm) concentration as a main parameter. The time-dependent change characteristic of radical scavenging activity which (AOW) expresses is shown. According to the figure, the subject characteristics of Examples 61 to 65 are almost the same as the control characteristics in the low concentration (Examples 61 to 62), but in the high concentration (Examples 63 to 65), It can be seen that after about 320 seconds from the start of measurement, the concentration is significantly lower than the control characteristic at any concentration. That is, it can be seen that the AOWs of Examples 63 to 65 begin to express good radical scavenging activity in a wide concentration range after a certain amount of elapsed time. Further, when the subject characteristics of Examples 63 to 65 are well analyzed, it is recognized that the time required for radical scavenging tends to be shorter as the concentration is higher, depending on the concentration of Pd colloid. That is, it can be seen that the radical scavenging activity expressed by AOW increases depending on the concentration of Pd colloid. In particular, in the subject characteristic of the highest concentration (Example 65), it begins to show a significant decrease in absorbance after about 830 seconds from the start of measurement. Assuming this reason, in the case of the high concentration (Example 65), the existing concentration (amount) of (.O ₂ ⁻ ) works like a switch and does not start to delete it actively. It is guessed.

  FIG. 34, which compares Reference Examples 22 and 23 with Examples 66 to 70, shows Pt colloid catalyst pre-added circulating electrolyzed water (Pt colloid catalyst pre-added water concentration (particle size distribution is 2 to 4 nm)) as a main parameter. 2 shows a time-dependent change characteristic of radical scavenging activity expressed by AOW). According to the figure, the subject characteristics of Examples 56-60 are almost the same as the control characteristics at low concentrations (Examples 66-67), but at high concentrations (Examples 68-70), It can be seen that after about 700 seconds from the measurement start time, the concentration is significantly lower than the control characteristic at any concentration. That is, it can be seen that the AOWs of Examples 68 to 70 begin to express good radical scavenging activity in a wide concentration range after a certain amount of elapsed time. Further, when the subject characteristics of Examples 68 to 70 are well analyzed, the time required for radical scavenging is shorter as the concentration is higher, depending on the concentration of Pt colloid. That is, it can be seen that the radical scavenging activity expressed by AOW increases depending on the concentration of Pt colloid.

FIG. 35 comparing the reference examples 22 and 23 with the examples 71 to 75 shows the Pd colloid catalyst pre-added circulating electrolyzed water (Pd colloid catalyst pre-added water concentration (particle size distribution is 2 to 4 nm)) as a main parameter. 2 shows a time-dependent change characteristic of radical scavenging activity expressed by AOW). According to this figure, the subject characteristics of Examples 71 to 75 begin to show a slight downward trend after about 950 seconds from the start of measurement, while those having a low concentration (Examples 71 to 72) show a high tendency. It can be seen that the concentration (Examples 73 to 75) is significantly lower than the control characteristic at any concentration after about 650 seconds from the start of measurement. That is, it can be seen that the AOWs of Examples 71 to 75 begin to exhibit good radical scavenging activity in a wide concentration range after a certain amount of elapsed time. Further, when the subject characteristics of Examples 71 to 75 are well analyzed, it is recognized that the time required for radical scavenging tends to be shorter as the concentration is higher, depending on the concentration of Pd colloid. That is, it can be seen that the radical scavenging activity expressed by AOW increases depending on the concentration of Pd colloid. In particular, in the case of the high concentration (Examples 73 to 75), after about 650 seconds, about 420 seconds, and about 230 seconds, respectively, from the measurement start time, the decrease in absorbance begins to show a significant value. Inferring this reason, in the case of the high concentration (Examples 73 to 75), the existing concentration (abundance) of (.O ₂ ⁻ ) works as if it is a switch and starts to delete it actively. It is guessed that.

  Here, in order to clarify the relationship between the electrolysis condition parameter (one-pass electrolysis / circulation electrolysis) and the radical scavenging activity in the Pt colloidal catalyst, FIG. Compared with FIG. 34, in which the Pt colloid catalyst pre-added circulating electrolyzed water is the test water. In order to eliminate the influence of the concentration parameter, for example, Example 58 and Example 68 having a common Pt concentration parameter (192 μg / L) will be compared. In Example 58, the absorbance peaked when about 680 seconds passed from the start of measurement, and then the subject characteristic gradually showed a downward trend, and the absorbance was suppressed to almost 0 after about 880 seconds passed. . On the other hand, in Example 68, the peak of absorbance reaches about 620 seconds after the start of measurement, and then the subject characteristic gradually decreases, and the absorbance reaches almost 0 after about 830 seconds. It is suppressed. Next, Example 59 and Example 69 having a common Pt concentration parameter (384 μg / L) will be compared. In Example 59, the peak of absorbance reaches about 530 seconds after the start of measurement, and then the subject characteristic gradually shows a downward trend, and the absorbance is suppressed to almost 0 after about 660 seconds. . On the other hand, in Example 69, the peak of absorbance reaches about 400 seconds after the start of measurement, and then the subject characteristic gradually shows a downward trend, and the absorbance reaches almost 0 after about 500 seconds. It is suppressed. Considering these comprehensively, the electrolysis conditions for producing the anti-oxidation functional water according to the present invention (however, electrolysis added before Pt colloidal catalyst) is compared with that of one-pass electrolysis and those of circulating electrolysis. This is more preferable from the viewpoint of exhibiting good radical scavenging activity (derived from the short time required to suppress absorbance to almost zero).

  On the other hand, in order to clarify the relationship between the electrolysis condition parameter (one-pass electrolysis / circulation electrolysis) and the radical scavenging activity in the Pd colloid catalyst, FIG. 33 using the Pd colloid catalyst pre-added one-pass electrolyzed water as test water, Contrast FIG. 35 where the Pd colloid catalyst pre-added circulating electrolyzed water is the test water. In order to eliminate the influence of the concentration parameter, for example, Example 63 and Example 73 having the same Pd concentration parameter (192 μg / L) will be compared. In Example 63, compared to the control characteristics of Reference Examples 22 and 23, the subject characteristics are lower than the main characteristics in all time regions from the measurement start time, but show a gradual upward trend. On the other hand, in the subject characteristic of Example 73, after following a gradual upward trend until about 650 seconds (absorbance peak) from the start of measurement, it turned around and showed a gradual downward trend. Absorbance is suppressed to almost 0 after the lapse of about 860 seconds. Next, Example 65 and Example 75 having a common Pd concentration parameter (768 μg / L) will be compared. In Example 65, after a very gradual upward trend from the start of measurement to the lapse of about 680 to 800 seconds (absorbance peak), it turns around and shows a gradual downward trend. On the other hand, in Example 75, the peak of absorbance is reached at the start of measurement, and thereafter, the subject characteristic gradually decreases, and the absorbance is suppressed to almost zero after about 320 seconds. Considering these comprehensively, as electrolysis conditions for producing the antioxidant functional water according to the present invention (however, electrolysis added before Pd colloidal catalyst), compared with one-pass electrolysis, that of circulation electrolysis This is more preferable from the viewpoint of exhibiting good radical scavenging activity (derived from the short time required to suppress absorbance to almost zero).

  FIG. 36 comparing Reference Examples 19 and 20 with Reference Examples 24 to 27 shows the time-dependent change characteristics of the radical scavenging activity expressed by the AsA aqueous solution with the AsA aqueous solution concentration as the main parameter. According to the figure, it can be seen that the radical scavenging activity characteristics exhibited by the AsA aqueous solutions of Reference Examples 24 to 27 are lower than those of Reference Examples 19 and 20 at any concentration. That is, it was confirmed that the AsA aqueous solutions of Reference Examples 24-27 exhibited radical scavenging activity over a wide concentration range, as is conventionally known. Moreover, it was confirmed that the radical scavenging activity expressed by the AsA aqueous solutions of Reference Examples 24-27 was increased in a concentration-dependent manner as is conventionally known. When comparing the radical scavenging activity expressed by the AsA aqueous solution with the radical scavenging activity expressed by the antioxidant functional water according to the present invention, for example, the antioxidant functional water of Example 75 is the AsA of Reference Example 24. It can be seen that the radical scavenging activity is far superior to that of the aqueous solution and comparable to the AsA aqueous solution of Reference Examples 25 to 27.

<< Palladium (Pd) colloids with poor oxygen reactivity, catalytic activity, hydrogen storage capacity >>
When an attempt is made to carry out the antioxidant method, antioxidant functional water and its use according to the present invention in an oxygen-dissolved solution system such as a living body, the presence of oxygen is a major barrier. In particular, in the living body, oxygen is abundant in relation to being used for the purpose of obtaining energy by oxidizing nutrients or for performing various oxygen addition reactions essential for the living body. The essence of the problem here is that the oxygen dissolved in the antioxidant functional water is consumed by oxygen through the noble metal colloid catalyst, in other words, the normal water is reacted with hydrogen through the noble metal colloid catalyst. And the radicals derived from the fact that oxygen itself is reduced by one electron with hydrogen activated via a noble metal colloid catalyst and (.O ₂ ⁻ ) to be erased is generated in reverse. Attenuation of erasure activity. It is recognized that the phenomenon related to this proposition tends to be amplified as the catalytic activity increases. That is, the catalytic activity and the radical scavenging activity are in a trade-off relationship, and the radical scavenging activity is attenuated as the catalytic activity increases. Therefore, it can be said that this is a deep problem that cannot be easily solved.

  In order to solve such an essential problem, the present inventors have intensively studied. As a result, among the noble metal colloid catalysts, in particular, palladium (Pd) colloid is more oxygen-resistant than platinum (Pt) colloid. As a result of finding that there is a tendency to show poor reactivity and proceeding further research based on this knowledge, as an important factor to be considered in searching for a noble metal colloid catalyst usable in the present invention, Clarifying that there are three types of oxygen reactivity, catalytic activity, and hydrogen storage capacity, and considering these three factors, it was determined that the noble metal colloidal catalyst that is superior from the viewpoint of total power is Pd colloid. Completed.

  First, the grounds for inferring that the Pd colloid exhibits poor oxygen reactivity compared to the Pt colloid will be described.

FIG. 37, which compares Reference Example 21 with Examples 76 and 77, shows radical elimination in which the catalyst-containing hydrogen-dissolved water (AOW) is expressed with the main parameter (concentration is fixed) as the difference in the type of noble metal catalyst. The time-dependent characteristic of activity is shown. In Reference Example 21 and Examples 76 and 77, the (.O ₂ ⁻ ) generation system is removed. According to the figure, the main characteristic of Example 76 is that about 0 to about 200 seconds from the start of measurement even though the (.O ₂ ⁻ ) generation system is removed. Absorbance peak (approx. 160 seconds) reaching about 0.046 is observed. In addition, after about 860 seconds from the start of measurement, a gentle increase in absorbance is observed. On the other hand, the subject characteristic of Example 77 shows almost the same tendency as the control characteristic of Reference Example 21, and no particular increase in absorbance is observed. Where the meaning of these, the subject characteristics of Example 76, during the period from the start of measurement until after about 160 seconds, (· O ₂ ^-) is actively generated, thus generated (· O ₂ ^- ) Is considered to have been erased by the radical scavenging activity expressed by the antioxidant functional water according to the present invention. In addition, after about 860 seconds from the start of measurement, the absorbance starts to gradually increase. This is because the radical scavenging activity of the antioxidant functional water according to the present invention is attenuated or exhausted (· O ₂ ^- the occurrence of) considered to no longer be erased suppression.

  Next, the inference about the action mechanism of the Pt colloid catalyst and the Pd colloid catalyst in the aqueous solution system in which hydrogen and oxygen coexist (the aqueous solution system in which oxygen is dissolved in the hydrogen-dissolved water of the present invention) will be developed.

  FIG. 38 shows the mechanism of action of the Pt colloid catalyst in a hydrogen / oxygen coexisting aqueous solution system.

As shown in the figure, the Pt colloidal catalyst adsorbs hydrogen and oxygen dissolved in the system, and passes one electron released from the activated hydrogen (.H) to oxygen (one electron of oxygen). reduction). At this time, the activated hydrogen (.H) loses one electron and is released into the system as H ⁺ ions (hereinafter, a duplicate description thereof is omitted). That is, oxygen itself is reduced by one electron by hydrogen activated via the Pt colloid catalyst, and (.O ₂ ⁻ ), which is the original erasure target, is generated in reverse. Thereafter, or at the same time, Pt colloid catalyst, and hydrogen dissolved in the system ^- as well as adsorption of the one electron released from the activated hydrogen (· O ₂₎ ^- passing the (· O ₂₎ (One-electron reduction of (.O ₂ ⁻ ) or two-electron reduction of oxygen). That is, (.O ₂ ⁻ ) itself is reduced by one electron with hydrogen activated via the Pt colloid catalyst, thereby generating (O ₂ ²⁻ ). The (O ₂ ²⁻ ) thus produced becomes hydrogen peroxide (H ₂ O ₂ ) by ionic bonding with the two H ⁺ ions present in the system. Thereafter, or at the same time, Pt colloid catalyst, as well as adsorption and hydrogen are dissolved hydrogen peroxide (H ₂ O ₂₎ to the system, the one electron released from the activated hydrogen (H ₂ O ₂ ) (One-electron reduction of ((H ₂ O ₂ ), or three-electron reduction of oxygen). That is, (H ₂ O ₂ ) itself is reduced by one electron by hydrogen activated through a Pt colloid catalyst. Thereafter, or simultaneously, the Pt colloidal catalyst adsorbs hydrogen dissolved in the system and (.OH) and releases 1 from the activated hydrogen. The electrons are transferred to (.OH) (one-electron reduction of (.OH) or four-electron reduction of oxygen), that is, (.OH) itself is reduced by one electron by hydrogen activated through a Pt colloid catalyst. To produce OH ⁻ ions The OH ⁻ thus produced forms water (H ₂ O) by ionic bonding with H ⁺ ions, thus stopping a series of reactions, and in the aqueous solution system in which hydrogen and oxygen coexist. It is an action mechanism of a Pt colloid catalyst.

  On the other hand, the mechanism of action of the Pd colloid catalyst is as follows.

  FIG. 39 shows the mechanism of action of the Pd colloid catalyst in a hydrogen / oxygen coexisting aqueous solution system. In the description of the mechanism of action of the Pd colloidal catalyst, the point of great difference from the mechanism of action of the Pt colloidal catalyst is the part derived from the poor reactivity to oxygen. A duplicate description is omitted.

As shown in the figure, the Pd colloid catalyst adsorbs hydrogen dissolved in the system, but does not actively adsorb oxygen, or there is negative adsorption (impact of oxygen colliding with the Pd colloid catalyst). Even so, there is a tendency that one electron released from the activated hydrogen (.H) is difficult to pass to oxygen (does not reduce oxygen molecules). Therefore, (.O ₂ ⁻ ) that is the original erasure target is hardly generated. The subsequent mechanism of action is the same as that of the Pt colloid catalyst, and is present in the system by the cooperative work of the Pd colloid catalyst and hydrogen dissolved in the system (.O ₂ ⁻ ), hydrogen peroxide ( H ₂ O ₂ ) or (.OH) is reduced, and finally water (H ₂ O) is generated to stop the series of reactions.

  Here, the characteristics of palladium (Pd) preferable as a noble metal colloid catalyst according to the present invention will be described. Palladium is a transition metal atom discovered by Wollaston in 1803 with an atomic number of 46 and an atomic weight of 106.42. Its name is named after the asteroid Pallas (Greek mythology Athens), which was discovered the previous year. It is a valuable element that exists only about 24,000 tons on the earth. Palladium has an excellent ability to take in hydrogen, and can occlude hydrogen of 740 to 935 times its own volume. Often used for hydrogenation catalysts and hydrogen purification. The field where palladium is most frequently used is as a catalyst. Starting with its use as a hydrogenation catalyst, palladium complexes have also been used as catalysts for the production of acetaldehyde from ethylene. Other uses include dental treatment metals and decorative items.

  Now, when thinking about the reaction object of the antioxidant functional water according to the present invention, for example, free radicals having unpaired electrons and strong oxidizing power, and oxidation having no unpaired electrons but oxidizing power It can be broadly classified into substances. Among these, in the former example, atomic hydrogen having a strong reducing power derived from the antioxidant functional water according to the present invention corresponds to the radical (giving the electron of atomic hydrogen to the radical), thereby eliminating the radical. It is considered that the activity is expressed. On the other hand, in the latter example, atomic hydrogen having strong reducing power derived from the antioxidant functional water according to the present invention selectively corresponds to the oxidizing substance according to the partner (the atomic hydrogen of the oxidizing substance is It is considered that the reduction activity is selectively expressed by giving an electron. Here, the selective reduction activity means that the compatibility between atomic hydrogen and the oxidant, that is, the frontier electron occupying the highest occupied orbit on the atomic hydrogen side according to the frontier electron theory, on the oxidant side. Depending on conditions such as ease of flow into the lowest empty orbit, it is considered that the reduction activity is selectively expressed. As a specific example for reference, vitamin B2 as an oxidizing substance is reduced in vitamin B2 in test water in which Pd colloid catalyst-containing (192 μg / L concentration) hydrogen-dissolved water (AOW) according to the present invention is dissolved. No activity was observed. In this example, since the atomic hydrogen having strong reducing power derived from the antioxidant functional water according to the present invention did not give electrons to the oxidizing substance (vitamin B2), the expression of the reducing activity was not recognized. It is considered a thing. That is, it can be said that atomic hydrogen and an oxidizing substance (vitamin B2) are incompatible. Furthermore, in the test water in which oxidized methylene blue as an oxidizing substance was dissolved in the Pd colloid catalyst-containing (192 μg / L concentration) hydrogen-dissolved water (AOW) according to the present invention, methylene blue reducing activity was observed. In this example, it is considered that the expression of the reducing activity was recognized because the atomic hydrogen having strong reducing power derived from the antioxidant functional water according to the present invention gave electrons to the oxidizing substance (oxidized methylene blue). It is done. That is, it can be said that atomic hydrogen and the oxidizing substance (oxidized methylene blue) are compatible.

  In order to increase the reactivity of the antioxidant functional water according to the present invention with respect to the above-described reaction target, for example, dissolved hydrogen by a method for quantitatively analyzing dissolved hydrogen concentration using a redox dye at a saturated concentration or higher under atmospheric pressure. It is considered preferable that hydrogen of the concentration effective value is dissolved and / or that a large amount of hydrogen is occluded in the noble metal catalyst itself contained in the hydrogen-dissolved water.

<< Disclosure of Additional Examples by DH Quantitative Analysis Method Using Redox Dye >>
In the following, additional examples by the DH quantitative analysis method using the above-described redox dye will be shown.

(Example 78)
The pre-catalyst-added circulating electrolyzed water similar to that in Example 73 was used as test water (AOW), and 200 mL of the test water was tested using 1 mL of the 40-fold concentration Pt standard solution substituted with nitrogen gas as described above using a syringe. After pouring into the water storage chamber and mixing well, the test water was visually observed with a methylene blue aqueous solution having a concentration of 10 g / L (volume molar concentration: 26773.8 μM) in the test water. While small amounts were injected using a syringe. The total injection amount of the methylene blue aqueous solution up to the end point was 7.8 mL, and the effective value of the dissolved hydrogen concentration DH obtained by substituting each value into Equation 7 was 2.09 (mg / L). . Various physical property values of the test water according to this working example 78 are shown in Table 4, and the effective value of the dissolved hydrogen concentration DH is shown in FIG.

(Example 79)
The basic water 6.86 as in Reference Example 22 was electrolyzed for 3 minutes in the continuous water circulation type (circulation water amount 0.8 liters) under the same electrolysis conditions as in Example 71. 1 mL of the above 40-fold concentrated Pt reference solution substituted with nitrogen gas is poured into the test water storage chamber using a syringe and mixed thoroughly with 200 mL of the test water. A methylene blue aqueous solution having a concentration of 10 g / L (volume molar concentration: 26773.8 μM) was injected into the test water little by little using a syringe while visually observing the color change of the test water. The total injection amount of the same methylene blue aqueous solution up to the end point was 8.5 mL, and the effective value of the dissolved hydrogen concentration DH obtained by substituting each value into Equation 7 was 2.28 (mg / L). . Various physical property values of the test water according to Example 79 are shown in Table 4, and the effective value of the dissolved hydrogen concentration DH is shown in FIG.

(Example 80)
Pd colloid-containing activated carbon-treated water is prepared by adding the same Pd standard solution as in Example 31 to the activated carbon-treated water obtained by passing Fujisawa city tap water through an activated carbon column in an amount such that its concentration is 384 μg / L. The Pd colloid-containing activated carbon-treated water thus prepared was subjected to pre-catalyst-added circulating electrolyzed water subjected to electrolytic treatment over 3 minutes in the continuous water circulation type (circulating water amount 0.8 liters) under the same electrolysis conditions as in Example 71. After the test water (AOW), 1 mL of the 40-fold concentration Pt standard solution substituted with nitrogen gas described above into 200 mL of the test water was poured into the test water storage chamber using a syringe, and the mixture was sufficiently stirred and mixed. A methylene blue aqueous solution having a concentration of 10 g / L (volume molar concentration: 26773.8 μM) was injected into the test water little by little using a syringe while visually observing the color change of the test water. The total injection amount of the same methylene blue aqueous solution up to the end point was 9.7 mL, and the effective value of the dissolved hydrogen concentration DH obtained by substituting each value into the above formula 7 was 2.60 (mg / L). . Various physical property values of the test water according to Example 80 are shown in Table 4, and the effective value of the dissolved hydrogen concentration DH is shown in FIG.

(Example 81)
Activated carbon treated with Fujisawa city tap water passed through an activated carbon column was electrolyzed for 3 minutes in the continuous water circulation system (circulated water volume 0.8 liters) under the same electrolysis conditions as in Example 79. Circulating electrolytically treated water is used as test water, and 200 mL of the test water is injected with 1 mL of the 40-fold concentration Pt reference solution substituted with the nitrogen gas described above into the test water storage chamber using a syringe, and is sufficiently stirred and mixed. Then, a methylene blue aqueous solution having a concentration of 10 g / L (volume molar concentration: 26773.8 μM) was injected into the test water little by little using a syringe while visually observing the color change of the test water. The total amount of methylene blue solution injected until reaching the end point was 10.6 mL, and the effective value of the dissolved hydrogen concentration DH determined by substituting each value in the above equation 7 was 2.84 (mg / L). . Various physical property values of the test water according to Example 81 are shown in Table 4, and the effective value of the dissolved hydrogen concentration DH is shown in FIG.

(Example 82)
Pd colloid-containing activated carbon-treated water is prepared by adding the same Pd standard solution as in Example 31 to the activated carbon-treated water obtained by passing Fujisawa city tap water through an activated carbon column in an amount of 192 μg / L. The Pd colloid-containing activated carbon-treated water thus prepared was subjected to the pre-catalyst-added circulating electrolyzed water subjected to electrolytic treatment for 3 minutes in the continuous water circulation type (circulating water amount 0.8 liter) under the same electrolysis conditions as in Example 80. After the test water (AOW), 1 mL of the 40-fold concentration Pt standard solution substituted with nitrogen gas described above into 200 mL of the test water was poured into the test water storage chamber using a syringe, and the mixture was sufficiently stirred and mixed. A methylene blue aqueous solution having a concentration of 10 g / L (volume molar concentration: 26773.8 μM) was injected into the test water little by little using a syringe while visually observing the color change of the test water. The total amount of methylene blue solution injected until reaching the end point was 12.0 mL, and the effective value of the dissolved hydrogen concentration DH determined by substituting each value in the above formula 7 was 3.21 (mg / L). . Various physical property values of the test water according to Example 82 are shown in Table 4, and the effective value of the dissolved hydrogen concentration DH is shown in FIG.

《抗酸化機能水（ＡＯＷ）が線虫Ｃ・エレガンスの寿命に与える影響を調べる》
線虫の一種であるCaenorhabditis elegans（C.elegans、以下、「Ｃ．エレガンス」）は、ショウジョウバエやマウス・ラット等と並んで、多細胞生物の老化モデルとして世界中で広く使用されている。また、Ｃ．エレガンスでは、全ゲノムの塩基配列が決定されており、遺伝子破壊やＧＦＰ融合遺伝子による発現解析などの手法を組み合せて、ヒトの遺伝病原因遺伝子や癌遺伝子などの個体レベルでの機能や作用機構を調べるための「生きた試験管」として注目されている。

<Investigating the Effect of Antioxidant Functional Water (AOW) on the Life of Nematode C. Elegance>
Caenorhabditis elegans (C. elegans, hereinafter referred to as “C. elegans”), which is a type of nematode, is widely used around the world as an aging model for multicellular organisms, along with Drosophila and mice / rats. In addition, C.I. In Elegance, the base sequence of the entire genome has been determined, and by combining methods such as gene disruption and expression analysis using GFP fusion genes, the functions and mechanisms of action at the individual level such as genes causing human genetic diseases and oncogenes It is attracting attention as a “living test tube” for investigating.

  Of particular note is the wild-type C.I. The longevity of elegance is as short as about 25 days ("Aging at the molecular level" written by Naoaki Ishii: Kodansha (2001), P102-P103). C. as an experimental animal When elegance is used, the effect of antioxidant functional water on the life of animals can be examined in a short period of time.

  Accordingly, the present inventors have obtained the guidance and cooperation of Tokai University School of Medicine Associate Professor Naoaki Ishii and other authors of the above-mentioned document “Aging at the Molecular Level”. C. when antioxidant function water (AOW) is used as breeding water for elegance. A test was conducted to investigate the effect on the life of elegance. The term “breeding water” as used herein refers to the following (A-2) test procedure performed for each test group of purified water and anti-oxidative functional water. The water used for each of the operations of standing still and the operation of dripping water on the surface of the agar medium when the insect is alive or dead in the item (8) or when the agar medium is dried.

  The outline of this test protocol is explained in the following (A), the examples and reference examples of the test are explained in the following (B), and the results and considerations of the test are explained in the following (C). . In addition, this test is described in “Reactive Oxygen Experiment Protocol-Measurement Method / Genetic Analysis / Pathophysiology Model” supervised by Naoyuki Taniguchi: Cell Engineering Separate Volume Experiment Protocol Series, published by Shujunsha Co., Ltd. (1994) P288-P292. Among the “aging model”, it conforms to “2. Lifetime measurement under various oxygen concentrations” described in P290-P292 (hereinafter, this reference is abbreviated as “compliance procedure”). The contents of the above “aging model” are incorporated herein by this reference. However, the C.I. In light of the peculiarity of this test, which examines the effect on the life of elegance, some of the compliance procedures have been modified. Therefore, the description of this test protocol will focus on the modified part of the compliant procedure.

(A) Outline of test protocol (A-1) Reagents used Reagents used in this test are as follows.

(1) Fluorodeoxyuridine (5-fluoro-2'-deoxyuridine: FudR) ... Wako Pure Chemical
(2) S buffer
Sodium chloride: NaCl (0.1M)
Potassium phosphate: pH6.0
C. Since elegance is hermaphroditic, it should be devised not to be confused with the next generation. Therefore, according to the compliant procedure, the reagent FudR was added to C.I. It is used for the purpose of inhibiting the next generation of elegance. Further, the S buffer is used for the purpose of removing the influence due to the difference in pH.

(A-2) Test procedure
(1) Collect wild-type first stage larvae that have been cultivated in accordance with a compliant procedure. About 500-1000 insects are put into 9 cm shearle with agar medium. The age of the insect at the time of this operation is about 4 days.

 (2) After pouring an appropriate amount of S-buffer with a Pasteur pipette into the petri dish, the S-buffer is aspirated with the insects in the petri dish with the same Pasteur pipette. This is transferred to a tube (1.5 mm diameter). If the tube is left standing in a vertical position, insects will settle on the bottom of the tube. After the insect has settled, remove the S buffer (supernatant) in the tube by gently aspirating with a Pasteur pipette, taking care not to suck the insect. Thereby, insects are collected in the tube with the S buffer in the tube removed.

 (3) Take out an appropriate amount (about 100 to 200) of the insects collected in the tube in (2) above, and distribute them into two tubes (1.5 mm diameter, about 1 to 2 cc capacity). Then, control (purified water of Reference Example 28 described later) is poured into each of the two tubes, and test water (antioxidation functional water of Example 83 described later) is poured into the other.

 (4) Attach lids to the openings of the above tubes, place the tubes sideways and let stand for 2 to 3 hours.

 (5) Transfer the insects from each of the tubes after standing horizontally to the two 9 cm shears containing the agar medium and let stand overnight at room temperature.

 (6) Prepare a 3 cm petri dish (20 sheets) containing an agar medium with a light and dry surface. A drop of Escherichia coli serving as a bait for insects is dropped on the center of each 3 cm dish. In this way, insects gather in the center in search of food and are easy to observe.

 (7) From each of the two 9cm shears that were left at room temperature overnight in (5) above, insects were prepared in (6) above using the isolation platinum wire described below. Transfer 10 animals each to a 3 cm petri dish of 10 petri dishes. These 100 animals are used as one test group. When there are two test groups, this operation is performed for each test group. During the insect sorting operation, the reagent FudR is added together. The isolation platinum wire is a platinum wire with a length of about 3 cm and a diameter of about 50-100 μm attached to the narrow mouth of a 3 cm Pasteur pipette. The tip of the platinum wire is sharpened with a file, etc. It is a self-made tool bent at a right angle at 5 mm. For each use, sterilize the tip (the part that touches the insect or agar medium) with a burner flame. Its usage is to scoop up insects from below. After picking up the insect, when the tip is lightly touched on the agar, the insect moves from itself to the agar medium.

 (8) Life and death (days of age) of insects belonging to each group are examined daily (in principle, every other day in this study). Insect life / death judgment is performed by touching the insect's head lightly with an isolation platinum wire, or by dripping water and judging that it does not react at all. When the agar medium has dried, drop 1 or 2 drops of water on the surface of the agar medium with a Pasteur pipette.

(B) Disclosure of Examples and Reference Examples (Reference Example 28)
C. elegans according to the test procedure described in (A-2) when adopting activated carbon treated water (purified water) obtained by passing Fujisawa city tap water through an activated carbon column as breeding water. The elegance life data is referred to as Reference Example 28.

(Example 83)
1 liter of activated carbon treated water (purified water) similar to that in Reference Example 28 was taken, and water added with the Pd standard solution described in Examples 6 to 8 in an amount such that the Pd colloid concentration was 192 μg / L was added every minute. Pre-catalyst-added circulating electrolyzed water subjected to electrolytic treatment (equivalent to 2-pass electrolysis) for 1 minute in a continuous water circulation system (circulating water amount is 0.8 liter) under electrolysis conditions of 5 A constant current at a flow rate of 1.5 liters C. elegans according to the test procedure described in (A-2) when (AOW) is employed as breeding water. The life data of elegance is defined as Example 83.

(C) Test results and discussion of the results FIG. 41 comparing Reference Example 28 (group using purified water as breeding water) and Example 83 (group using antioxidant functional water as breeding water), 42, electrolyzed water containing Pt colloid catalyst (AOW) is C.I. Shows the effect on the life of elegance. In addition, Table 5 shows the results of a significant difference test of the average lifespan between the two independent groups according to this test performed by Student's t-test.

表５に示すように、危険率０．１％においてt=4.03>t 境界値両側（3.34）であるから、「飼育用水として抗酸化機能水を用いた群と、浄水を用いた群の２つのグループの平均寿命は等しい」という帰無仮説は棄却された。したがって、飼育用水として抗酸化機能水を用いた群（標本数は９９）の平均寿命（２０．０５日）は、浄水を用いた群（標本数は９５）の平均寿命（１７．７５日）よりも２．３日だけ長く、この差は有意であった (ｔ(192)=4.03，SD=0.57，ｐ <0.001)。ここで、「ｔ(192)=4.03」はｔ値を、このうち「192」は自由度を、SDは２群の平均寿命間における差の標準偏差を、ｐは危険率を表す。

As shown in Table 5, since t = 4.03> t boundary value both sides (3.34) at a risk rate of 0.1%, “2 of the group using antioxidant functional water and the group using purified water as breeding water” The null hypothesis that “the average lifespan of two groups is equal” was rejected. Therefore, the average life span (20.05 days) of the group using the antioxidant functional water as breeding water (99 samples) is the average life span (17.75 days) of the group using clean water (95 samples). The difference was significant (t (192) = 4.03, SD = 0.57, p <0.001). Here, “t (192) = 4.03” represents the t value, among which “192” represents the degree of freedom, SD represents the standard deviation of the difference between the average lifespans of the two groups, and p represents the risk factor.

  When this test result is considered, it is considered that the life of the nematode C. elegans has been extended as a result of the antioxidant functional water suppressing oxidative damage derived from reactive oxygen species. Reactive oxygen species are toxic to living cells through oxidative damage to intracellular molecules such as proteins and nucleic acids. In other words, it has been elucidated by research using nematodes and Drosophila that oxidative damage derived from reactive oxygen species is involved in aging (Naoki Ishii, “Mechanism for determining lifespan in nematodes”, Cell Engineering Vol.21 No. 7 2002, Agarwal, S. et al., Proc. Natl. Acad. Sci. USA, 91, 12332-12335, 1994, Larsen, PL Proc. Natl. Acad. Sci. USA, 90, 8905-8909, 1993, Sohal, RS et al., J. Biol. Chem., 270, 15671-15674, 1995, etc.). As with these studies, we are confident that the results obtained in this study suggest that oxidative damage derived from reactive oxygen species is involved in aging.

《Does antioxidant function water (AOW) scavenge hydroxy radicals (.OH)? >>
Hydroxyl radicals (.OH) have a strong oxidizing power and are known to cause extremely damaging damage to living organisms, such as cleaving gene DNA strands and inducing lipid peroxidation in living organisms. It has been. In other words, it is important for a living body how to suppress the amount of hydroxy radical (.OH) produced.

  So, does antioxidant functional water (AOW) erase hydroxy radicals (.OH)? On the other hand, the scavenging activity of hydroxy radicals (.OH) generated by ultraviolet irradiation of hydrogen peroxide was evaluated using the spin trap ESR method based on the samples of 4 samples described later. The spin trap ESR method is a method for measuring radical species (active oxygen, transition metals, organic radicals, etc.) having unpaired electrons, which is performed in a measurement system that combines an electron spin resonance (ESR) device and a spin trap reagent. This is a measurement method that can be selectively detected with high sensitivity. The outline of the measurement procedure is shown below.

(A) Overview of measurement procedure (A-1) Sample The samples used for the main measurement are as follows.

(1) Sample 1: distilled water purged with nitrogen gas by bubbling
(2) Sample 2: Distilled water purged with hydrogen gas by bubbling
(3) Sample 3: Pd colloid manufactured by Tanaka Kikinzoku Co., Ltd. (with a particle size distribution of 2 to 4 nm and containing polyvinylpyrrolidone (PVP) as a dispersant) at a concentration of about 200 μg / L and then bubbling Distilled water substituted with hydrogen gas (AOW)
(4) Sample 4: Distilled water containing the same Pd colloid made by Tanaka Kikinzoku Co., Ltd. as in Sample 3 at a concentration of about 200 μg / L, and purged with nitrogen gas by bubbling (A-2) Reagents used The reagents used in were as follows.

(1) 30% hydrogen peroxide water: Wako Pure Chemical
(2) 5,5-Dimethyl-1-pyrroline-N-oxide (DMPO) ・ ・ ・ Nacalai Tesque (A-3) Used Equipment The equipment used for this measurement is as follows.

(1) ESR equipment: ESP350E ... BRUKER
(2) Attached equipment:
i. Microwave frequency counter: HP5351 ... made by HEWLETT PACKARD
ii. Gaussmeter: ER035M ... BRUKER (A-4) Measurement procedure
(1) Solution preparation:
All the solutions to be mixed with the sample were prepared under a nitrogen gas flow. The pure water described below was used after nitrogen gas bubbling. As a sample or solution container, a whole pipette (0.5 mL, 1.0 mL) and a volumetric flask (10 mL, 50 mL) were used.

(2) 1mM hydrogen peroxide solution:
i. 0.5 mL of 30% hydrogen peroxide solution (9.8 M) was taken and diluted with pure water to make a total volume of 50 mL to obtain a 100 mM solution.

  ii. 0.5 mL of the above solution i was taken and diluted with pure water to make a total volume of 50 mL to obtain a 1 mM solution. At the time of storage, the aluminum foil was wound and light-shielded.

(3) ESR measurement:
i. 1 mL of hydrogen peroxide solution (H ₂ O ₂ ) prepared to 1 mM and 15 μL of DMPO were taken and diluted with a sample to make a total volume of 10 mL. At this time, the H ₂ O ₂ concentration is 0.1 mM, and the DMPO concentration is 13 mM.

  ii. The solution of i was sucked into an ESR flat cell and measured while irradiating with ultraviolet rays. For ultraviolet irradiation, an ultra-high pressure mercury lamp (manufactured by Ushio Inc.) was used and irradiated through a water filter.

(4) Measurement conditions:
Measurement temperature Room temperature magnetic field sweep range 3440-3540 G
Modulation 100kHz, 1G
Microwave 9.80 G Hz, 16mW
Sweep time 41.943 s * 1 times
Time constant 81.92ms
Number of data points 1024 points
Cavity TM ₁₁₀ , Cylindrical type (B) Measurement results and discussion of the results In all of the samples 1 to 4, DMOH-OH radical adducts (DMPO-OH) were observed. This is because the hydroxyl radical (.OH) derived from hydrogen peroxide generated by ultraviolet irradiation on the samples 1 to 4 was captured by DMPO and DMPO-OH was generated. Table 6 shows the relative intensities of DMPO-OH obtained from ESR spectra after 60 seconds from the start of ultraviolet irradiation on samples 1 to 4.

試料１（相対強度：1）と試料２（相対強度：0.29）、並びに、試料３（相対強度：0.10）と試料４（相対強度：0.90）をそれぞれ対比してみると、試料２、３中の溶存水素に由来すると考えられる強いヒドロキシラジカル（・ＯＨ）消去活性が認められた。これは、ヒドロキシラジカル（・ＯＨ）がもつ強力な酸化力によって、分子状水素から電子が引き抜かれたものと考えられる。また、試料２（相対強度：0.29）と試料３（相対強度：0.10）を対比してみると、試料３中の水素とパラジウムコロイドの組み合わせに由来すると考えられる強いヒドロキシラジカル（・ＯＨ）消去活性が認められた。これは、水素とパラジウムコロイドの組み合わせに由来する還元力が、ヒドロキシラジカル（・ＯＨ）に対して作用したものと考えられる。

When comparing sample 1 (relative intensity: 1) and sample 2 (relative intensity: 0.29) and sample 3 (relative intensity: 0.10) and sample 4 (relative intensity: 0.90), respectively, Strong hydroxy radical (.OH) scavenging activity, which is thought to be derived from dissolved hydrogen, was observed. This is thought to be because electrons were extracted from molecular hydrogen by the strong oxidizing power of the hydroxy radical (.OH). In addition, when comparing sample 2 (relative intensity: 0.29) and sample 3 (relative intensity: 0.10), strong hydroxy radical (.OH) scavenging activity that is thought to be derived from the combination of hydrogen and palladium colloid in sample 3 Was recognized. This is considered that the reducing power derived from the combination of hydrogen and palladium colloid acts on the hydroxy radical (.OH).

  From the above measurement results, it became clear that the antioxidant functional water (AOW) erases the hydroxy radical (.OH) having the strongest oxidizing power among the active oxygen species.

《Does antioxidant water (AOW) suppress oxidation of reduced vitamin C? >>
Clear ^- Vitamin C is a vitamin soluble, these ascorbic acid is reduced vitamin C has a strong reducing power, in vivo reactive oxygen species such as superoxide anion radical (· O ₂₎ In addition, the oxidized vitamin E is regenerated into a reduced form. However, when ascorbic acid (reduced vitamin C) is oxidized by exposure to oxygen or the like, it changes to dehydroascorbic acid (oxidized vitamin C) via monodehydroascorbic acid. Such oxidized vitamin C cannot exert a reducing power in a living body. That is, it is important that vitamin C is maintained in a reduced state when taken into the living body. Therefore, antioxidative functional water (AOW) suppresses oxidation of reduced vitamin C, assuming the commercialization of reduced vitamin C-containing AOW that contains reduced vitamin C in antioxidant functional water (AOW). ? The test about was conducted. The outline of the test protocol is shown below.

(A) Outline of test protocol (A-1) Reagents used Reagents used in this test are as follows.

(1) Distilled water: Wako Pure Chemical
(2) L (+)-ascorbic acid reagent special grade: Wako Pure Chemical
(3) pH buffer solution: Tris-HCl (7.4), Tris-HCl (9.0), Glycine-HCl (2.2) (A-2) Analytical instruments used The instruments used for this measurement are as follows. It is as follows.

(1) UV / Visible Spectrophotometer: Ultrospec 3300 pro ・ ・ ・ Amersham Pharmacia Biotech
(2) Attached equipment: Constant temperature cell holder: Amersham Pharmacia Biotech (A-3) Solution preparation
(1) Add 50 mg of ascorbic acid (AsA) to 100 mL of distilled water purged with nitrogen gas to obtain an ascorbic acid aqueous solution. However, since the ascorbic acid aqueous solution gradually oxidizes when left in an air exposure environment, a new ascorbic acid aqueous solution is prepared and used for each test.

 (2) pH buffer solution: Prepared distilled water containing 100 mM Tris-HCl (7.4), distilled water containing 100 mM Tris-HCl (9.0), and distilled water containing 10 mM Glycine-HCl (2.2) These were used as distilled water at each pH, and these were called distilled water (7.4), distilled water (9.0), and distilled water (2.2). On the other hand, hydrogen water substituted at each pH for distilled water prepared at each pH is referred to as hydrogen water at each pH, and these are referred to as hydrogen water (7.4), hydrogen water (9.0), and hydrogen water (2.2).

 (3) In order to prepare the antioxidant functional water by adding the noble metal colloid catalyst to the hydrogen water prepared at each pH of (2) above, the noble metal colloid catalyst (Pt) is added to the hydrogen water prepared at each pH.・ Pd / Pt / Au alloy / Pd / Au alloy, any one of the four types, all manufactured by Tanaka Kikinzoku Co., Ltd., particle size distribution 2 to 4 nm, containing polyvinylpyrrolidone (PVP) as a dispersant) After that, hydrogen gas replacement is further performed.

(A-4) Test procedure
(1) A rubber plug made by ALDRICH (Aldrich) is placed in a quartz cell (optical path length: 1 cm, capacity: 3 cc) of a spectrophotometer, and the air inside the cell is replaced with hydrogen gas.

 (2) Take 2 mL of the antioxidant functional water prepared in (A-3)-(3) above into a syringe (made of plastic), and inject it into a quartz cell.

 (3) 100 μL of the ascorbic acid aqueous solution prepared in (A-3)-(1) above is taken into a syringe (made of plastic), and this is injected into a quartz cell. At this time, the concentration of ascorbic acid in the quartz cell is 135 μM.

 (4) The quartz cell is quickly set in the spectrophotometer, and the time-dependent change of absorption wavelength 250 nm for 30 minutes, that is, the change in absorbance (A250) from 0 to 1800 minutes, Measure and record the absorption spectrum every 30 minutes. The temperature in the quartz cell was set to 37 ° C. using a constant temperature cell holder.

 (5) During the measurement, oxygen (air) is gradually mixed into the quartz cell through the rubber plug made by ALDRICH. As a result, oxidation of reduced vitamin C proceeds.

 (6) The test result was expressed as a residual ratio (%) of reduced vitamin C every 30 minutes from the start of the test. In obtaining the residual ratio (%) of reduced vitamin C, correction is performed by subtracting the absorbance derived from oxidized vitamin C from the measured absorbance.

  The method for obtaining the residual ratio (%) of reduced vitamin C and the basis for absorbance correction are described below.

  First, how to determine the residual ratio (%) of reduced vitamin C will be described. The absorption maximum wavelength in the ultraviolet region of reduced vitamin C (AsA) shifts depending on the liquidity of the solution. Specifically, it is around 240 nm in the acidic region and shifts to around 270 nm in the neutral to basic region. In this test, the absorption wavelength of reduced vitamin C was selected to be 250 nm, which allows characteristic detection in the entire liquid region.

  The residual ratio (%) of reduced vitamin C at a wavelength of 250 nm selected as described above is obtained from the calculation formula {A250 (T) -A250 (min.)} / {A250 (0) -A250 (min.)}. It was. However, (T = 0, 30, 60, 90, 120, 150, 180) and A250 (min.) = 0.311. When absorption of reduced vitamin C (AsA) ceases, absorption of oxidized vitamin C in general remains, but this is A250 (min.) = 0.111. Incidentally, this A250 (min.) Also includes the absorption spectrum of distilled water.

  Next, the basis for such absorbance correction will be described. The specific absorption spectrum of reduced vitamin C (AsA) in the ultraviolet region is derived from the enediol group of reduced vitamin C (AsA). The enediol group forms a conjugated structure of reduced vitamin C (AsA), and this conjugated structure is an essential element that causes a specific absorption spectrum in the ultraviolet region. The enediol group has two hydrogen atoms, and this bears the reducing power of reduced vitamin C.

  On the other hand, vitamin C that has lost both hydrogen atoms of the enediol group changes to oxidized vitamin C (DHA), and further changes to oxidative degradation products. Since the enediol group is lost at this time, the specific absorption in the ultraviolet region is lost as a result of the loss of the conjugated structure.

  This means that there is no absorption spectrum specific to reduced vitamin C (AsA), and it does not mean that the vitamin C body is completely eliminated. In other words, oxidized vitamin C remains, and it does not mean that vitamin C is completely decomposed into water and carbon dioxide, leaving no trace. The absorption spectrum of oxidized ascorbic acid (DHA) may be considered to be obtained by subtracting the effect of the enediol group from the absorption spectrum of reduced vitamin C (AsA).

  When reduced vitamin C (AsA) and oxidized vitamin C (DHA) coexist, the molar extinction coefficient ε of reduced vitamin C (AsA) is larger than that of oxidized vitamin C (DHA). The absorption spectrum of reduced vitamin C (AsA) is not hidden by the absorption spectrum of oxidized vitamin C (DHA). Therefore, even if the absorption spectrum of oxidized vitamin C (DHA) is subtracted from the absorption spectrum of reduced vitamin C (AsA), the absorption spectrum peculiar to reduced vitamin C still remains. Even if correction is performed, the accuracy of the residual ratio (%) of reduced vitamin C is not adversely affected.

(B) Disclosure of Examples and Reference Examples (Reference Example 29)
Measurement of residual ratio of reduced vitamin C according to the test procedure described in (A-4) above when distilled water (7.4) adjusted in pH according to (A-3)-(2) above is adopted as test water The data is referred to Reference Example 29.

(Reference Example 30)
Measurement of residual ratio of reduced vitamin C according to the test procedure described in (A-4) above when distilled water (9.0) adjusted in pH in (A-3)-(2) above is adopted as test water The data is referred to as Reference Example 30.

(Reference Example 31)
Measurement of residual ratio of reduced vitamin C according to the test procedure described in (A-4) above when distilled water (2.2) adjusted in pH according to (A-3)-(2) above is adopted as test water The data is referred to as Reference Example 31.

(Reference Example 32)
Measurement of residual ratio of reduced vitamin C according to the test procedure described in (A-4) above when hydrogen water (7.4) adjusted in pH according to (A-3)-(2) above is adopted as test water The data is referred to as Reference Example 32.

(Reference Example 33)
Measurement of residual ratio of reduced vitamin C according to the test procedure described in (A-4) above, when hydrogen water (9.0) adjusted in pH according to (A-3)-(2) above is adopted as test water The data is referred to as Reference Example 33.

(Reference Example 34)
Measurement of residual ratio of reduced vitamin C according to the test procedure described in (A-4) above when hydrogen water (2.2) adjusted in pH according to (A-3)-(2) above is adopted as test water The data is referred to as Reference Example 34.

(Example 84)
As the test water, an antioxidant functional water obtained by adding the Pt standard solution described in Examples 3 to 5 to the hydrogen water (7.4) in an amount that gives a colloid concentration of about 200 μg / L (above ( The residual ratio measurement data of reduced vitamin C according to the test procedure described in A-4) is referred to as Example 84.

(Example 85)
As the test water, the above-mentioned (A-) when the antioxidant functional water obtained by adding the same Pt standard solution as in Example 84 to hydrogen water (9.0) in an amount that the colloid concentration is about 200 μg / L is adopted. The residual ratio measurement data of reduced vitamin C according to the test procedure described in 4) is referred to as Example 85.

(Example 86)
As the test water, the above-mentioned (A-) when the antioxidant functional water obtained by adding the same Pt standard solution as in Example 84 to the hydrogen water (2.2) in an amount such that the colloid concentration is about 200 μg / L is adopted. The residual ratio measurement data of reduced vitamin C according to the test procedure described in 4) is referred to as Example 86.

(Example 87)
As the test water, an antioxidant functional water obtained by adding the Pd reference solution described in Examples 6 to 8 to the hydrogen water (7.4) in an amount that gives a colloid concentration of about 200 μg / L (above ( The residual ratio measurement data of reduced vitamin C according to the test procedure described in A-4) is referred to as Example 87.

(Example 88)
As the test water, the above-mentioned (A-) when the antioxidant functional water obtained by adding the same Pd standard solution as in Example 87 to the hydrogen water (9.0) in an amount such that the colloid concentration is about 200 μg / L is adopted. The residual ratio measurement data of reduced vitamin C according to the test procedure described in 4) is taken as Example 88.

Example 89
As the test water, the above-mentioned (A-) when the antioxidant functional water obtained by adding the same Pd standard solution as in Example 87 to the hydrogen water (2.2) in an amount such that the colloid concentration is about 200 μg / L is adopted. The residual ratio measurement data of reduced vitamin C according to the test procedure described in 4) is taken as Example 89.

(Example 90)
As test water, hydrogen water (7.4), Pt / Au alloy colloid manufactured by Tanaka Kikinzoku Co., Ltd. (alloy having Pt as core, Au as shell, and Pt core completely covered with Au shell) The metal molar ratio of Pt / Au is 3.71 / 6.29, and the Pt / Au atomic ratio in one Pt / Au alloy cluster is 55/92, that is, the Pt / Au alloy cluster is , A Pt core (55 atoms) completely covered with an Au shell (92 atoms), which is a icosahedral alloy cluster with a magic number of 147.) The colloidal concentration is about 200 μg / L. Example 90 is the measurement data of the residual ratio of reduced vitamin C according to the test procedure described in (A-4) above when the antioxidant functional water added in an amount is employed.

(Example 91)
As the test water, an antioxidant functional water obtained by adding the same Pt / Au alloy colloid-containing solution as in Example 90 to hydrogen water (9.0) in an amount such that the colloid concentration is about 200 μg / L. The residual ratio measurement data of reduced vitamin C according to the test procedure described in (A-4) above is taken as Example 91.

(Example 92)
As the test water, an antioxidant functional water obtained by adding a Pt / Au alloy colloid-containing solution similar to that in Example 90 to hydrogen water (2.2) in an amount such that the colloid concentration is about 200 μg / L. The residual ratio measurement data of reduced vitamin C according to the test procedure described in (A-4) above is taken as Example 92.

(Example 93)
As test water, hydrogen water (7.4), Pd / Au alloy colloid manufactured by Tanaka Kikinzoku Co., Ltd. (alloy having Pd as a core, Au as a shell, and Pd core completely covered with an Au shell) The Pd / Au molar ratio is 3.72 / 6.28, and the Pd / Au atomic ratio in one Pd / Au alloy cluster is 55/92, that is, the Pd / Au alloy cluster is Pd / Au alloy cluster. The core (55 atoms) is completely covered with an Au shell (92 atoms), which is a icosahedral alloy cluster having a magic number of 147.) The solution containing the colloid concentration is about 200 μg / L. Example 93 is the residual ratio measurement data of reduced vitamin C according to the test procedure described in (A-4) above when the added antioxidant functional water is employed.

(Example 94)
As the test water, an antioxidant functional water obtained by adding the same Pd / Au alloy colloid-containing solution as in Example 93 to hydrogen water (9.0) in an amount such that the colloid concentration is about 200 μg / L. The residual ratio measurement data of reduced vitamin C according to the test procedure described in (A-4) above is taken as Example 94.

(Example 95)
As the test water, an antioxidant functional water obtained by adding the same Pd / Au alloy colloid-containing solution as in Example 93 to hydrogen water (2.2) in such an amount that the colloid concentration becomes about 200 μg / L. The residual ratio measurement data of reduced vitamin C according to the test procedure described in (A-4) above is taken as Example 95.

(C) Test results FIG. 43 comparing Reference Examples 29 and 32 with Examples 84, 87, 90, and 93 shows various test waters whose liquidity is neutral with a buffer solution (pH 7.4). The time-dependent change characteristics of the reduced vitamin C residual rate (%) when reduced vitamin C is contained in are shown. Based on the same figure, when compared with Reference Example 29 (distilled water), Example 84 (hydrogen water containing Pt colloid) is particularly superior with respect to the storage stability of reduced vitamin C when the liquidity is neutral. Then, Example 90 (Pt / Au alloy colloid-containing hydrogen water), Example 93 (Pd / Au alloy colloid-containing hydrogen water), Example 87 (Pd colloid-containing hydrogen water), and Reference Example 32 (hydrogen water) In order, it showed good shelf life.

  FIG. 44 comparing Reference Examples 30 and 33 with Examples 85, 88, 91, and 94 shows that reduced vitamin C was added to various test waters whose liquidity was made basic with a buffer solution (pH 9.0). The time-dependent change characteristic of the reduced vitamin C residual rate (%) is shown. Based on the same figure, when compared with Reference Example 30 (distilled water), the storage stability of reduced vitamin C when the liquidity was made basic, Example 85 (Pt colloid-containing hydrogen water), Example 88 ( Pd colloid-containing hydrogen water) is particularly excellent, followed by Reference Example 33 (hydrogen water), Example 94 (Pd / Au alloy colloid-containing hydrogen water), and Example 91 (Pt / Au alloy colloid-containing hydrogen water). In order, it showed good shelf life.

  FIG. 45 comparing Reference Examples 31 and 34 with Examples 86, 89, 92, and 95 shows that reduced vitamin C is added to various test waters that are made acidic by a buffer solution (pH 2.2). The time-dependent change characteristic of the reduced vitamin C residual rate (%) when it is contained is shown. Based on the same figure, compared with Reference Example 31 (distilled water), the storage stability of reduced vitamin C when the liquidity was made acidic was found to be Example 86 (Pt colloid-containing hydrogen water), Example 89 (Pd Colloid-containing hydrogen water) and Example 95 (Pd / Au alloy colloid-containing hydrogen water) are particularly excellent, followed by Reference Example 34 (hydrogen water) and Example 92 (Pt / Au alloy colloid-containing hydrogen water). It showed good storage stability.

(D) Discussion of results First, the results obtained will be considered comprehensively. When compared with Reference Examples 19 to 31 (distilled water) in all neutral, acidic, and basic liquid regions, the other examples showed good storage stability. For one of the reasons, in other examples, it is considered that the lower dissolved oxygen concentration than in Reference Examples 19 to 31 (distilled water) worked favorably for suppressing the oxidation of reduced vitamin C. It can also be seen that the acidic side of the liquid is more advantageous for enhancing the storage stability of reduced vitamin C. This is presumably because vitamin C is an acid, so that the acid side has a lower proton dissociation property and electrons are less likely to be emitted. On the contrary, when the liquid property is inclined toward the base side, it is considered that the proton dissociation property becomes high and electrons are easily released. Therefore, it can be seen that the liquid property of the solution is preferably inclined toward the acidic side in order to enhance the storage stability of the reduced vitamin C contained in the aqueous solution.

  Next, we will discuss the results obtained in a theoretical manner. First, about the preservation | save property of the reduced vitamin C in a neutral area | region, Example 84 (Pt colloid containing hydrogen water) is overwhelmingly excellent compared with the reference example 32 (hydrogen water). Why is this? Incidentally, the common point between Example 84 (Pt colloid-containing hydrogen water) and Reference Example 32 (hydrogen water) is that the dissolved oxygen concentration is low at least immediately after the electrolytic treatment. In other words, in both examples, the reduced vitamin C is oxidized over time due to the action of oxygen mixed into the quartz cell over time. There seems to be almost no difference between the two. Then, since the difference between the two is the presence or absence of the noble metal catalyst (Pt colloid), it can be inferred that the presence or absence of the noble metal catalyst is involved in the preservation of reduced vitamin C. And the mechanism of action is considered as follows.

First, when two molecules of reduced vitamin C (AsA) are one-electron-oxidized to one molecule of oxygen, two radicals of monodehydroascorbic acid (MDA.) And one molecule of hydrogen peroxide are generated. When one molecule of reduced vitamin C (AsA) is oxidized by one electron to one molecule of oxygen, one molecule of monodehydroascorbic acid (MDA ·) and one molecule of superoxide anion radical (· O ₂ ⁻ ) are generated. There is also a case.

2AsA + O ₂ ⇒ 2MDA ・ + H ₂ O _{2
(AsA + O 2 ⇒ MDA ·} + · O 2 -)
Further, two monodehydroascorbic acid (MDA.) Molecules generate reduced vitamin C (AsA) and dehydroascorbic acid (DHA) by disproportionation reaction. Dehydroascorbic acid (DHA) is a two-electron oxide of reduced vitamin C (AsA).

MDA ・ + MDA ・ ⇒ AsA + DHA
Through such a process, reduced vitamin C (AsA) is gradually oxidized, and finally all reduced vitamin C (AsA) is changed to dehydroascorbic acid (DHA). As described above, such a process is suppressed as the liquid property is inclined toward the acidic side.

  Moreover, as a preliminary experiment of this test, the reactivity of dehydroascorbic acid (DHA) with Example 84 (Pt colloid-containing hydrogen water) and the reaction of dehydroascorbic acid (DHA) with Reference Example 32 (hydrogen water) When sex was examined, there was no reaction between them. This means that what has been oxidized to dehydroascorbic acid (DHA) can no longer be returned to reduced vitamin C (AsA), depending on the hydrogen molecule, regardless of the presence or absence of a noble metal catalyst.

Here, as shown in FIG. 43, the reactivity between reduced vitamin C (AsA) and oxygen molecules is quite high. It is also known that the reactivity between reduced vitamin C (AsA) and superoxide anion radical (.O ₂ ⁻ ) is quite high. In this case, the superoxide anion radical (.O ₂ ⁻ ) is reduced by one electron and converted to hydrogen peroxide.

  Therefore, as a reaction between reduced vitamin C (AsA) and oxygen molecules, the reaction that generates hydrogen peroxide can be typically used.

  Consider a case where oxygen molecules are mixed into the water of Example 84 (Pt colloid-containing hydrogen water) over time. In this case, two molecules of reduced vitamin C (AsA) are one-electron-oxidized to one molecule of oxygen to generate two monodehydroascorbic acid (MDA.) Radicals and one molecule of hydrogen peroxide.

  At this time, Example 84 (Pt colloid-containing hydrogen water) reduced monodehydroascorbic acid (MDA.) By one electron before the monodehydroascorbic acid (MDA.) 2 molecule caused a disproportionation reaction. It is considered that the production of dehydroascorbic acid (DHA) is delayed in time by returning to reduced vitamin C (AsA).

MDA ・ + (H ₂ + Pt) ⇒ AsA + (H ・ + Pt)
In proportion to the time for which the production of dehydroascorbic acid (DHA) is delayed, the time for maintaining the state as reduced vitamin C (AsA) also increases. This is considered to be the reason why Example 84 (Pt colloid-containing hydrogen water) is superior in preservability of reduced vitamin C (AsA) compared to Reference Example 32 (hydrogen water).

  In Reference Example 32 (hydrogen water), one-electron reduction of monodehydroascorbic acid (MDA.) Does not occur at all or only a slight amount occurs, so the production of dehydroascorbic acid (DHA) takes time. Can not be delayed.

  On the other hand, it is considered that the reason why platinum (Pt) is particularly excellent as a noble metal catalyst for enhancing the storage stability of reduced vitamin C (AsA) in the neutral region is as follows.

  First, as described above, when reduced vitamin C (AsA) is one-electron oxidized to oxygen molecules, monodehydroascorbic acid (MDA.) Radicals and hydrogen peroxide are generated.

2AsA + O ₂ ⇒ 2MDA · + H ₂ O ₂
Example 84 (Pt colloid-containing hydrogen water) is very reactive with respect to the hydrogen peroxide produced at this time, and can be rapidly reduced to water. Further, Example 84 (Pt colloid-containing hydrogen water) is very reactive with respect to the oxygen molecules mixed in, and can be rapidly reduced to hydrogen peroxide or water.

O ₂ + (H ₂ + Pt) ⇒ H ₂ O ₂ + Pt
H ₂ O ₂ + (H ₂ + Pt) ⇒ 2 (H ₂ O) + Pt
On the other hand, the noble metal catalyst contained in Example 90 (Pt / Au alloy colloid-containing hydrogen water), Example 93 (Pd / Au alloy colloid-containing hydrogen water), and Example 87 (Pd colloid-containing hydrogen water) Compared with platinum (Pt), the reactivity with oxygen is low, and the reactivity with hydrogen peroxide is also considered to be low.

  However, in Example 90 (Pt / Au alloy colloid-containing hydrogen water), Example 93 (Pd / Au alloy colloid-containing hydrogen water), and Example 87 (Pd colloid-containing hydrogen water), Reference Example 32 (hydrogen water) and In the comparison, reduced vitamin C (AsA) can be retained for a longer time. In Examples 90, 93, and 87, reactivity with oxygen molecules and hydrogen peroxide can hardly be expected. However, for monodehydroascorbic acid (MDA), Example 84 (Pt colloid-containing hydrogen water) This is considered to be because it has almost the same effect as).

  In other words, the hydrogen water (antioxidation functional water) containing the noble metal catalyst is generally used to quickly remove oxygen or hydrogen peroxide before the reduced vitamin C (AsA) is oxidized to oxygen or hydrogen peroxide. This means that the production of dehydroascorbic acid (DHA) or monodehydroascorbic acid (MDA.) Can be suppressed.

  Therefore, hydrogen water (antioxidation functional water) containing a noble metal catalyst is preferred for use in improving the storage stability of reduced vitamin C (AsA).

  Next, in the basic region, Example 94 (Pd / Au alloy colloid-containing hydrogen water) and Example 91 (Pt / Au alloy colloid-containing hydrogen water) were reduced compared to Reference Example 33 (hydrogen water). It is inferior in the preservation property of type vitamin C. Why is this? This is because Pd / Au alloy colloid or Pt / Au alloy colloid contained in Example 94, Example 91 has a reactivity between reduced vitamin C (AsA) and oxygen molecules regardless of hydrogen. It is thought that it is increasing or catalyzing hydrolysis of reduced vitamin C (AsA), not oxidative degradation.

  In the acidic region, Example 92 (Pt / Au alloy colloid-containing hydrogen water) is inferior in storage stability of reduced vitamin C as compared with Reference Example 34 (hydrogen water). Why is this? This is because, regardless of hydrogen, the Pt / Au alloy colloid contained in Example 92 increases the reactivity between reduced vitamin C (AsA) and oxygen molecules, or is not oxidative decomposition, It is thought to catalyze the hydrolysis of reduced vitamin C (AsA).

Does Antioxidant Function Water (AOW) inhibit lipid peroxidation in rats? >>
Lipid peroxide is a harmful substance that is generated when free radicals containing reactive oxygen species are combined with unsaturated fatty acids in the living body (rich in vegetable oil and fish fat). This lipid peroxide is used to treat liver and kidney damage caused by drugs and harmful substances, ischemic reperfusion injury, cardiovascular diseases such as arteriosclerosis, gastrointestinal diseases such as gastric ulcer and gastric mucosal damage, respiratory diseases, and diabetes. It has been pointed out that it is deeply involved in complications (for example, hypertension, cerebral infarction, myocardial infarction, etc.), cataracts, skin diseases, various inflammatory diseases, neurological diseases, cancer, aging and the like. How to suppress such lipid peroxidation is extremely important for the living body.

  Therefore, when antioxidative functional water (AOW) is supposed to be consumed, does antioxidant functional water (AOW) exhibit a pharmacological function such as inhibiting the production of lipid peroxide in rats? About, the pharmacological test was done by 7 group structure of 10 animals per group. The outline of the test protocol is shown below.

(A) Outline of test protocol (A-1) Experimental animals and breeding environment Male SD rats (SPF: specific pathogen free) purchased at 6 weeks of age from Japan Claire Co., Ltd. are preliminarily raised for 7 days and used for experiments. did. Rats were raised in a plastic cage installed in a breeding room (lighting time: 8:00 to 20:00, air conditioning equipment: All Fresh system) at a room temperature of 24 ± 1 ° C and a humidity of 55 ± 5% throughout the preliminary breeding period and experimental period. .

  Regarding feed, all groups were given solid feed (CE-2, manufactured by CLEA Japan, Inc.) freely. Regarding water supply, during the preliminary breeding period, distilled water was filled in a water supply bottle and allowed to freely ingest. After the start of the test, test substances to be described later were filled in water bottles and freely ingested.

(A-2) Main equipment, equipment and reagents used in the test
(1) Cooling centrifuge: Model 5930 ... KUBOTA
(2) Homogenizer: HG-92G ... TAITEC
(3) UV / Visible Spectrophotometer: Ultrospec 3100 pro ・ ・ ・ Amersham Pharmacia Biotech
(4) Radical initiator (AAPH: 2,2-Azobis-amidinopropane dihydrochloride)
(5) 8-OHdG measurement kit: Japan Institute of Aging Control (A-3) Outline of test substance
(1) Purified water (used in control groups 1-0 and 1-1)
(2) Purified water containing Pt colloid catalyst (concentration of about 200 μg / L) (used in Control Group 1-2)
(3) Purified water containing Pd colloid catalyst (concentration about 200μg / L) (used in control group 1-3)
(4) Non-catalyzed circulating electrolyzed water (electrolytic hydrogen water, used in test group 1-1)
(5) Pre-catalyst-added circulating electrolyzed water (Pt colloidal catalyst (about 200 μg / L concentration) containing electrolytic hydrogen water, used in Test Group 1-2)
(6) Pre-catalyst-added circulating electrolyzed water (Pd colloidal catalyst (about 200 μg / L concentration) containing electrolytic hydrogen water, used in Test Group 1-3)
(A-4) Test method and test items
(1) Measurement of body weight, food intake, water intake The body weight, food intake, and water intake were measured every day between 10 am and 11 am.

(2) Test substance administration method During the 7 days from the first day of the test to the 7th day, each test substance assigned to each group of rats (200 mL enclosed in a 200 mL light-shielding glass bottle) was opened. Immediately thereafter, 2 mL of each individual was forcibly orally administered using a disposable gastric sonde. At that time, the water in the water bottle was replaced with fresh one. In other words, after throwing away the old water remaining in the water bottle, the fresh water remaining after use for oral gavage is gently reduced to the water bottle's capacity so that the air layer in the water bottle is removed as much as possible. The water supply mouth was set and given freely. In addition, about gavage administration, it carried out twice a day at 10-11 am and 5-6 pm. Further, immediately before administration of the radical initiator AAPH (hereinafter sometimes abbreviated as AAPH), the test substance was orally administered by gavage as described above. At that time, the water in the water bottle was replaced with fresh water as described above, and was freely given until dissection.

(3) Preparation of radical initiator AAPH and induction of lipid peroxidation
Since AAPH is water-soluble, it was adjusted to 50 mg / kg BW using physiological saline. The preparation was performed on the day of AAPH administration. Lipid peroxidation was induced by intraperitoneally administering AAPH prepared in this manner to the rats of 6 groups except the control group 1-0 described later on the 7th day after the start of the test. For control group 1-0, physiological saline was administered intraperitoneally.

(4) Collecting urine samples
Urine was collected using metabolic cages for 12 hours from AAPH administration until dissection (fasted during this period). The collected urine was filtered after impurities and stored frozen at −80 ° C. until analysis.

(5) Anatomy
After 12 hours from the end of AAPH administration (fasted during this time), the animals were dissected under ether anesthesia. After visual observation mainly on the liver, the liver was removed and stored frozen at −80 ° C. until analysis.

(6) Measurement of urinary 8-OHdG (8-hydroxy-2'-deoxyguanosine) concentration The urine collected in the above (A-4)-(4) was measured for 8-OHdG concentration. 8-OHdG is widely used as an index of oxidative stress.

(7) Measurement of lipid peroxide (TBARS: Thiobarbituric Acid Reactive Substances) in liver After thawing the liver extracted in (A-4)-(5) above, under ice-cooling After homogenization, the amount of lipid peroxide (TBARS: thiobarbituric acid reactant) in the liver was measured by the thiobarbituric acid (TBA) method. TBARS is widely used as an index of lipid peroxidation.

(8) Statistical processing The average value ± standard error for each group was calculated for the obtained measurement data. Student's t-test is performed to test the statistically significant difference between each group, and the p-value is 5% or less (p <0.05). It was said that.

(B) Disclosure of test group and control group (control group 1-0)
The operation according to the test procedure described in (A-4) was performed on 10 rats when adopting activated carbon treated water (purified water) obtained by passing Fujisawa city tap water through an activated carbon column as breeding water. The group is referred to as control group 1-0. The control group 1-0 is a group bred in an ordinary environment. In the control group 1-0, physiological saline is administered intraperitoneally instead of AAPH. That is, in the control group 1-0, there is no induction of lipid peroxide.

(Control group 1-1)
A group in which the operation according to the test procedure described in (A-4) was performed on 10 rats when the same purified water as in the control group 1-0 was adopted as the breeding water was designated as a control group 1-1. . The difference between the control group 1-0 and the control group 1-1 is whether or not AAPH is administered.

(Control group 1-2)
As the water for breeding, when the same purified water as in the control group 1-0 and containing the Pt standard solution described in Examples 3 to 5 in an amount such that the Pt colloid concentration is 192 μg / L, ( A group in which the operation according to the test procedure described in A-4) was performed on 10 rats was defined as a control group 1-2.

(Control group 1-3)
As the water for breeding, when the same purified water as in the control group 1-0 and containing the Pd reference solution described in Examples 6 to 8 in an amount such that the Pd colloid concentration is 192 μg / L, ( A group in which the operation according to the test procedure described in A-4) was performed on 10 rats was defined as a control group 1-2. The difference between the control group 1-2 and the control group 1-3 is the kind of the noble metal colloid to be contained.

(Study Group 1-1)
As a breeding water, 1 liter of purified water similar to the control group 1-0 is used for 1 minute in a continuous water circulation system (circulating water volume is 0.8 liter) under a 5 A constant current electrolysis condition at a flow rate of 1.5 liters per minute. A test was conducted on a group in which 10 rats were subjected to the operation according to the test procedure described in (A-4) when the non-catalyst-added circulating electrolyzed water subjected to electrolysis (corresponding to 2-pass electrolysis) was adopted. Group 1-1.

(Study group 1-2)
As the breeding water, 1 liter of purified water similar to the control group 1-0 containing the Pt standard solution described in Examples 3 to 5 in an amount that the Pt colloid concentration was 192 μg / L was used as the test group 1 When the pre-catalyst-added circulating electrolyzed water subjected to electrolytic treatment (equivalent to 2-pass electrolysis) for 1 minute in a continuous water circulation type (circulation water amount is 0.8 liter) under the same electrolysis conditions as -1, A group in which the operation according to the test procedure described in (A-4) was performed on 10 rats was designated as test group 1-2.

(Test group 1-3)
As a breeding water, 1 liter of purified water similar to the control group 1-0 containing the Pd standard solution described in Examples 6 to 8 in an amount such that the Pd colloid concentration was 192 μg / L was used as the test group 1 When the pre-catalyst-added circulating electrolyzed water subjected to electrolytic treatment (equivalent to 2-pass electrolysis) for 1 minute in a continuous water circulation type (circulation water amount is 0.8 liter) under the same electrolysis conditions as -1, A group in which the operation according to the test procedure described in (A-4) was performed on 10 rats is referred to as test group 1-3. The difference between Test Group 1-2 and Test Group 1-3 is the type of noble metal colloid to be included.

(C) Test results Body weight, food intake, water intake
Regarding the change in body weight for 7 days before AAPH administration, no difference was found between the 7 groups of the control group 1-0 to 3 and the test group 1-1 to 3. Regarding the food intake and water intake during the same period, there were no differences between groups in the same group.

Condition observation
Regarding the observation of the condition for 7 days before AAPH administration and after AAPH administration, no abnormality was observed in appearance or behavior before administration. On the other hand, after the administration, each group was slightly upside down, but no abnormal changes were observed in the behavior compared to before administration.

Urinary 8-OHdG Concentration FIG. 46 and Table 7 comparing the control group 1-0 to 3 and the test group 1-1 to 3 with respect to the urinary 8-OHdG concentration show noble metal colloid (Pt Or, Pd) shows the effect of drinking of catalyst-containing electrolytic hydrogen water (AOW) on suppression of oxidative damage of rat gene DNA.

図４６並びに表７に示す尿中の8-OHdG濃度について、対照群1-1（浄水飲用群）との比較において、試験群1-1（電解水素水飲用群）、試験群1-2（Ｐｔコロイド触媒含有の電解水素水飲用群）、試験群1-3（Ｐｄコロイド触媒含有の電解水素水飲用群）の３群が有意に低値を示した。また、対照群1-2（Ｐｔコロイド触媒含有の浄水飲用群）、対照群1-3（Ｐｄコロイド触媒含有の浄水飲用群）との比較において、試験群1-2~3の２群が有意に低値を示した。さらに、試験群1-1との比較において、試験群1-2~3の２群が低値傾向を示したが、有意差は認められなかった。試験群1-2~3の２群比較において、両者はほぼ同等の値を示した。

46 and Table 7, in comparison with the control group 1-1 (purified water drinking group), the test group 1-1 (electrolytic hydrogen water drinking group), the test group 1-2 ( Pt colloidal catalyst-containing electrolytic hydrogen water drinking group) and test group 1-3 (Pd colloidal catalyst-containing electrolytic hydrogen water drinking group) showed significantly lower values. In addition, in comparison with Control Group 1-2 (Pt colloidal catalyst-containing purified water drinking group) and Control Group 1-3 (Pd colloidal catalyst-containing purified water drinking group), Test Groups 1-2 to 3 were significant. Showed a low value. Further, in comparison with test group 1-1, two groups of test groups 1-2 to 3 showed a tendency toward a low value, but no significant difference was observed. In the two groups comparison of test groups 1-2 to 3, both showed almost the same value.

Macroscopic observation of the liver In the macroscopic observation of the liver removed at the time of dissection, the three groups of the test groups 1-1 to 3 showed elasticity in comparison with the three groups of the control groups 1-1 to 3, and normal. It was close to the liver.

Amount of lipid peroxide in the liver (TBARS: Thiobarbituric acid reactant) The amount of lipid peroxide in the liver is compared between the 7 groups of the control group 1-0 to 3 and the test group 1-1 to 3 47 and Table 8 show the effect of drinking noble metal colloid (Pt or Pd) catalyst-containing electrolytic hydrogen water (AOW) on lipid peroxidation inhibition in rats.

図４７並びに表８に示す肝臓中の過酸化脂質量について、対照群1-1（浄水飲用群）、対照群1-2（Ｐｔコロイド触媒含有の浄水飲用群）、対照群1-3（Ｐｄコロイド触媒含有の浄水飲用群）との比較において、試験群1-1（電解水素水飲用群）、試験群1-2（Ｐｔコロイド触媒含有の電解水素水飲用群）、試験群1-3（Ｐｄコロイド触媒含有の電解水素水飲用群）の３群が有意に低値を示した。また、試験群1-1との比較において、試験群1-2~3の２群が低値傾向を示したが、有意差は認められなかった。さらに、試験群1-2~3の２群比較において、試験群1-3のほうが低値傾向を示したが、有意差は認められなかった。

47 and Table 8, with respect to the amount of lipid peroxide in the liver, control group 1-1 (purified water drinking group), control group 1-2 (purified water drinking group containing Pt colloid catalyst), control group 1-3 (Pd In comparison with colloidal catalyst-containing purified water drinking group), test group 1-1 (electrolytic hydrogen water drinking group), test group 1-2 (Pt colloidal catalyst-containing electrolytic hydrogen water drinking group), test group 1-3 ( Three groups (Pd colloid catalyst-containing electrolytic hydrogen water drinking group) showed significantly low values. In comparison with test group 1-1, two groups of test groups 1-2 to 3 showed a tendency toward a low value, but no significant difference was observed. Further, in the comparison between the two groups of the test groups 1-2 to 3, the test group 1-3 showed a lower value tendency, but no significant difference was observed.

(D) Discussion of results The antioxidant effect of test substance forced oral administration and free intake was compared using a model animal in which lipid peroxidation was induced in vivo by administering the radical initiator AAPH intraperitoneally. The antioxidant activity in the present invention means oxidative including DNA damage, cell mutation, morphological change, cell death, etc. caused by irreversible oxidation reaction of cell components derived from free radicals and lipid peroxides. It refers to the action of preventing or inhibiting cell damage, and broadly encompasses free radical scavenging activity and lipid peroxidation inhibiting activity.

  As a result, both of the test groups 1-2 to 3 showed a significant increase suppression of the urinary 8-OHdG concentration and a significant increase suppression of the amount of lipid peroxide in the liver. In addition, there was no difference between the 7 groups of the control group 1-0 to 3 and the test group 1-1 to 3 regarding the body weight change, food consumption, and water consumption for 7 days before AAPH administration (no side effects) Grounds).

  From the above results, drinking antioxidant functional water (pharmacological functional water) related to 2 groups of test groups 1-2 to 3 without affecting the factors of body weight transition, food intake, water intake, It has been found that it exhibits an antioxidant effect such as suppressing oxidative damage of gene DNA in vivo and suppressing lipid peroxidation, that is, pharmacological function water exhibits pharmacological function without side effects.

  In recent years, free radicals and lipid peroxides in the body have been affected by liver damage caused by drugs and harmful substances, ischemic reperfusion injury, cardiovascular diseases such as arteriosclerosis, gastrointestinal diseases such as gastric ulcer and gastric mucosal disorder, respiratory system Deeply involved in oxidative stress diseases such as diseases, diabetes complications (eg hypertension, cerebral infarction, myocardial infarction), cataracts, skin diseases, various inflammatory diseases, neurological diseases, cancer, aging, etc. Has been pointed out. Here, the oxidative stress disease refers to all diseases derived from free radicals and lipid peroxides in a living body. Lipid peroxides are produced by using highly unsaturated fatty acids constituting cell membranes as a substrate and undergoing oxidation at the unsaturated group sites by the action of free radicals containing reactive oxygen species. When the cell membrane function is impaired along with lipid oxidation, it develops into cytotoxicity in combination with the action of the produced lipid peroxide. Examples of lipid peroxides produced in vivo include fatty acid free radicals L, lipid hydroperoxide (LOOH), LCHO, and free radicals derived therefrom, such as lipid radicals such as peroxy radical LOO. And alkoxy radical LO.

  Now, the involvement of free radicals containing reactive oxygen species and lipid peroxide in the oxidative stress disease described above will be described below.

Since the liver is a central organ for detoxification and metabolism, it is susceptible to damage by hepatotoxic factors and drugs. For example, in the case of carbon tetrachloride (CCl ₄ ) poisoning, the mechanism of free radical cytotoxicity is presented when attempting to clarify the pathology of liver damage caused by liver damage, drug addiction, and the like. Carbon tetrachloride has been found to have carcinogenic and hepatotoxic toxicity. It has been known for a long time that the leading role of its toxicity is the (.CCl ₃ ) radical. This radical induces lipid peroxidation and causes liver damage ("Active Oxygen and Medical Food Dosage" edited by Masayasu Inoue, Kyoritsu Shuppan Co., Ltd., p.135-137). Therefore, radicals are also involved in liver damage caused by such drugs. Similarly, in paraquat poisoning, typical symptoms derived from cell injury caused by reactive oxygen species are observed. The toxicity of paraquat is caused by the generation of active oxygen in vivo, and the active oxygen causes lipid peroxidation, cell membrane degeneration, and cell damage. In severe cases, pathological conditions such as gastrointestinal symptoms, liver dysfunction, and renal dysfunction progress irreversibly, and eventually, progressive pulmonary fibrosis results in respiratory failure and death.

Ischemic reperfusion injury (I / R) is a disorder that occurs when ischemia due to blockage of blood flow or hypoperfusion occurs for a certain period of time and blood flow subsequently recovers. It is known that active oxygen and free radicals are generated in the ischemic state and reoxygenation process, resulting in lipid peroxidation, cell membrane damage, tissue damage, and paradoxically worsening of symptoms. The mechanisms include (1) oxidative stress after reoxygenation, (2) fluctuation of intracellular pH, (3) mitochondrial damage before and after ischemia, (4) activation of inflammatory cells after reoxygenation, (5) Fluctuation of intracellular Ca ²⁺ concentration, (6) induction of hypoxia inducing factor during ischemia, (7) apoptosis due to caspase 3 activation after reoxygenation, etc. It is known that active oxygen production of phagocytic cells such as neutrophils and Kupffer cells is deeply involved in reperfusion injury.

  Regarding involvement in arteriosclerosis, active oxygen acts on the oxidation of LDL (low density lipoprotein), and lipid peroxidation such as cholesterol occurs in the process of denaturation of oxidized LDL and deposits on the blood vessel wall. It causes the progression of atherosclerosis such that macrophages take up denatured LDL and turn into foam cells. Even in digestive system diseases, reactive oxygen species are assumed to be an important pathogenic factor of peptic ulcer. Infection with Helicobacter pylori, a Gram-negative bacilli, infiltrates inflammatory cells into the stomach and duodenal mucosa, induces cytokines, and generates active oxygen to cause cytotoxicity. This is considered to be a cause of digestive system diseases such as gastric ulcer, gastric mucosal disorder, and duodenal ulcer.

  In diabetes, reactive oxygen is generated when excess glucose results in protein glycation (non-enzymatic glycation) followed by advanced glycation endproduct (AGE). Pancreatic islet β cells, which secrete insulin, are weakened by active oxygen attack.

  One of the etiologies of cataract is said to be that the lens lens, which is a protein, is damaged by the attack of active oxygen generated by the action of ultraviolet rays or the like.

  As an involvement in skin diseases, active oxygen is generated in skin tissues such as the epidermis and dermis by irradiation with ultraviolet rays, radiation, etc., which oxidizes collagen, elastin and the like and causes “stains” and “wrinkles”. In addition, it has been pointed out that active oxygen is also involved in skin disorders such as atopic dermatitis, keloids, burns and skin cancer.

  Involvement in cancer is that DNA damage caused by active oxygen leads to mistranslation of gene information and abnormal regulation of gene expression, leading to the development of cancer cells.

  With respect to aging, defense system activities such as superoxide dismutase (SOD) decrease with aging and the ability to eliminate reactive oxygen species decreases, and thus organ and tissue injury accelerates natural aging. Accumulation of lipid peroxide has been found in the brain and nerves of aged animals.

  Therefore, the drinking of antioxidant functional water related to Group 5 of Test Groups 2-2 to 6 is related to liver damage caused by drugs and harmful substances, ischemic reperfusion injury, cardiovascular diseases such as arteriosclerosis, gastric ulcer, gastric mucosal damage Digestive system diseases such as respiratory diseases, diabetes complications (eg hypertension, cerebral infarction, myocardial infarction, etc.), cataracts, skin diseases, various inflammatory diseases, neurological diseases, cancer, aging, etc. It will be useful as a prophylactic / therapeutic agent without side effects for preventing and / or treating all oxidative stress diseases caused by lipid peroxide. In addition, the side effect said by this invention means the concept including the effect (side effect) and adverse reaction (adverse reaction) which are not useful for the treatment of a disease. For example, symptoms such as bruising, vomiting, hair loss, fatigue, anemia, infection, poor blood coagulation, pain in mouth, gums, throat, diarrhea, constipation, numbness in limbs, adverse effects on skin and nails, cold In addition to swelling, dependence, abuse, teratogenicity, recoil at the time of discontinuation, carcinogenesis, radical chain reaction (even if free radicals and lipid peroxides can be erased instantaneously, they themselves become radical Involvement in adverse effects on the above) corresponds to the side effect referred to in the present invention.

Does antioxidant functional water (AOW) suppress adjuvant arthritis in rats? >>
Rat adjuvant arthritis is often used as an animal model of rheumatoid arthritis belonging to the category of autoimmune diseases. Autoimmune diseases are diseases of unknown cause that are defined as those that are triggered by the destruction of their own cells, can produce autoantibodies against the destroyed cells or their components, and continue to be destroyed by their own white blood cells. . The number of patients suffering from these autoimmune diseases has been increasing year by year, and a new preventive / therapeutic agent that exhibits pharmacological functions without side effects, which is completely different from existing therapeutic agents that necessarily have side effects. The development of is strongly awaited.

  Therefore, when antidote for functional water (AOW) is assumed, does antioxidant functional water (AOW) exert a pharmacological function to suppress adjuvant arthritis in rats? The pharmacological test was conducted in a 7-group configuration with 8 animals per group. The outline of the test protocol is shown below. In this pharmacological test, arthritis is induced in rats by administering a fungus-derived adjuvant. The sensitized limb at the injection site shows joint inflammation (primary inflammation) in several hours, but systemic joint inflammation (secondary inflammation) is observed from about 10 days after injection. In addition, it is around 20 days after injection that this joint inflammation state shows a peak. Therefore, this test period is set to 24 days.

(A) Outline of test protocol (A-1) Experimental animals and breeding environment Female Lewis rats (SPF: specific pathogen free) purchased at 8 weeks of age from Japan Charles River Co., Ltd. were preliminarily raised for 7 days for experiments. Provided. Four rats per cage in the SPF barrier breeding room (lighting time 8:00 to 18:00, ventilation rate 18 times / hour) with a room temperature of 24 ± 3 ° C and a relative humidity of 55 ± 15% throughout the preliminary breeding period and experimental period Was reared.

  As for the feed, all groups were freely given solid feed (MF, Oriental Yeast Co., Ltd.). Regarding the water supply, deionized water was filled in a water supply bottle and allowed to freely ingest during the preliminary breeding period. After the start of the test, test substances to be described later were filled in water bottles and freely ingested. In addition, the water bottle improved by our company (Miz Co., Ltd.) was used as a water bottle used after the preliminary breeding period and after the start of the test so as to suppress air (oxygen) mixing into the liquid inside the bottle.

(A-2) Main equipment, equipment and reagents used in the test
(1) Foot volume measuring device: Model TK-105 ... Muromachi Machine
(2) Mycobacterium tuberculosis: M. tuberculosis H37Ra ... Wako Pure Chemicals, lot No. 2116641
(3) Liquid paraffin: Wako Pure Chemicals, lot No.EWQ1149
(A-3) Outline of test substance
(1) Purified water (used in control group 2-1)
(2) Catalyst-free circulating electrolyzed water (electrolytic hydrogen water, used in test group 2-1)
(3) Post-catalyst-added circulating electrolyzed water (Pd colloidal catalyst (approximately 300 μg / L concentration) containing electrolytic hydrogen water, used in Test Group 2-2)
(4) Pre-catalyst-added circulating electrolyzed water (Pd colloid catalyst (about 600 μg / L concentration) containing electrolytic hydrogen water, used in test group 2-3)
(5) Pre-catalyst-added circulating electrolyzed water (Pt colloidal catalyst (approximately 300 μg / L concentration) containing electrolytic hydrogen water, used in test group 2-4)
(6) Pre-catalyst added circulating electrolyzed water (Pt / Au alloy colloidal catalyst (about 300μg / L concentration) containing electrolytic hydrogen water, used in Test Group 2-5)
(7) Pre-catalyst-added circulating electrolyzed water (Pd / Au alloy colloidal catalyst (approximately 300 μg / L concentration) containing electrolytic hydrogen water, used in test group 2-6)
(A-4) Test method and observation and inspection items
(1) Preparation of adjuvant and induction of arthritis Tuberculosis: M. tuberculosis H37Ra (Wako Pure Chemical Industries, Ltd., Lot No. 2116641) heat-killed bacteria, weighed an appropriate amount, made fine powder in an agate mortar, then liquid paraffin (Wako Pure Chemical Industries, Ltd., Lot No. EWQ1149) was added little by little and suspended to prepare a 3 mg / ml suspension. The rats were fixed on a fixed base under ether anesthesia, and 0.1 ml of the prepared adjuvant was injected into the footpad skin of the right hind limb to induce arthritis. The induction date was day 0.

(2) Administration method
During the 24 days from Day 0 to Day 23, each test substance assigned to each group of rats (200 mL enclosed in a 200 mL capacity light-shielding glass bottle) was placed in a disposable gastric sonde immediately after opening. Only 3 mL of gavage was administered per individual. At that time, the water in the water bottle was replaced with fresh one. In other words, after throwing away the old water remaining in the water bottle, the fresh water remaining after use for oral gavage is gently reduced to the water bottle's capacity so that the air layer in the water bottle is removed as much as possible. The water supply mouth was set and given freely.

(3) Observation of general condition The general condition was observed once a day and entered on a record sheet.

(4) Body weight measurement The body weight of each group of rats was measured with a scale. The weight measurement days were day 0, 3, 8, 13, 16, and 23.

(5) Observation of arthritis score The same examiner randomly observed macroscopically the degree of redness, swelling and tonicity of the right forelimb, left forelimb and left hindlimb excluding the right hindlimb of the sensitized site. A score of 0-4 points was given according to the rating, with a total of up to 12 points. The observation date was the same as the weight measurement date.

0: No symptoms at all (nil)
1: Only one small joint such as limbs shows redness and swelling (mild)
2: Two or more small joints or relatively large joints such as wrists and ankles show redness and swelling (moderate)
3: Moderately-severe in one hand or entire leg showing redness and swelling
4: Maximum overall swelling of one hand or foot, with joint stiffness (severe)
(6) Paw volume measurement The right hind limb volume of each group of rats was measured using a paw volume measuring device. The measurement date was the same as the weight measurement date.

(7) Statistical processing The obtained body weight, arthritis score, and right hind limb volume were shown as an average value ± standard error for each group. Statistical tests were performed using analysis software (Stat View, Abacus Inc., USA) in order to test for statistical significance between groups (n = 8). The body weight and limb volume data were subjected to analysis of variance (ANOVA) to confirm that they were equivariant, and then subjected to the multiple comparison test, which is the Fisher's PLSD method, to compare the groups. Arthritis score data were compared between groups using the Mann-Whitney U test. In all cases, a risk rate of less than 5% (p <0.05) was considered statistically significant.

(B) Disclosure of test group and control group (Control group 2-1)
The operation according to the test procedure described in (A-4) was performed on eight rats when adopting activated carbon treated water (purified water) obtained by passing Fujisawa city tap water through an activated carbon column as breeding water. The group is referred to as control group 2-1.

(Test Group 2-1)
As breeding water, 1 liter of purified water similar to control group 2-1 was used for 1 minute in a continuous water circulation system (circulating water volume 0.8 liters) at a flow rate of 1.5 liters per minute and at a constant current of 5 A. A group in which the operation according to the test procedure described in (A-4) was performed on 8 rats when the non-catalyst-added circulating electrolyzed water subjected to electrolytic treatment (corresponding to 2-pass electrolytic treatment) was employed was tested. Group 2-1.

(Study Group 2-2)
As breeding water, 1 liter of purified water similar to control group 2-1 was electrolyzed for 1 minute in a continuous water circulation system (circulating water volume 0.8 liter) under the same electrolysis conditions as in test group 2-1. When the post-catalyst-added circulating electrolyzed water in which the Pd colloid solution described in Examples 6 to 8 is contained in an amount corresponding to a Pd colloid concentration of about 300 μg / L is employed in the electrolyzed water corresponding to the pass electrolysis process) The group in which the operation according to the test procedure described in (A-4) was performed on 8 rats is defined as test group 2-2.

(Test group 2-3)
As a breeding water, a test group containing 1 liter of purified water similar to the control group 2-1 and containing the Pd standard solution described in Examples 6 to 8 in an amount such that the Pd colloid concentration is about 600 μg / L. When the pre-catalyst-added circulating electrolyzed water subjected to electrolytic treatment (corresponding to 2-pass electrolysis) for 1 minute in a continuous water circulation system (circulation water amount is 0.8 liter) under the same electrolysis conditions as in 2-1 is adopted. The group in which the operation according to the test procedure described in (A-4) was performed on 8 rats is designated as test group 2-3. The difference between the test group 2-2 and the test group 2-3 is the addition timing and concentration of the precious metal colloid (Pd) to be contained.

(Study group 2-4)
As a breeding water, a test group containing 1 liter of purified water similar to the control group 2-1 and containing the Pt standard solution described in Examples 3 to 5 in an amount such that the Pt colloid concentration is about 300 μg / L. When the pre-catalyst-added circulating electrolyzed water subjected to electrolytic treatment (corresponding to 2-pass electrolysis) for 1 minute in a continuous water circulation system (circulation water amount is 0.8 liter) under the same electrolysis conditions as in 2-1 is adopted. The group which performed operation according to the test procedure as described in (A-4) to 8 rats is defined as test group 2-4.

(Test group 2-5)
As water for breeding, a test was carried out in which 1 liter of purified water similar to Control Group 2-1 was mixed with a Pt / Au alloy colloid-containing solution similar to that in Example 90 in an amount such that the colloid concentration was about 300 μg / L. When pre-catalyst-added circulating electrolyzed water subjected to electrolytic treatment (equivalent to 2-pass electrolysis) for 1 minute in a continuous water circulation system (circulation water volume is 0.8 liter) under the same electrolysis conditions as in Group 2-1 The group in which the operation according to the test procedure described in (A-4) was performed on 8 rats was defined as test group 2-5.

(Test group 2-6)
As water for breeding, a test was carried out in which 1 liter of purified water similar to Control Group 2-1 was mixed with a Pd / Au alloy colloid-containing solution similar to that in Example 93 in an amount such that the colloid concentration was about 300 μg / L. When pre-catalyst-added circulating electrolyzed water subjected to electrolytic treatment (equivalent to 2-pass electrolysis) for 1 minute in a continuous water circulation system (circulation water volume is 0.8 liter) under the same electrolysis conditions as in Group 2-1 The group in which the operation according to the test procedure described in (A-4) was performed on 8 rats was designated as test group 2-6.

(C) Test result body weight FIG. 48 and Table 9 comparing the control group 2-1 and the seven groups of the test groups 2-1 to 6 with respect to the body weight change over the entire test period show the electrolytic hydrogen water containing a noble metal colloid catalyst. The influence which drinking of (AOW) has on a rat body weight transition is shown. In FIG. 48, the standard error display is omitted in order to ensure the visibility of the diagram.

図４８並びに表９に示すラット体重推移について、対照群2-1と比較して、試験のほぼ全期間にわたり、試験群2-1~6の６群が体重改善傾向を示した。特に、(day13)における試験群2-5を除く試験群2-1~4 ,2-6の５群、並びに、(day21)における試験群2-3 ,2-6の２群では、いずれも有意な体重改善がみられた。

Regarding the rat body weight transition shown in FIG. 48 and Table 9, 6 groups of test groups 2-1 to 6 showed a tendency to improve body weight over almost the entire period of the test compared to the control group 2-1. In particular, in test groups 2-1 to 4 and 2-6 except for test group 2-5 on (day 13), and in test groups 2-3 and 2-6 on (day 21), both Significant weight improvement was seen.

Condition observation With regard to condition observation throughout the entire study period, no abnormal changes other than joint inflammation were observed in all groups.

Arthritis Score Regarding the arthritis score transition over the whole test period, FIG. 49 and Table 10 comparing the control group 2-1 and the seven groups of the test groups 2-1 to 6 show noble metal colloid catalyst-containing electrolytic hydrogen water (AOW). Shows the effect of drinking on arthritis score transition. In FIG. 49, the standard error display is omitted in order to ensure the visibility of the diagram.

図４９並びに表１０に示す関節炎スコア推移について、対照群2-1は (Day8) まで関節炎の発症を示さなかったが、(Day13)以降に強い関節炎の発症が認められた。(Day13~23) の観察日において、対照群2-1と比較して、試験群2-1を除いた試験群2-2~6の５群が、関節炎スコアの上昇抑制傾向または有意な上昇抑制を示した。特に、(day13)における試験群2-2~3 , 2-5の３群、(day16)における試験群2-2~5の４群、並びに、(day23)における試験群2-3の１群では、いずれも有意な関節炎スコアの上昇抑制がみられた。

Regarding the arthritis score transition shown in FIG. 49 and Table 10, control group 2-1 did not develop arthritis until (Day 8), but strong arthritis was observed after (Day 13). On the observation day of (Day 13 to 23), compared with Control Group 2-1, five groups of Test Groups 2-2 to 6 except Test Group 2-1, showed a tendency to suppress or significantly increase the arthritis score. Inhibited. In particular, 3 groups of test groups 2-2 to 3 and 2-5 on (day 13), 4 groups of test groups 2-2 to 5 on (day 16), and 1 group of test groups 2-3 on (day 23) In both cases, the increase in arthritis score was significantly suppressed.

Sensitized limb (right hind limb) volume FIG. 50 and Table 11 comparing 7 groups of control group 2-1 and test groups 2-1 to 6 with respect to volume transition of sensitized limb (right hind limb) throughout the entire test period. These show the influence which drinking of noble metal colloid catalyst containing electrolytic hydrogen water (AOW) has on the sensitized limb volume transition. In FIG. 50, the standard error display is omitted in order to ensure the visibility of the diagram.

図５０並びに表１１に示す感作肢容積推移について、(Day8)までは、対照群2-1と比較して、試験群2-1~6の６群が、感作肢容積の増加傾向または有意な増加を示したが、これは偶発的な変化に過ぎないものと考えられる。(Day13)では、対照群2-1と比較して、試験群2-1 , 2-4 , 2-6の３群が、感作肢容積の増加傾向を示す一方、試験群2-2~3 , 2-5の３群が、感作肢容積の増加抑制傾向を示しはじめた。(Day16)では、対照群2-1と比較して、試験群2-2を除いた試験群2-1 , 2-3~6の５群が、感作肢容積の増加抑制傾向または有意な増加抑制を示し、特に、試験群2-6において、感作肢容積の有意な増加抑制がみられた。(Day21)では、対照群2-1と比較して、試験群2-1~6の６群が、感作肢容積の増加抑制傾向または有意な増加抑制を示し、特に、試験群2-2 , 2-4~6の４群において、感作肢容積の有意な増加抑制がみられた。(Day23)では、対照群2-1と比較して、試験群2-1~6の６群が、感作肢容積の増加抑制傾向または有意な増加抑制を示し、特に、試験群2-3~6の４群において、感作肢容積の有意な増加抑制がみられた。

As for the sensitized limb volume transition shown in FIG. 50 and Table 11, up to (Day 8), compared with the control group 2-1, the six groups of the test groups 2-1 to 6 have increased sensitized limb volume or Although there was a significant increase, this is considered to be only an accidental change. In (Day 13), compared with the control group 2-1, the test groups 2-1, 2-4 and 2-6 showed an increasing tendency of the sensitized limb volume, while the test groups 2-2 to Three groups, 3 and 2-5, started to show a tendency to suppress the increase in sensitized limb volume. In (Day 16), compared with the control group 2-1, the test groups 2-1 and 2-3 to 6 except for the test group 2-2 showed a tendency to suppress the increase in sensitized limb volume or In particular, in the test groups 2-6, significant increase suppression of the sensitized limb volume was observed. In (Day 21), compared with the control group 2-1, 6 groups of the test groups 2-1 to 6 showed an increase suppression tendency or a significant increase suppression of the sensitized limb volume. , 2-4 to 6 groups, significant increase suppression of sensitized limb volume was observed. In (Day 23), compared with the control group 2-1, 6 groups of the test groups 2-1 to 6 showed an increase suppression tendency or a significant increase suppression of the sensitized limb volume. In 4 groups of ~ 6, significant increase suppression of sensitized limb volume was observed.

(D) Discussion of results The effects of the test substance forced oral administration and free intake on adjuvant arthritis were compared using a model animal in which arthritis was induced by injecting adjuvant into the footpad of the right hind limb. .

  As a result, all five groups of test groups 2-2 to 6 showed significant weight improvement or weight improvement tendency, significant increase suppression or increase suppression tendency of arthritis score, and significant increase suppression of sensitized limb volume. Indicated. For each test item throughout the entire study period, organizing from the viewpoint of the number of significant differences (the greater the number of significant differences, the better it is). Good weight improvement was seen in 2 groups of 6 and arthritis score transition was good suppression suppression of arthritis score in 3 groups of test groups 2-2 to 3 and 2-5, and sensitized limb volume transition As for, the increase in sensitized limb volume was favorably suppressed in the three groups of test groups 2-4 to 6. Regarding the state observation throughout the entire test period, no abnormal changes other than joint inflammation were observed in all groups (the basis for no side effects).

  Based on the above results, the body weight derived from rat adjuvant arthritis without inducing abnormal changes other than joint inflammation symptoms when drinking antioxidant functional water (pharmacological functional water) according to Test Groups 2-2 to 6 The effect of improving the reduction, delaying and preventing the onset of rat adjuvant arthritis, and suppressing the increase in the volume of sensitized limbs derived from rat adjuvant arthritis, that is, pharmacological water shows pharmacological function without side effects I understood it.

  Therefore, drinking antioxidant functional water (pharmacological functional water) in Group 5 of Test Groups 2-2 to 6 has no side effects on rat adjuvant arthritis, which is one of the animal models of human rheumatoid arthritis. It was suggested to show the effectiveness. That is, the drinking of antioxidant functional water according to Group 5 of Test Groups 2-2 to 6 would be useful as an anti-rheumatic agent for preventing and / or treating rheumatoid arthritis. In addition, since human rheumatoid arthritis is an autoimmune disease, if drinking of antioxidant functional water according to Group 5 of Test Groups 2-2 to 6 is effective against rat adjuvant arthritis, other self It will be effective against immune diseases without side effects. In other words, the drinking of antioxidant functional waters related to group 5 of test groups 2-2 to 6 is systemic lupus erythematosus (SLE), Sjogren's syndrome, scleroderma, insulin-dependent diabetes in which pancreatic insulin-producing cells are destroyed, Platelet destruction Idiopathic thrombocytopenic purpura, thyroid gland destruction Hashimoto's disease, Graves' disease, pernicious anemia, Addison's disease, atrophic gastritis, hemolytic anemia, ulcerative colitis, neuronal receptor destruction Myasthenia gravis, multiple sclerosis, non-insulin-dependent diabetes mellitus, chronic nephritis, Meniere, sudden hearing loss, emphysema, Behcet's disease, viral hepatitis, muscular dystrophy, and motor neuron destruction Side effects to prevent and / or treat autoimmune diseases such as depression (ALS), depression due to cranial nerve cell receptor disorder, atopic dermatitis, hay fever It may be useful as free anti autoimmune disease agent.

<< Disclosure of Additional Examples by DH Quantitative Analysis Method Using Redox Dye >>
In the following, additional reference examples and examples by the DH quantitative analysis method using the above-described redox dye will be shown.

(Reference Example 35)
The purified water used in the control groups 1-0, 1-1, 2-1 in the pharmacological test described above was used as test water, and 200 mL of the test water was replaced with nitrogen gas as described above for 40-fold concentration Pt standard solution. 1 mL was injected into the test water storage chamber using a syringe and sufficiently stirred and mixed, and then a methylene blue aqueous solution having a concentration of 10 g / L (volume molar concentration: 26773.8 μM) was added to the test water. A small amount of syringe was used to inject while visually observing the color change. The total amount of methylene blue solution injected until reaching the end point was 0 mL, and the effective value of the dissolved hydrogen concentration DH determined by substituting each value in the equation 7 was 0 (mg / L). Various physical property values and effective values of the dissolved hydrogen concentration DH of the test water according to Reference Example 35 are shown in Table 12, and effective values of the dissolved hydrogen concentration DH are shown in FIG.

(Reference Example 36)
The purified water containing Pt colloid catalyst (concentration of about 200 μg / L) used in Control Group 1-2 in the pharmacological test described above was used as the test water, and the DH quantitative analysis method by methylene blue titration was performed in the same manner as in Reference Example 35. As a result, the total amount of methylene blue solution injected until reaching the end point was 0 mL, and the effective value of the dissolved hydrogen concentration DH obtained by substituting each value into Equation 7 was 0 (mg / L). Various physical property values and effective values of the dissolved hydrogen concentration DH of the test water according to Reference Example 36 are shown in Table 12, and effective values of the dissolved hydrogen concentration DH are shown in FIG.

(Reference Example 37)
Using the purified water containing Pd colloid catalyst (concentration of about 200 μg / L) used in Control Group 1-3 in the above pharmacological test as the test water, DH quantitative analysis method by methylene blue titration in the same manner as in Reference Example 35 As a result, the total amount of methylene blue solution injected until reaching the end point was 0 mL, and the effective value of the dissolved hydrogen concentration DH obtained by substituting each value into Equation 7 was 0 (mg / L). Various physical property values and effective values of the dissolved hydrogen concentration DH of the test water according to Reference Example 37 are shown in Table 12, and effective values of the dissolved hydrogen concentration DH are shown in FIG.

(Reference Example 38)
DH determination by methylene blue titration in the same manner as in Reference Example 35, using the catalyst-free circulating electrolyzed water (electrolytic hydrogen water) used in Test Groups 1-1 and 2-1 in the above pharmacological test as test water. When the analysis method was carried out, the total amount of methylene blue solution injected up to the end point was 6.4 mL, and the effective value of the dissolved hydrogen concentration DH determined by substituting each value in Equation 7 was 1.71 (mg / L). Various physical property values and effective values of the dissolved hydrogen concentration DH of the test water according to Reference Example 38 are shown in Table 12, and the effective values of the dissolved hydrogen concentration DH are shown in FIG.

(Example 96)
The same procedure as in Reference Example 35, using the pre-catalyst circulating electrolyzed water (Pt colloidal catalyst (approximately 200 μg / L concentration)) used in test group 1-2 in the aforementioned pharmacological test as test water. When the DH quantitative analysis method by methylene blue titration was carried out, the total injection amount of the methylene blue aqueous solution up to the end point was 6.3 mL, and the effective dissolved hydrogen concentration DH found by substituting each value into the above equation 7 The value was 1.69 (mg / L) Various physical property values and effective values of the dissolved hydrogen concentration DH of the test water according to Example 96 are shown in Table 12, and the effective dissolved hydrogen concentration DH is shown in Table 12. The values are shown in FIG.

(Example 97)
The same procedure as in Reference Example 35, using the pre-catalyst-added circulating electrolyzed water (Pd colloidal catalyst (about 200 μg / L concentration)) used in Test Group 1-3 in the aforementioned pharmacological test as test water When the DH quantitative analysis method by the methylene blue titration was carried out, the total injection amount of the methylene blue aqueous solution up to the end point was 6.4 mL, and the effective dissolved hydrogen concentration DH determined by substituting each value into the above equation 7 The value was 1.71 (mg / L) Table 12 shows various physical property values and effective values of the dissolved hydrogen concentration DH of the test water according to Example 97, and shows the effective dissolved hydrogen concentration DH. The values are shown in FIG.

(Example 98)
The same procedure as in Reference Example 35, using post-catalyst-added circulating electrolyzed water (Pd colloidal catalyst (approximately 300 μg / L concentration)) used in Test Group 2-2 in the aforementioned pharmacological test as test water. When the DH quantitative analysis method by the methylene blue titration was carried out, the total injection amount of the methylene blue aqueous solution up to the end point was 6.4 mL, and the effective dissolved hydrogen concentration DH determined by substituting each value into the above equation 7 The value was 1.71 (mg / L) Table 12 shows the effective values of various physical properties and dissolved hydrogen concentration DH of the test water according to Example 98, and the effective dissolved hydrogen concentration DH. The values are shown in FIG.

Example 99
The same procedure as in Reference Example 35, using pre-catalyst-added circulating electrolyzed water (Pd colloidal catalyst (approximately 600 μg / L concentration)) used in Test Group 2-3 in the aforementioned pharmacological test as test water When the DH quantitative analysis method by methylene blue titration was carried out, the total injection amount of the methylene blue aqueous solution up to the end point was 6.7 mL, and the effective dissolved hydrogen concentration DH obtained by substituting each value into the above formula 7 The value was 1.79 (mg / L) Table 12 shows the various physical property values and the effective value of the dissolved hydrogen concentration DH of the test water according to Example 99, and the effective value of the dissolved hydrogen concentration DH. The values are shown in FIG.

(Example 100)
The same procedure as in Reference Example 35, using pre-catalyst-added circulating electrolyzed water (Pt colloidal catalyst (about 300 μg / L concentration)) used in Test Group 2-4 in the pharmacological test as test water. When the DH quantitative analysis method by methylene blue titration was carried out, the total injection amount of the methylene blue aqueous solution up to the end point was 6.3 mL, and the effective dissolved hydrogen concentration DH found by substituting each value into the above equation 7 The value was 1.69 (mg / L) Various physical property values and effective values of the dissolved hydrogen concentration DH of the test water according to Example 100 are shown in Table 12, and the effective dissolved hydrogen concentration DH is shown in Table 12. The values are shown in FIG.

(Example 101)
Recycled electrolytically treated water (Pt / Au alloy colloidal catalyst (about 300 μg / L concentration) containing pre-catalyst used in Test Group 2-5 in the above pharmacological test was used as test water. When the DH quantitative analysis method by methylene blue titration was carried out in the same manner, the total injection amount of the methylene blue aqueous solution up to the end point was 6.4 mL, and the dissolved hydrogen concentration obtained by substituting each value into the above formula 7 The effective value of DH was 1.71 (mg / L) Table 12 shows the various physical property values of the test water according to Example 101 and the effective value of the dissolved hydrogen concentration DH. The effective value of DH is shown in FIG.

(Example 102)
Recycled electrolytically treated water (Pd / Au alloy colloidal catalyst (about 300 μg / L concentration) containing pre-catalyst used in Test Group 2-6 in the aforementioned pharmacological test was used as test water, and Reference Example 35 and When the DH quantitative analysis method by methylene blue titration was carried out in the same manner, the total injection amount of the methylene blue aqueous solution up to the end point was 6.4 mL, and the dissolved hydrogen concentration obtained by substituting each value into the above formula 7 The effective value of DH was 1.71 (mg / L) Table 12 shows the various physical property values and the effective value of the dissolved hydrogen concentration DH of the test water according to Example 102, and the dissolved hydrogen concentration The effective value of DH is shown in FIG.

表１２によれば、試験群1-2~3 ,試験群2-2~6 にかかる抗酸化機能水（薬理機能水）は、いずれも雰囲気圧力下で飽和濃度以上（溶存水素濃度実効値換算）の水素を溶存した水であることがわかる。ちなみに、雰囲気圧力下（水温：２０℃）での溶存水素飽和濃度は、およそ１．６（ｍｇ／Ｌ）程度である。

According to Table 12, the anti-oxidation functional water (pharmacological functional water) applied to test groups 1-2 to 3 and test groups 2-2 to 6 is all over the saturated concentration under the atmospheric pressure (dissolved hydrogen concentration effective value conversion) It can be seen that this is water in which hydrogen is dissolved. Incidentally, the dissolved hydrogen saturation concentration under atmospheric pressure (water temperature: 20 ° C.) is about 1.6 (mg / L).

  The embodiment described above is described for facilitating the understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.

  Specifically, in the description of the embodiments, reference examples, and examples of the present invention, methylene blue is exemplified as the redox dye, but the redox dye usable in the present invention is limited to this example. For example, the pigments with prefixes include Acid Yellow 3, Acid Yellow 23, Acid Yellow 25, Acid Yellow 36, Acid Orange 5, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, and Acid Orange 52, Acid Green 16, Acid Green 25, Acid Violet 43, Acid Brown 2, Acid Black 1, Acid Black 31, Acid Blue 3, Acid Blue 9, Acid Blue 40, Acid Blue 45, Acid Blue 47, Acid Blue 5 Acid Blue 74, Acid Blue 113, Acid Blue 158, Acid Red 1, Acid Red 2, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 37, Acid Red 51, Acid Red 52, Acid Red 87, Acid Red 88, Acid Red 91, Acid Red 92, Acid Red 94, Acid Red 95, Acid Red 111, Solvent Yellow 2, Solvent Black 3, Solvent Blue 7, Solvent Blue 11, Solvent Blue 25, Solvent Red 3, Solvent Red 19 Solvent Red 23, Solvent Red 24, Solvent Red 73, Direct Yellow 1, Direct Yellow 9, Direct Yellow 12, Direct Yellow 59, Direct Green 1, Direct Green 6, Direct Green 59, Direct Brown 1, Direct Brown 6, Direct Black 4, Direct Black 22, Direct Black 38, Direct Blue 1, Direct Blue 6, Direct Blue 53, Direct Blue 86, Direct Blue 106, Direct Red 2, Direct Red 28, Direct Red 79, Disperse Yellow 3, Disperse Yellow 5, Disperse Yellow 8, Disperse Yellow 42, Disperse Yellow 60, Disperse Yellow 64, Disperse Orange 3 , Disperse Orange 30, Disperse Violet 26, Disperse Violet 28, Disperse Blue 1, Disperse Blue 26, Disper Thread 1, Disper Thread 4, Disper Thread 60, Disper Thread 65, Disper Thread 73, Bat Yellow 2, Bat Green 1, Bat Green 3, Bat Brown 1, Bat Brown 3, Bat Black 25, Bat Blue 1, Bat Blue 4, Bat Blue 20, Bat Red 10, Bat Red 41, Pigment Yellow 1, Pigment Yellow 3, Pigment Yellow 10, Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 17, Pigment Yellow 24, Pigment Yellow 55, Pigment Yellow 81, Pigment Yellow 83, Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 97 Pigment Yellow 98, Pigment Yellow 99, Pigment Yellow 108, Pigment Yellow 109, Pigment Yellow 110, Pigment Yellow 116, Pigment Yellow 117, Pigment Yellow 138, Pigment Yellow 151, Pigment Yellow 154, Pigment Orange 5, Pigment Orange 13, Pigment Orange 14, Pigment Orange 16, Pigment Orange 36, Pigment Orange 38, Pigment Orange 40, Pigment Orange 43, Pigment Green 4, Pigment Green 7, Pigment Green 8, Pigment Green 10, Pigment Green 36, Pigment Violet 1, Pigment Violet 3, Pigment Violet 19 and Pigment Violet 2 Pigment Violet 33, Pigment Brown 25, Pigment Black 1, Pigment Blue 2, Pigment Blue 15, Pigment Blue 16, Pigment Blue 17, Pigment Blue 18, Pigment Blue 24, Pigment Red 1, Pigment Red 3, Pigment Red 5, Pigment Red 9, Pigment Red 22, Pigment Red 38, Pigment Red 48: 1, Pigment Red 48: 2, Pigment Red 48: 3, Pigment Red 48: 4, Pigment Red 49: 1, Pigment Red 52: 1, Pigment Red 53 : 1, Pigment Red 57: 1, Pigment Red 60, Pigment Red 63: 2, Pigment Red 64: 1, Pigment Red 81, Pigment Red 83, Pigment Red 88, Pigment Red 112, Pigment Red 122, Pigment Red 123, Pigment Red 144, Pigment Red 146, Pigment Red 149, Pigment Red 151, Pigment Red 166, Pigment Red 168, Pigment Red 170, Pigment Red 174, Pigment Red 175 , Pigment Red 176, Pigment Red 177, Pigment Red 178, Pigment Red 179, Pigment Red 185, Pigment Red 187, Pigment Red 208, Hood Yellow 3, Hood Green 3, Hood Red 6, Hood Red 17, Basic Yellow 1, Basic Yellow 2, Basic Yellow 11, Basic Orange 1, Basic Orange 11, Basic Gri 4, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet 14, Basic Brown 1, Basic Blue 1, Basic Blue 3, Basic Blue 9, Basic Blue 24, Basic Red 1, Basic Red 2, Basic Red 5 , Basic Red 9, Basic Red 18, Mordant Yellow 1, Mordant Yellow 3, Mordant Orange 1, Mordant Violet 26, Mordant Black 11, Mordant Blue 13, Mordant Blue 29, Mordant Red 3, Mol Dant Red 11, Mordant Red 15, Reactive Yellow 2, Reactive Yellow 3, Reactive Yellow 17, Reactive Orange 1, Reactive Orange , Reactive Orange 16, Reactive Violet 2, Reactive Black 5, Reactive Blue 2, Reactive Blue 5, Reactive Blue 7, Reactive Blue 19, Reactive Red 1, Reactive Red 3, Reactive Red 6 , Reactive Red 17, Reactive Red 22, Reactive Red 41, etc. can be used, and the dyes that are not prefixed include acridine yellow G, alizarin, indamine, indoaniline, indocyanine green, urothion, urobilin, p. -Ethoxychrysoidine hydrochloride, m-cresol purple, o-cresolphthalein, cresol red, crocenic acid, chlorophyll (a, b, c, d), chlorophenol red, new methylene blue, neutral Red, bariamin blue B hydrochloride, methyl viologen, pyocyanin, indigo carmine, safranin T, phenosafranine, capri blue, nile blue, diphenylamine, xylene cyanol, nitrodiphenylamine, ferroin, N-phenylanthranilic acid Sodium dichloroindophenol, sodium 4-diphenylaminesulfonate, N, N'-diphenylbenzidine, cinnabarine (antibiotic), toluylene blue, riboflavin (vitamin B2), acridine yellow G, p-ethoxychrysoidine hydrochloride, blue tetrazolium , Diformazan (reduced form of blue tetrazolium), etc. can be used, and methyl viologen, variaminbu, etc., among them, are particularly clear because the color change in this titration is as clear as methylene blue. - B hydrochloride, neutral red, pyocyanin, 2,6-dichloro indophenol sodium, sodium 4-diphenylamine sulfonate, N, N'-diphenyl benzidine, Shin'nabarin (antibiotics), such as toluylene blue can be preferably used.

  In the description of the embodiments, reference examples, and examples of the present invention, platinum (Pt) is exemplified as the noble metal colloid catalyst used for the quantitative analysis of the dissolved hydrogen concentration. However, it is used for the quantitative analysis of the dissolved hydrogen concentration. The noble metal colloid catalyst that can be used is not limited to this example. For example, colloidal particles such as platinum, palladium, rhodium, iridium, ruthenium, gold, silver, rhenium, salts of these noble metal elements, alloy compounds, complex compounds, etc. As such, a mixture of these can be used as appropriate.

  Finally, in the description of the embodiments of the present invention, as an oxidative stress disease derived from free radicals or lipid peroxides, circulatory system such as liver / kidney injury due to drugs or harmful substances, ischemic reperfusion injury, arteriosclerosis, etc. Diseases, gastrointestinal diseases such as gastric ulcers, gastric mucosal disorders, respiratory diseases, diabetes complications (eg hypertension, cerebral infarction, myocardial infarction, etc.), cataracts, skin diseases, various inflammatory diseases, neurological diseases, cancer, Although aging etc. were illustrated and demonstrated, it is not limited to these. That is, not only those that are currently clarified as diseases involving oxidative cytotoxicity derived from free radicals or lipid peroxides, but also derived from free radicals or lipid peroxides to which the pharmacological functional water according to the present invention can be applied. It is intended to encompass all diseases involving oxidative cell injury, specifically, for example, diseases designated as “specific diseases” by the Ministry of Health, Labor and Welfare.

  11 Reduction potential water generator

Claims (6)

No precious metal colloid as a catalyst for decomposing molecular hydrogen into active hydrogen is added, and no active hydrogen is contained as a product generated from molecular hydrogen through the process of acting the catalyst,
A hydroxy radical-selective free radical scavenger containing high-concentration hydrogen-dissolved water that reacts with the radical through a forced hydrogen abstraction reaction by a hydroxy radical but does not have superoxide anion radical scavenging activity in an XOD experimental system,
The hydrogen-dissolved water is water obtained by treating a raw water containing distilled water by aeration or pressure filling with molecular hydrogen, and at the time of the treatment, the hydrogen-dissolved water is 0.89 mg / L or more of molecules. Containing a hydroxy radical selective free radical scavenger characterized by containing hydrogen, cerebral infarction, myocardial infarction, arteriosclerosis, diabetes, stroke, cataract, angina pectoris, dementia, liver disorder, renal disorder, Composition for prevention or treatment of malignant tumors, ischemic reperfusion injury, skin diseases, inflammatory diseases, burns, organ transplantation, gene oxidative damage, mitochondrial damage, aging / degeneration, side effects of drugs, radiation damage, or neurological diseases object. No precious metal colloid as a catalyst for decomposing molecular hydrogen into active hydrogen is added, and no active hydrogen is contained as a product generated from molecular hydrogen through the process of acting the catalyst,
A hydroxy radical-selective free radical scavenger containing high-concentration hydrogen-dissolved water that reacts with the radical through a forced hydrogen abstraction reaction by a hydroxy radical but does not have superoxide anion radical scavenging activity in an XOD experimental system,
The hydrogen-dissolved water is water obtained by treating a raw water containing distilled water by aeration or pressure filling with molecular hydrogen, and at the time of the treatment, the hydrogen-dissolved water is 0.89 mg / L or more of molecules. A transplanted organ preservation solution comprising a hydroxy radical-selective free radical scavenger characterized by containing hydrogen. No precious metal colloid as a catalyst for decomposing molecular hydrogen into active hydrogen is added, and no active hydrogen is contained as a product generated from molecular hydrogen through the process of acting the catalyst,
A hydroxy radical-selective free radical scavenger containing high-concentration hydrogen-dissolved water that reacts with the radical through a forced hydrogen abstraction reaction by a hydroxy radical but does not have superoxide anion radical scavenging activity in an XOD experimental system,
The hydrogen-dissolved water is water obtained by treating a raw water containing distilled water by aeration or pressure filling with molecular hydrogen, and at the time of the treatment, the hydrogen-dissolved water is 0.89 mg / L or more of molecules. A dialysate containing a hydroxy radical-selective free radical scavenger characterized by containing gaseous hydrogen. No precious metal colloid as a catalyst for decomposing molecular hydrogen into active hydrogen is added, and no active hydrogen is contained as a product generated from molecular hydrogen through the process of acting the catalyst,
A hydroxy radical-selective free radical scavenger containing high-concentration hydrogen-dissolved water that reacts with the radical through a forced hydrogen abstraction reaction by a hydroxy radical but does not have superoxide anion radical scavenging activity in an XOD experimental system,
The hydrogen-dissolved water is water obtained by treating a raw water containing distilled water by aeration or pressure filling with molecular hydrogen, and at the time of the treatment, the hydrogen-dissolved water is 0.89 mg / L or more of molecules. A peritoneal flow-through agent containing a hydroxy radical-selective free radical scavenger characterized by containing hydrogen. No precious metal colloid as a catalyst for decomposing molecular hydrogen into active hydrogen is added, and no active hydrogen is contained as a product generated from molecular hydrogen through the process of acting the catalyst,
A hydroxy radical-selective free radical scavenger containing high-concentration hydrogen-dissolved water that reacts with the radical through a forced hydrogen abstraction reaction by a hydroxy radical but does not have superoxide anion radical scavenging activity in an XOD experimental system,
The hydrogen-dissolved water is water obtained by treating a raw water containing distilled water by aeration or pressure filling with molecular hydrogen, and at the time of the treatment, the hydrogen-dissolved water is 0.89 mg / L or more of molecules. An eye drop containing a hydroxy radical-selective free radical scavenger characterized by containing hydrogen. No precious metal colloid as a catalyst for decomposing molecular hydrogen into active hydrogen is added, and no active hydrogen is contained as a product generated from molecular hydrogen through the process of acting the catalyst,
A hydroxy radical-selective free radical scavenger containing high-concentration hydrogen-dissolved water that reacts with the radical through a forced hydrogen abstraction reaction by a hydroxy radical but does not have superoxide anion radical scavenging activity in an XOD experimental system,
The hydrogen-dissolved water is water obtained by treating a raw water containing distilled water by aeration or pressure filling with molecular hydrogen, and at the time of the treatment, the hydrogen-dissolved water is 0.89 mg / L or more of molecules. Oral rhinitis drug containing a hydroxy radical-selective free radical scavenger characterized by containing gaseous hydrogen.

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