WO2004048356A1 - Cristal moleculaire ionique inorganique - Google Patents

Cristal moleculaire ionique inorganique Download PDF

Info

Publication number
WO2004048356A1
WO2004048356A1 PCT/JP2003/014624 JP0314624W WO2004048356A1 WO 2004048356 A1 WO2004048356 A1 WO 2004048356A1 JP 0314624 W JP0314624 W JP 0314624W WO 2004048356 A1 WO2004048356 A1 WO 2004048356A1
Authority
WO
WIPO (PCT)
Prior art keywords
crystal
ascorbic acid
inorganic ionic
ascorbate
ionic molecular
Prior art date
Application number
PCT/JP2003/014624
Other languages
English (en)
Japanese (ja)
Inventor
Hideo Sato
Motoji Ikeya
Original Assignee
Osaka Industrial Promotion Organization
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Osaka Industrial Promotion Organization filed Critical Osaka Industrial Promotion Organization
Priority to AU2003284557A priority Critical patent/AU2003284557A1/en
Publication of WO2004048356A1 publication Critical patent/WO2004048356A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C01F11/182—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds
    • C01F11/183—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by an additive other than CaCO3-seeds the additive being an organic compound
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/335—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin
    • A61K31/365—Lactones
    • A61K31/375—Ascorbic acid, i.e. vitamin C; Salts thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/06—Aluminium, calcium or magnesium; Compounds thereof, e.g. clay
    • A61K33/10—Carbonates; Bicarbonates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00—Drugs for dermatological disorders
    • A61P17/16—Emollients or protectives, e.g. against radiation
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P3/00—Drugs for disorders of the metabolism
    • A61P3/02—Nutrients, e.g. vitamins, minerals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R33/00—Arrangements or instruments for measuring magnetic variables
    • G01R33/20—Arrangements or instruments for measuring magnetic variables involving magnetic resonance
    • G01R33/60—Arrangements or instruments for measuring magnetic variables involving magnetic resonance using electron paramagnetic resonance

Definitions

  • the present invention can be used, for example, as an ultraviolet absorber, a vitamin c supplement, a detection element material of an electron spin resonance (ESR) radiation dosimeter, and the like.
  • ESR electron spin resonance
  • Ascorbic acid also known as vitamin C, is a vital nutrient in the body.
  • proline cannot be converted to hydroxyproline in the collagens that make up the skin, resulting in scurvy.
  • ascorbic acid has an antioxidant function and eliminates free radicals generated in a living body. For this reason, ascorbic acid is generally marketed as a nutritional supplement. Focusing on the antioxidant function, ascorbic acid is widely used as an antioxidant for foods and pharmaceuticals. As such, ascorbic acid has been studied in various ways for its function, and is used in various fields. However, all studies on ascorbic acid so far have been in aqueous solutions, and few studies have been performed on solids.For example, studies on inorganic ionic molecular crystals have not been studied. .
  • UV absorbers include paraaminobenzoic acid derivatives such as octyl paradimethylaminobenzoate, benzophenone derivatives such as oxybenzone, methoxycinnamic acid derivatives, and salicylic acid derivatives.
  • paraaminobenzoic acid derivatives such as octyl paradimethylaminobenzoate
  • benzophenone derivatives such as oxybenzone, methoxycinnamic acid derivatives
  • salicylic acid derivatives such as octyl paradimethylaminobenzoate
  • these conventional UV absorbers when used on human skin, they may bind to the entire epidermis and cause contact dermatitis or photo-contact dermatitis. ing.
  • an ultraviolet scattering agent has been used instead of the above-mentioned ultraviolet absorber.
  • the ultraviolet scattering agent include titanium oxide and zinc oxide.
  • vitamin C supplements include those using ascorbic acid or its salts as they are, and those obtained by tableting with excipients.
  • vitamin C is easily dissolved in water and decomposed by reacting with oxygen.
  • vitamin C since vitamin C has an acid taste, if it is added to foods and soft drinks as it is, there is a problem that the taste is altered.
  • conventional radiation measuring instruments include a film badge that uses blackening of photographic film, a scintillation measuring instrument that uses the recombination emission of electrons and holes generated by radiation, and a semiconductor PN junction that emits ionization current pulses.
  • semiconductor detectors for measurement thermoluminescence dosimeters, and photostimulated luminescence dosimeters.
  • the dose is obtained by observing the microwave absorption of the exposed body using the principle of electron spin resonance (ESR). The development of SR dosimeter is in progress.
  • Electron spin resonance means that when an unpaired electron with a spin quantum number S is placed in a static magnetic field, the energy level is Zemman-split into 2 S + 1, but the microphones that are equal between these adjacent levels A phenomenon in which absorption occurs resonatingly when a mouth wave is applied.
  • the ESR radiation dosimeter described in Japanese Patent Publication No. 6-59-5959 uses electron spin resonance to determine the number of unpaired electrons generated when a chemical bond is broken when an inorganic crystal material is irradiated with radiation. Measurement to obtain the exposure dose.
  • the ESR dosimeter is a non-destructive measuring instrument, it has the legal proof that the absorbed dose does not disappear even if the absorbed dose is read, which is an advantage over thermoluminescence dosimeters and photostimulated luminescence dosimeters. Having. Organic substances such as amino acids and sugar may be used as the detection element material of the ESR radiation dosimeter.
  • the ESR radiation dosimeter using alanine as the detection element material is a standard dosimeter in the middle and high line area. As popular. This detection element is produced, for example, by compressing alanine powder into a pellet and embedding it in paraffin to solidify.
  • the detector is exposed to radiation and light, and the amount of the radical is measured with an ESR dosimeter.
  • This measuring method is performed as follows. That is, first, the exposed detector material is placed in a quartz sample tube with an inner diameter of about 4 mm and placed in a microwave cavity resonator. The microwave output is kept constant and the magnetic field is modulated. The signal modulated by the magnetic field modulation is amplified by an amplifier, and the signal is extracted as a first derivative form dPZdH of the microwave absorption signal P (H), which is converted into a radiation dose.
  • conventional ESR radiation dosimeters have the problem of having extremely low sensitivity.
  • the conventional ESR radiation dosimeter can be used for radiation sterilization of blood for transfusion that requires 0.1 Gy to 20 Gy. Did not. There are two reasons for the lower sensitivity. The first reason is that the ESR radiation dosimeter using alanine as the detector element has a wide ESR absorption curve (up to 0.6 mT), so its signal intensity is low and its radial density is low. This is because the measurement range becomes lower. This is because the radical concentration is proportional to the area of the ESR absorption curve. The second reason is that signals generated when pulverizing the aranine crystal into powder are overlapped.
  • the present invention has been made in view of such circumstances, and can be used as an ultraviolet absorber, a benzoin C supplement, a detection element material of an ESR radiation dosimeter, and the like, and solves these conventional problems.
  • the aim is to provide possible new inorganic ionic molecular crystals.
  • the inorganic ionic molecular crystal of the present invention is an inorganic ionic molecular crystal containing an inorganic acid and a metal, in which ascorbic acid, ascorbate, an ascorbic acid derivative and Contains at least one ascorbate ion (hereinafter also referred to as "ascorbic acid, etc.”).
  • this inorganic ionic molecular crystal contains ascorbic acid and the like inside, it can be used as, for example, an ultraviolet absorber, a vitamin C supplement, and a detection element material of an ESR radiation dosimeter.
  • an ultraviolet absorber a vitamin C supplement
  • a detection element material of an ESR radiation dosimeter a detection element material of an ESR radiation dosimeter.
  • an ultraviolet absorber containing the same does not cause inconvenience due to binding to the skin and a photocatalytic reaction, and exhibits a favorable ultraviolet absorbing effect.
  • the inorganic ionic molecular crystal of the present invention contains ascorbic acid and the like inside thereof, ascorbic acid and the like do not dissolve in non-acidic water and are shielded from the outside, and thus are oxidatively decomposed by oxygen. And it does not affect the taste of food or soft drinks. If the inorganic ionic molecular crystal of the present invention is used as a detection element material for an ESR radiation dosimeter, the line width of the ESR absorption curve can be reduced to, for example, about 60 times smaller than the conventional one, and the microwave output intensity can be reduced. For example, the modulating magnetic field is reduced to about 1/100 of the conventional;
  • FIG. 1 shows an example of applying the inorganic ionic molecular crystal of the present invention to an ultraviolet absorber. It is a figure showing the measurement result of light absorbency in an example.
  • FIG. 2 is a diagram showing the measurement results of absorbance in another example in which the inorganic ionic molecular crystal of the present invention was applied to an ultraviolet absorber.
  • FIG. 3 is a diagram showing the measurement results of absorbance in other examples in which the inorganic ionic molecular crystals of the present invention were applied to an ultraviolet absorber.
  • FIG. 4 is a diagram showing the measurement results of absorbance in other examples in which the inorganic ionic molecular crystals of the present invention were applied to an ultraviolet absorber.
  • FIG. 5 is a diagram showing an ESR spectrum in one embodiment in which the inorganic ionic molecular crystal of the present invention is applied to a detection element of an ESR radiation dosimeter.
  • FIG. 6 is a diagram showing a relationship between an ESR signal intensity and a modulation magnetic field in another embodiment in which the inorganic ionic molecular crystal of the present invention is applied to a detection element of an ESR radiation dosimeter.
  • FIG. 7 is a diagram showing the relationship between ESR signal intensity and microphone mouth wave output in still another embodiment in which the inorganic ionic molecular crystal of the present invention is applied to a detection element of an ESR radiation dosimeter.
  • FIG. 8 is a diagram showing an ESR spectrum in still another example in which the inorganic ionic molecular crystal of the present invention is applied to a detection element of an ESR radiation dosimeter.
  • FIG. 9 is a diagram showing an ESR signal in still another example in which the inorganic ionic molecular crystal of the present invention is applied to a detection element of an ESR radiation dosimeter.
  • FIG. 10 is a diagram showing a relationship between an annealing temperature and an ESR signal intensity in still another embodiment in which the inorganic ionic molecular crystal of the present invention is applied to a detection element of an ESR radiation dosimeter.
  • Fig. 11 shows the radiation dose and ESR in still another embodiment in which the inorganic ionic molecular crystal of the present invention was applied to the detection element of an ESR radiation dosimeter. It is a figure showing relation with signal strength.
  • the metal includes, for example, sodium, potassium, lithium, strontium, calcium, magnesium, and barium. These metals may be used alone or in combination of two or more. Of these, magnesium, calcium, and strontium are preferred, and calcium and d are more preferred.
  • the inorganic acid includes, for example, carbonic acid, sulfuric acid, and phosphoric acid. Of these, carbonic acid is preferred.
  • the inorganic ionic molecular crystal of the present invention include calcium carbonate crystal, magnesium carbonate crystal, barium carbonate crystal, calcium sulfate crystal, magnesium sulfate crystal, barium sulfate crystal, calcium phosphate crystal, magnesium calcium carbonate [CaM] g (C 0 3) 2] crystals, there is a carbonate stolons lithium crystal or the like.
  • preferred are calcium carbonate crystals.
  • the inorganic ionic molecular crystal of the present invention contains at least one of ascorbic acid, ascorbate, an ascorbic acid derivative and an ascorbate ion.
  • Ascorbate includes, for example, sodium ascorbate, rhascorbate, and ascorbate There are lucidium salts and the like, which may be used alone or in combination of two or more. Ascorbate ion is monovalent and divalent, and varies with pH. ⁇ ⁇ ⁇ when changing from ascorbic acid to ascorbate ion (monovalent) is 4.1, and p K when changing from ascorbate ion (monovalent) to ascorbate ion (divalent) '. 2 is 1 1.57.
  • the total or single content of ascorbic acid, ascorbate, ascorbic acid derivative and ascorbate ion is not particularly limited, but may be, for example, 0.001 to 1 with respect to the entire inorganic ionic molecular crystal including this.
  • the method for producing the inorganic ionic molecular crystal of the present invention is not particularly limited, and includes, for example, the following first production method and second production method.
  • the first production method at least one of an aqueous solution of an inorganic acid ion and an aqueous solution of a metal ion contains at least one of ascorbic acid, an ascorbate salt, and an ascorbic acid derivative.
  • the method of mixing the two aqueous solutions is not particularly limited. For example, a method in which one solution is added to the other solution Is also good.
  • the two aqueous solutions may be mixed by injecting the two aqueous solutions into a certain container. In the case of the latter method, for example, mixing can be performed by using a spray.
  • Examples of the inorganic acid aqueous solution include an aqueous solution of sodium carbonate, an aqueous solution of potassium carbonate, an aqueous solution of ammonium carbonate, an aqueous solution of sodium sulfate, an aqueous solution of potassium sulfate, and an aqueous solution of ammonium phosphate.
  • Examples of the aqueous metal ion solution include an aqueous solution of calcium chloride, an aqueous solution of calcium acetate, an aqueous solution of magnesium chloride, an aqueous solution of strontium chloride, and an aqueous solution of barium chloride.
  • the molar ratio between the inorganic acid ion and the metal ion is preferably 1: 1.
  • a 1 M aqueous solution of 1 M calcium chloride may be added to a 0.1 M aqueous solution of sodium carbonate to precipitate calcium carbonate crystals.
  • calcium carbonate crystals may be precipitated by pouring the mixture into a container while mixing the 0.1 M aqueous solution of calcium chloride with the aqueous solution of 0.1 M sodium carbonate.
  • the water used in the solution of the present invention is not particularly limited, but is preferably ion-exchanged water, distilled water, ultrapure water, or the like.
  • ascorbic acid or ascorbate it is only necessary to adjust ⁇ of an aqueous solution of an inorganic acid and add ascorbic acid or ascorbate to this.
  • ascorbic acid or a salt thereof is added to an aqueous solution of sodium carbonate having a pH of 11.41, a large amount of divalent ions will be present, and a mixture of potassium carbonate and carbonic acid (pH 1.05) will be added. If ascorbic acid or a salt thereof is added, many monovalent ions are present.
  • the method for adjusting the pH is not particularly limited, and may be adjusted by, for example, adding an alkaline substance such as sodium hydroxide, potassium hydroxide, or calcium hydroxide, or an acidic substance such as hydrochloric acid or sulfuric acid.
  • the second production method comprises the steps of: adding an ascorbic acid metal salt to an aqueous solution of an inorganic acid ion to precipitate an inorganic ionic molecular crystal; reducing the amount of ascorbic acid, ascorbate and ascorbate ions in the crystal; It is a production method in which both are contained.
  • the ultraviolet absorbent of the present invention contains the inorganic ionic molecular crystals of the present invention.
  • the absorption wavelength of the inorganic ionic molecular crystal of the present invention is, for example, in the range of 250 to 320 nm, and is characterized by having an absorption wavelength in the UVB region (280 to 315 nm). In addition, ascorbic acid itself does not have a remarkable absorption wavelength in the UVB region.
  • the content ratio of the inorganic ionic molecular crystals with respect to the entire ultraviolet absorber is not particularly limited, and is, for example, in the range of 0.001 to 100% by mass.
  • the proportion of ascorbic acid or the like in the inorganic ionic molecular crystals in the ultraviolet absorbent of the present invention is not particularly limited, but is, for example, in the range of 0.1 to 5% by mass relative to the whole inorganic ionic molecular crystals. Preferably, it is in the range of 0.5 to 2% by mass, more preferably in the range of 1 to 2% by mass.
  • the ultraviolet absorber may include, as other components, an ultraviolet scattering agent, glycerin, other ultraviolet absorbers, etc. By using the ultraviolet absorber in combination with the ultraviolet scattering agent, the ultraviolet absorber of the present invention can block ultraviolet rays. The wavelength bandwidth expands. Examples of the ultraviolet light scattering agent include titanium oxide and zinc oxide.
  • the ultraviolet scattering agent is preferably contained in the inorganic ion molecule crystal.
  • the content ratio of the ultraviolet light scattering agent is not particularly limited, and is, for example, in the range of 0.01 to 10% by mass based on the whole ultraviolet light absorbing agent.
  • the particle size of the ultraviolet light scattering agent is not particularly limited, but is, for example, in the range of 0.001 to 0.1 zm.
  • the form of the inorganic ionic molecular crystals can be changed from powder to a fluid form, thereby expanding the applications.
  • the ratio of inorganic ionic molecular crystals on the surface of the UV absorber can be increased as compared with powder, and as a result, the UV absorption effect is maintained.
  • the mixing ratio of glycerin is not particularly limited, and is, for example, in a range of 10 to 70% by mass based on the whole ultraviolet absorber.
  • the ultraviolet absorbent of the present invention can be used for various uses such as cosmetics, pharmaceuticals, clothing, resin additives, paper, rubber, and plastics.
  • the vitamin C supplement of the present invention contains the inorganic ionic molecular crystal of the present invention.
  • the inorganic ionic molecular crystal contains ascorbic acid and the like inside, the ascorbic acid and the like are in a state of being cut off from the outside.
  • the ratio of the inorganic ionic molecular crystals is not particularly limited, and is, for example, 0.001 to 100% by mass based on the entire supplement.
  • the proportion of ascorbic acid and the like in the inorganic ionic molecular crystals in the vitamin C supplement of the present invention is not particularly limited, but
  • the vitamin C supplement of the present invention may contain other components such as other vitamins (A, B group, D, E, etc.), amino acids, minerals (zinc, calcium, etc.). Good.
  • the form of the vitamin C supplement of the present invention is not particularly limited, and may be, for example, a powder, a tablet or the like.
  • the vitamin C supplement of the present invention can be used in addition to ordinary vitamins (supplements), for example, toothpaste (bleeding prevention, etc.), potash supplements (helping calcium absorption, etc.), milk such as yogurt, etc. May be used for products.
  • the detection element material of the ESR radiation dosimeter of the present invention includes the inorganic ionic molecular crystal of the present invention.
  • the detection element material is a powder
  • the detection element may be one in which this powder is put in a capsule, or one in which this powder is immobilized with polystyrene or paraffin using a flux.
  • the shape of the detection element is not particularly limited, and various shapes such as a rod shape, a plate shape, and a tape shape are possible.
  • the ratio of ascorbic acid or the like in the inorganic ionic molecular crystals in the detection element material of the present invention is not particularly limited, but may be, for example, 0.01 to 0.3% by mass based on the entire inorganic ionic molecular crystals.
  • the range is preferably in the range of 0.05 to 0.2% by mass.
  • the detection can be performed by adjusting the content of those metal ions, or by adjusting the amount of ascorbic acid or the like to be added. It is possible to adjust the sensitivity of the device material to radiation.
  • the sensitivity of the detection element material to radiation can be adjusted by heating the detection element material to thermally decompose the added ascorbic acid and the like.
  • the inorganic ion molecular crystal contains a paramagnetic metal ion for correcting the intensity of unpaired electrons or radicals.
  • the permanent metal ions include, for example, manganese ions, chromium ions, copper ions, and the like. These may be used alone or in combination of two or more. Of these, manganese ions and chromium ions are preferred, and manganese ions are more preferred.
  • an ESR radiation dosimeter includes a detection element in which a detection material that generates unpaired electrons due to radiation is stylized, and a device that measures ESR in the detection material.
  • An ESR radiation dosimeter for measuring the concentration of a pair of electrons or the concentration of a radical containing the unpaired electron, and determining a radiation dose from the measured value, wherein the detection material is the detection element material of the present invention.
  • the measurement of radiation using the ESR radiation dosimeter of the present invention is performed, for example, as follows. That is, first, an inorganic ionic molecular crystal of the present invention, which is compression-molded into a pellet, is embedded in paraffin and solidified to produce a detection element. This detection element is exposed to radiation or light. After the exposure, the detection element is placed in a quartz sample tube with an inner diameter of about 4 mm and placed in a microwave cavity resonator.
  • the microwave output is kept constant and the magnetic field is modulated.
  • the signal modulated by the magnetic field modulation is amplified by an amplifier, and a signal is extracted as a first derivative form dPZdH of the microwave absorption signal P (H), which is converted into a radiation dose.
  • Example 1 400 ml of a 0.1 M aqueous sodium carbonate solution and 40 ml of a 1 M aqueous calcium chloride solution were prepared. Then, 3.1 lg or 0.31 g of ascorbic acid was added to the aqueous sodium carbonate solution. The amount of ascorbic acid added is adjusted so as to be 1% by mass or 0.1% by mass of the entire calcium carbonate crystal including the same. Then, the calcium carbonate aqueous solution was added to the sodium carbonate aqueous solution to precipitate calcium carbonate crystals containing ascorbic acid inside the crystals. The obtained crystals have two kinds of ascorbic acid concentrations of 0.1% by mass and 1% by mass.
  • the curve shows the absorbance of ascorbic acid (vitamin C) alone.
  • vitamin C ascorbic acid
  • Example 2 calcium carbonate containing 1% by mass of ascorbic acid was prepared. Mix this with glycerin in a volume ratio of 1: 1 Then, the absorbance was measured. This measurement was also performed in the same manner as in Example 1. As a reference example, the absorbance of calcium carbonate containing 1% by mass of ascorbic acid was also measured. The result is shown in FIG. In the figure, the upper curve shows the absorbance when mixed with glycerin, and the lower curve shows the absorbance when not mixed with glycerin. As shown, the absorbance was improved by mixing with dalyserin.
  • Example 2 zinc oxide (particle size: 0.02 m) was added to an aqueous solution of sodium carbonate by lO Omg, and 6.2 g or 0.62 g of ascorbic acid was added.
  • the zinc oxide was obtained by uniformly dispersing particles in the aqueous solution by ultrasonic waves.
  • calcium carbonate containing ascorbic acid and zinc oxide was prepared in the same manner as in Example 1, and the absorbance was measured. This measurement was also performed in the same manner as in Example 1. Further, as a reference example, the absorbance of calcium carbonate containing 1% by mass of ascorbic acid was also measured.
  • Figure 3 shows the results.
  • the solid line shows the absorbance when zinc oxide is contained
  • the dotted line shows the absorbance when zinc oxide is not contained.
  • absorption was confirmed in the UVA region (315-380 nm) in addition to the UVB region (280-315 nm).
  • Example 1 Ascorbic acid was added to the aqueous sodium carbonate solution at various concentrations. Except for this, calcium carbonate containing ascorbic acid at various concentrations was prepared in the same manner as in Example 1, and the absorbance (293 nm) was measured. This measurement is performed in the same manner as in Example 1. Was. Figure 4 shows the results. As shown, the absorbance increased as the ascorbic acid content increased.
  • the conditions for this measurement are: absorbed dose of 70 Gy (gray), modulated magnetic field width of 0.02 mT, magnetic field sweep width of 2 mT, and microwave output intensity of OlmW.
  • Figure 5 shows the measurement results.
  • the upper curve is the ESR absorption signal of DL-alanine.
  • the lower curve is the ESR absorption signal of calcium carbonate containing ascorbic acid.
  • the signal width of ascorbic acid-containing calcium carbonate is about 1/60 smaller than the signal in the middle of DL-alanine.
  • Figure 6 shows the results of the magnetic field modulation
  • Figure 7 shows the results of the microwave output.
  • the calcium carbonate containing ascorbic acid is more optimal than the DL-alanine in the optimal condition of each modulating magnetic field (the modulating magnetic field immediately before the signal intensity is saturated).
  • the ESR signal strength is about 3 times better.
  • the modulation magnetic field is 0.02 mT
  • the calcium carbonate containing ascorbic acid has a higher ESR under the optimum conditions of the microwave output (modulation magnetic field immediately before the signal intensity is saturated) than DL-alanine.
  • the signal strength is about 10 times better.
  • the thermal stability of ascorbic acid-containing calcium carbonate radical and DL-alanine radical in ESR measurement was examined.
  • the thermal stability of manganese ion-containing calcium carbonate was also investigated. Heating was performed by annealing at various temperatures for 15 minutes. That is, while the temperature is gradually increased from room temperature, the temperature is kept constant at a certain temperature for 15 minutes, the ESR is measured, and then the temperature is raised and the temperature is kept constant at the next temperature for 15 minutes. The same sample was kept at various temperatures for 15 minutes, and the ESR was measured each time. Such an experiment is called isochronous annealing experiment.
  • the conditions for ESR measurement were as follows: in the case of calcium carbonate containing ascorbic acid, a microwave output of 0.02 mW and a modulation magnetic field of 0.02 mT, and in the case of DL-alanine, a microwave output of lmW and a modulation magnetic field of 0.lmT, In the case of Mn 2 + , the microwave output is lmW and the modulation magnetic field is 0.1 lmT.
  • Figure 10 shows these results. As shown in the figure, ascorbic acid-containing calcium carbonate was superior in thermal stability by about 10 ° C to DL-alanine, and was superior in thermal stability at high temperatures. In addition, ascorbic acid-containing calcium carbonate had a sufficiently low decay rate at room temperature.
  • the ascorbic acid-containing calcium carbonate was irradiated with ⁇ rays at various doses, and its ESR signal intensity was measured.
  • the measurement conditions were as follows: microwave output 0.0 2 mW, modulation field 0.02 mT.
  • the results are shown in FIG.
  • the ESR signal intensity also increased in proportion to the X-ray absorption.
  • the minimum detection sensitivity (20 mGy) was determined by the SZN ratio.
  • the inorganic ionic molecular crystal of the present invention has ascorbic acid and the like inside the crystal.
  • This inorganic ion crystal can be applied to, for example, an ultraviolet absorber, a vitamin C supplement, and an ESR detection element material, and can solve these conventional problems.
  • the inorganic ionic molecular crystal of the present invention can be used for other purposes.

Abstract

La présente invention a trait à un cristal moléculaire ionique inorganique pouvant être utilisé en tant qu'absorbant d'ultraviolet, un supplément de la vitamine C ou un matériau d'élément de détection pour dosimètre de rayonnement par résonance du spin électronique. On ajoute 40 ml de 0,1 M de solution aqueuse de chlorure de calcium à 400 ml de 0,1 M d'une solution aqueuse de carbonate de sodium contenant de l'acide ascorbique en vue de la précipitation de cristaux de carbonate de calcium. Le carbonate de calcium dans son cristal ainsi obtenu contient de l'acide ascorbique. Grâce à l'activité de l'acide ascorbique, ce carbonate de calcium présente une absorption de l'ultraviolet dans la plage de rayonnement ultraviolet B comme représenté dans la Figure 1 et peut être utilisé dans un dosimètre de rayonnement par résonance du spin électronique ou comme suppléments de la vitamine C.
PCT/JP2003/014624 2002-11-19 2003-11-18 Cristal moleculaire ionique inorganique WO2004048356A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003284557A AU2003284557A1 (en) 2002-11-19 2003-11-18 Inorganic ionic molecular crystal

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002-335753 2002-11-19
JP2002335753A JP2004168701A (ja) 2002-11-19 2002-11-19 無機イオン性分子結晶

Publications (1)

Publication Number Publication Date
WO2004048356A1 true WO2004048356A1 (fr) 2004-06-10

Family

ID=32375732

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2003/014624 WO2004048356A1 (fr) 2002-11-19 2003-11-18 Cristal moleculaire ionique inorganique

Country Status (3)

Country Link
JP (1) JP2004168701A (fr)
AU (1) AU2003284557A1 (fr)
WO (1) WO2004048356A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101707175B (zh) * 2009-11-12 2011-06-15 江苏泽铭荧光材料有限公司 一种节能灯用电子粉及其制备方法
US9695390B2 (en) 2010-08-23 2017-07-04 President And Fellows Of Harvard College Acoustic waves in microfluidics
US20190015449A1 (en) * 2017-07-17 2019-01-17 Dr. Marlowe's Weight Loss Institute, P.L.L.C. Supplement for treating side effects of medications which cause metabolic acidosis
US10258987B2 (en) 2014-06-26 2019-04-16 President And Fellows Of Harvard College Fluid infection using acoustic waves
US11559806B2 (en) 2015-08-27 2023-01-24 President And Fellows Of Harvard College Acoustic wave sorting
US11701658B2 (en) 2019-08-09 2023-07-18 President And Fellows Of Harvard College Systems and methods for microfluidic particle selection, encapsulation, and injection using surface acoustic waves

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7887882B2 (en) * 2005-02-09 2011-02-15 Essilor International (Compagnie Generale D'optique) Stabilized ultra-violet absorbers

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56135171A (en) * 1980-03-27 1981-10-22 Jeol Ltd Measuring method of radiation amount using electron spin
JPS59203728A (ja) * 1983-05-06 1984-11-17 Earth Chem Corp Ltd 炭酸カルシウム結晶の製造方法
JPH01253681A (ja) * 1988-04-01 1989-10-09 Kagaku Gijutsucho Hoshasen Igaku Sogo Kenkyusho 電子スピン共鳴吸収放射線量計用測定体
US5120762A (en) * 1987-10-19 1992-06-09 Takeda Chemical Industries, Ltd. Method for production of stabilized sodium ascorbate powder
JPH0775728A (ja) * 1993-06-18 1995-03-20 Suzuki Yushi Kogyo Kk 無機質均一微小球体の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56135171A (en) * 1980-03-27 1981-10-22 Jeol Ltd Measuring method of radiation amount using electron spin
JPS59203728A (ja) * 1983-05-06 1984-11-17 Earth Chem Corp Ltd 炭酸カルシウム結晶の製造方法
US5120762A (en) * 1987-10-19 1992-06-09 Takeda Chemical Industries, Ltd. Method for production of stabilized sodium ascorbate powder
JPH01253681A (ja) * 1988-04-01 1989-10-09 Kagaku Gijutsucho Hoshasen Igaku Sogo Kenkyusho 電子スピン共鳴吸収放射線量計用測定体
JPH0775728A (ja) * 1993-06-18 1995-03-20 Suzuki Yushi Kogyo Kk 無機質均一微小球体の製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SATO H. ET AL: "Electron spin resonance of ascorbyl (Vitamin C) radicals in synthetic CaCO3 by UV irradiation", JPN. J. APPL. PHYS., vol. 42, no. 2A, 2003, pages 428 - 433, XP002978029 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101707175B (zh) * 2009-11-12 2011-06-15 江苏泽铭荧光材料有限公司 一种节能灯用电子粉及其制备方法
US9695390B2 (en) 2010-08-23 2017-07-04 President And Fellows Of Harvard College Acoustic waves in microfluidics
US10570361B2 (en) 2010-08-23 2020-02-25 President And Fellows Of Harvard College Acoustic waves in microfluidics
US11229911B2 (en) 2010-08-23 2022-01-25 President And Fellows Of Harvard College Acoustic waves in microfluidics
US10258987B2 (en) 2014-06-26 2019-04-16 President And Fellows Of Harvard College Fluid infection using acoustic waves
US11559806B2 (en) 2015-08-27 2023-01-24 President And Fellows Of Harvard College Acoustic wave sorting
US20190015449A1 (en) * 2017-07-17 2019-01-17 Dr. Marlowe's Weight Loss Institute, P.L.L.C. Supplement for treating side effects of medications which cause metabolic acidosis
US10342824B2 (en) * 2017-07-17 2019-07-09 Dr. Marlowe's Weight Loss Institute, P.L.L.C. Supplement for treating side effects of medications which cause metabolic acidosis
US11701658B2 (en) 2019-08-09 2023-07-18 President And Fellows Of Harvard College Systems and methods for microfluidic particle selection, encapsulation, and injection using surface acoustic waves

Also Published As

Publication number Publication date
JP2004168701A (ja) 2004-06-17
AU2003284557A1 (en) 2004-06-18

Similar Documents

Publication Publication Date Title
Lu et al. High energy X-ray radiation sensitive scintillating materials for medical imaging, cancer diagnosis and therapy
US5871708A (en) Radioactive patch/film and process for preparation thereof
US8684898B2 (en) Ionizing-radiation-responsive compositions, methods, and systems
US8227204B2 (en) Ionizing-radiation-responsive compositions, methods, and systems
ES2602048T3 (es) Nanopartículas inorgánicas de alta densidad para destruir células in vivo
WO2004048356A1 (fr) Cristal moleculaire ionique inorganique
US20090101838A1 (en) Ionizing-radiation-responsive compositions, methods, and systems
US20170224821A1 (en) Ionizing-radiation-responsive compositions, methods, and systems
US20060000977A1 (en) Device for generating images and/or projections
Rautray et al. Analysis of Indian pigment gallstones
Clark The physiological action of light
US20100176343A1 (en) Energy-transfer nanocomposite materials and methods of making and using same
CN105440188A (zh) 一种新型三维凝胶剂量计材料及其制备方法
US8168958B2 (en) Ionizing-radiation-responsive compositions, methods, and systems
CN108904466A (zh) 一种含ZnO的水凝胶珠包封难溶性药物的方法
Kovacs et al. Alcohol solutions of triphenyl-tetrazolium chloride as high-dose radiochromic dosimeters
Gualtieri et al. The Chernobyl accident: EPR dosimetry on dental enamel of children
US20090104113A1 (en) Ionizing-radiation-responsive compositions, methods, and systems
US8529426B2 (en) Ionizing-radiation-responsive compositions, methods, and systems
JP3491286B2 (ja) 平均的にクラスターの小さい水
Wielopolski et al. Continuous three‐dimensional radiation dosimetry in tissue‐equivalent phantoms using electron paramagnetic resonance in L‐α‐alanine
US11971510B2 (en) Gel dosimeter for measuring radiation dose
Yao et al. X-ray excited luminescent nanoparticles for deep photodynamic therapy
JP2719713B2 (ja) 電子スピン共鳴による放射線線量測定用線量計素子材料
JP2012041406A (ja) ダイヤモンド

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase