WO2021075332A1 - Ultrafine bubble-containing aqueous solution and beverage containing said aqueous solution - Google Patents

Abstract

[Problem] Since an ultrafine bubble can exist for a long period of time, an ROS scavenging action of the ultrafine bubble may also last for a long period of time. An effect of various gases on scavenging active oxygen in an ultrafine bubble beverage is unknown, and the purpose of the present invention is to examine the effect. [Solution] According to an ultrafine bubble-containing solution of the present invention and a beverage containing the same, it is possible to provide an ultrafine bubble-containing aqueous solution containing at least one gas among carbon dioxide and hydrogen inside an ultrafine bubble which has an active oxygen scavenging action and is expected to have a health promoting effect and an anti-fatigue effect, etc., and a beverage containing the same.

Description

Ultrafine bubble-containing aqueous solution and beverage containing the aqueous solution

The present invention relates to an aqueous solution containing ultrafine bubbles and a beverage containing the aqueous solution, and more particularly to an aqueous solution containing ultrafine bubbles containing at least one of carbon dioxide and hydrogen and a beverage containing the aqueous solution.

Active oxygen (hereinafter, also referred to as "ROS") is a causative agent of many diseases including cancer, and elimination of active oxygen has been considered as one approach to the prevention and treatment of diseases.

In order to efficiently eliminate active oxygen, it is necessary to efficiently ingest the active oxygen scavenging component. However, the intake of the active oxygen scavenging component from foods or beverages is very small and limited, and a long-lasting effect cannot be expected. Among active oxygen, it is said that the elimination of hydroxyl radical (OH ·) and superoxide anion radical (O ₂ · ⁻ ) is particularly important for the prevention and treatment of diseases.

On the other hand, Ultrafine Bubble (hereinafter, also referred to as "UFB (Ultrafine Bubble)") has a high negative zeta potential in a neutral solution and has an antioxidant ability. The size of UFB decreases with the passage of time, and it is considered that the UFB can exist even after the passage of one month.

Sufficient studies have not yet been conducted on the sustained antioxidant capacity of ultrafine bubbles. For example, hydrogen has a high reducing power, but the antioxidant capacity of nanofine bab hydrogen water (ultrafine bubble aqueous solution containing hydrogen) has not been sufficiently investigated.

Uemura et al. Have developed a technology to eject a large amount of ultrafine bubbles by resonance foaming and vacuum cavitation. Furthermore, "Hydrogen ultrafine bubble water has an antioxidant function and hypertension in the aging society. , Hyperlipidemia, diabetes, heart disease, cerebral infarction and other so-called lifestyle-related diseases, as well as cancer prevention. " Neither has it been proven.

Regarding the preparation of ultrafine bubbles, Ahmed et al. Considered ultrafine bubble-containing aqueous solutions of air, nitrogen, and oxygen using cylindrical ceramic nanofiltration membranes instead of the conventional method of generation by hydrodynamics, acoustics, particles, and optical cavitation. However, it has been reported that the size of air bubbles can be reduced to the nano level (see Non-Patent Document 1 below).

Japanese Unexamined Patent Publication No. 2016-104474

Ultra fine bubbles can exist for a long period of time, so their antioxidant capacity may also last for a long period of time. However, the effect of ultrafine bubbles of various gases on the elimination of active oxygen is unknown, and its examination has been an issue.

The present inventors have investigated the antioxidative ability and the effect on various diseases of nanofine bubbles of various gases, and include at least one of carbon dioxide and hydrogen in the ultrafine bubbles. Based on the finding that the solution containing ultrafine bubbles has a continuous ROS scavenging ability, a cytotoxic effect on cancer cells, and an antitumor effect on cancer-bearing mice, it has an active oxygen scavenging ability and cancer. PCT / JP2019 / 041060 for a solution containing at least one of carbon dioxide and hydrogen inside the ultrafine bubble, which has a cytotoxic effect on cells and an antitumor effect on cancer-bearing mice. Disclosed in.

In the present invention, in view of the above problems, the present inventors are studying the antioxidant capacity of nanofine bubbles of various gases and their application to various uses, and are considering carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles. It has been found that an ultrafine bubble-containing aqueous solution containing at least one ultrafine bubble selected from the group consisting of bubbles has a continuous ROS scavenging effect and can be applied to various beverages.

Therefore, an object of the present invention is to provide an ultrafine bubble-containing aqueous solution and the aqueous solution containing at least one ultrafine bubble selected from the group consisting of carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles having an active oxygen scavenging action. The purpose is to provide a beverage containing the substance.

That is, the present invention is as follows.
[1]
An ultrafine bubble-containing aqueous solution containing at least one ultrafine bubble selected from the group consisting of carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles.
[2]
The ultrafine bubble-containing aqueous solution of [1], which is an ethanol-free non-alcoholic aqueous solution containing at least one ultrafine bubble selected from the group consisting of carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles.
[3]
The ultrafine bubble-containing aqueous solution of [2] containing carbon dioxide ultrafine bubbles.
[4]
The ultrafine bubble-containing aqueous solution of [2] containing hydrogen ultrafine bubbles.
[5]
The ultrafine bubble-containing aqueous solution of [2] containing carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles.
[6]
The ultrafine bubble-containing aqueous solution according to any one of [3] to [5], which has a hydroxyl radical scavenging action.
[7]
The ultrafine bubble-containing soft drink according to any one of [3] to [5], which has a superoxide anion scavenging effect.
[8]
The ultrafine bubble-containing aqueous solution according to any one of [3] to [5], which has an action of scavenging hydroxyl radicals and superoxide anions.
[9]
The ultrafine bubble-containing aqueous solution of [2], which contains carbon dioxide ultrafine bubbles and has a hydroxyl radical scavenging action.
[10]
The ultrafine bubble-containing aqueous solution of [2], which contains carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles and has a hydroxyl radical scavenging action.
[11]
The ultrafine bubble-containing aqueous solution of [2], which contains hydrogen ultrafine bubbles and has a superoxide anion scavenging action.
[12]
The ultrafine bubble-containing aqueous solution of [2], which contains carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles and has a superoxide anion scavenging action.
[13]
A soft drink containing the ultrafine bubble-containing aqueous solution according to any one of [2] to [12].
[14]
The soft drink of [13], which is any soft drink selected from the group consisting of carbonated drinks, fruit tree drinks, vegetable drinks, coffee drinks, tea-based drinks, sports drinks, and mineral water.
[15]
A method for producing an ultrafine bubble-containing aqueous solution of [5], [10] or [12] containing carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles, wherein the ultrafine bubble-containing aqueous solution containing hydrogen ultrafine bubbles is used. A method for producing an ultrafine bubble-containing aqueous solution, which further blows carbon dioxide to produce an ultrafine bubble-containing aqueous solution containing carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles.
[16]
A method for producing an ultrafine bubble-containing aqueous solution of [5], [10] or [12] containing carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles, wherein the ultrafine bubble-containing aqueous solution containing carbon dioxide ultrafine bubbles is used. A method for producing an ultrafine bubble-containing aqueous solution, which comprises further injecting hydrogen to produce an ultrafine bubble-containing aqueous solution containing carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles.
[17]
The ultrafine bubble-containing alcohol aqueous solution of [1], which is an ethanol-containing alcoholic aqueous solution containing at least one ultrafine bubble selected from the group consisting of carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles.
[18]
[17] Ultrafine bubble-containing alcohol aqueous solution containing carbon dioxide ultrafine bubbles.
[19]
[17] Ultrafine bubble-containing alcohol aqueous solution containing hydrogen ultrafine bubbles.
[20]
The ultrafine bubble-containing alcohol aqueous solution of [17], which comprises carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles.
[21]
[18] to [20] ultrafine bubble-containing alcohol aqueous solutions having a hydroxyl radical scavenging action.
[22]
[18] to [20] ultrafine bubble-containing alcohol aqueous solutions having a superoxide anion scavenging action.
[23]
[18] to [20] ultrafine bubble-containing alcohol aqueous solutions having an action of scavenging hydroxyl radicals and superoxide anions.
[24]
[17] Ultrafine bubble-containing alcohol aqueous solution containing carbon dioxide ultrafine bubbles and having a hydroxyl radical scavenging action.
[25]
[17] Ultrafine bubble-containing alcohol aqueous solution containing hydrogen ultrafine bubbles and having a hydroxyl radical scavenging action.
[26]
The ultrafine bubble-containing alcohol aqueous solution of [17], which contains carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles and has a hydroxyl radical scavenging action.
[27]
[17] Ultrafine bubble-containing alcohol aqueous solution containing carbon dioxide ultrafine bubbles and having a superoxide anion scavenging action.
[28]
The ultrafine bubble-containing alcohol aqueous solution of [17], which contains carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles and has an action of scavenging hydroxyl radicals and superoxide anions.
[29]
An alcoholic beverage containing the ultrafine bubble-containing alcohol aqueous solution according to any one of [17] to [28].
[30]
The alcoholic beverage of [29], which is any alcoholic beverage selected from the group consisting of sake, peel, wine, and whiskey.
[31]
A method for producing an ultrafine bubble-containing alcohol aqueous solution according to [23], [26], or [28], which comprises a carbon dioxide ultrafine bubble and a hydrogen ultrafine bubble, and is an ultrafine bubble-containing aqueous solution containing a hydrogen ultrafine bubble. A method for producing an ultrafine bubble-containing alcohol aqueous solution, which comprises further injecting carbon dioxide into an ultrafine bubble-containing aqueous solution containing carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles.

According to the present invention, an aqueous solution containing ultrafine bubbles and the aqueous solution containing at least one ultrafine bubble selected from the group consisting of carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles having an active oxygen scavenging action are contained. Beverages can be served.

It is a figure which shows the carbon dioxide ultrafine bubble making apparatus which concerns on this invention. It is a figure which shows the hydrogen ultra fine bubble making apparatus which concerns on this invention. It is a figure which shows the main part of the IFA measuring apparatus of the ultrafine bubble which concerns on this invention. It is a figure which shows the particle size distribution of the ultrafine bubble which concerns on this invention. It is a figure which shows the stability of the ultrafine bubble which concerns on this invention. It is a figure which shows the adduct of G-CYPMPO and active oxygen in the active oxygen detection method (spin trap method / ESR method) in this invention. It is a figure which shows the hydroxyl radical scavenging action of the ultrafine bubble-containing non-alcoholic aqueous solution which concerns on this invention. It is a figure which shows the superoxide anion scavenging action of the non-alcoholic aqueous solution containing an ultrafine bubble which concerns on this invention. It is a figure which shows the hydroxyl radical scavenging action of the ultrafine bubble containing 100% ethanol solution which concerns on this invention. It is a figure which shows the hydroxyl radical scavenging action of the ultrafine bubble containing 50% ethanol solution which concerns on this invention. It is a figure which shows the hydroxyl radical scavenging action of the 20% ethanol aqueous solution containing an ultrafine bubble which concerns on this invention. It is a figure which shows the hydroxyl radical scavenging action of the ultrafine bubble containing 10% ethanol aqueous solution which concerns on this invention. It is a figure which shows the superoxide anion scavenging action of the ultrafine bubble containing 100% ethanol solution which concerns on this invention. It is a figure which shows the superoxide anion scavenging action of the ultrafine bubble containing 50% ethanol aqueous solution which concerns on this invention. It is a figure which shows the superoxide anion scavenging action of the 20% ethanol aqueous solution containing an ultrafine bubble which concerns on this invention. It is a figure which shows the superoxide anion scavenging action of the ultrafine bubble containing 10% ethanol aqueous solution which concerns on this invention.

Hereinafter, embodiments of the present invention will be described in detail.

(Ultra fine bubble-containing aqueous solution)
The ultrafine bubble-containing aqueous solution according to the present invention is characterized by being an ultrafine bubble-containing aqueous solution containing at least one gas of carbon dioxide and hydrogen inside the ultrafine bubble.

In the ultrafine bubble-containing aqueous solution, at least one of carbon dioxide and hydrogen gas may be contained inside each ultrafine bubble contained in the solution.

The ultrafine bubble-containing aqueous solution may also contain an ultrafine bubble-containing aqueous solution containing both carbon dioxide and hydrogen gases inside the ultrafine bubble.

A bubble is a closed space composed of a gas surrounded by a gas other than a gas, and a bubble completely surrounded by a liquid is a planktonic gas. Among these planktonic gases, bubbles having a diameter of 1 micrometer or less are called ultrafine bubbles (Fine Bubble Society Association).

Since ultrafine bubbles are extremely small bubbles, it is known that the bubbles have a negative potential called the zeta potential, and the bubbles can exist in the liquid for an extremely long time.

In the present invention, carbon dioxide, hydrogen, and an ultrafine bubble containing both carbon dioxide and hydrogen are provided inside the ultrafine bubble, respectively, carbon dioxide ultrafine bubble, hydrogen ultrafine bubble, and carbon dioxide and hydrogen. Also called ultra fine bubble.

Examples of the aqueous solution containing the carbon dioxide ultrafine bubble and the hydrogen ultrafine bubble include water, a salt solution containing various ions, an amino acid solution, and a mixed solution of water and a water-soluble organic solvent. In particular, the aqueous solution containing ultrafine bubbles according to the present invention is preferably a non-alcoholic aqueous solution containing no ethanol and an aqueous alcohol solution containing ethanol.

The ultrafine bubbles in the present invention preferably also have a specific 50% average particle size. Since the gas contained inside the ultrafine bubble has a particle size smaller than a specific 50% average particle size, the stability of the ultrafine bubble is improved and the ultrafine bubble can exist as an ultrafine bubble for a long time. The 50% average particle size in the present invention usually refers to the 50% average particle size with respect to the number of ultrafine bubbles.

The 50% average particle size of the ultrafine bubble containing carbon dioxide inside the ultrafine bubble is preferably in the range of 50 nm to 300 nm, and more preferably in the range of 50 nm to 150 nm. A 50% average particle size in this range allows it to exist as an ultrafine bubble for several days. It is difficult to prepare ultrafine bubble carbon dioxide with a 50% average particle size less than 50 nm.

The 50% average particle size of the ultrafine bubble containing hydrogen inside the ultrafine bubble is preferably in the range of 10 nm to 500 nm, and more preferably in the range of 10 nm to 150 nm. A 50% average particle size in this range allows it to exist as an ultrafine bubble for several days. It is difficult to prepare ultrafine bubbles with a 50% average particle size less than 10 nm.

The ultrafine bubble-containing aqueous solution in the present invention preferably has a specific ultrafine bubble content. In order to exert the antioxidant effect of the ultrafine bubble-containing aqueous solution, it is necessary that a certain amount of gas is contained in the ultrafine bubble.

In the ultrafine bubble-containing aqueous solution of the present invention, the content of the ultrafine bubbles containing carbon dioxide inside the ultrafine bubbles is preferably in the range of 100 million cells / mL to 10 billion cells / mL. More preferably, it is in the range of 10 billion pieces / mL.

In the ultrafine bubble-containing aqueous solution of the present invention, the content of the ultrafine bubbles containing hydrogen inside the ultrafine bubbles is preferably in the range of 10 million cells / mL to 100 billion cells / mL. It is more preferably in the range of 100 million pieces / mL to 50 billion pieces / mL.

(Preparation of ultrafine bubble-containing aqueous solution)
Examples of the method for preparing the ultrafine bubble-containing aqueous solution include spiral flow system method, Pressurized Dissolution System, ultrasonic wave method, passage through porous ceramics, and porosity. Various methods such as passing through a plastic film and a double bottle hydrogen generator are known.

The carbon dioxide ultrafine bubble can be prepared by various methods. Among them, the carbon dioxide ultrafine bubble is prepared by passing carbon dioxide from a pressurized tank through porous ceramics (the porous ceramics passing method) or passing through a porous plastic membrane, and then blowing it into a liquid. (See FIG. 1). As the porous plastic film, a film that removes ordinary fine particles can also be used for nanobubble preparation.

The hydrogen ultrafine bubble can be prepared by various methods. Among them, the hydrogen ultra fine bubble is prepared by electrolysis (electrolysis method for producing fine bubble) using a double bottle hydrogen generator (Woo Co., Ltd., Gas & Water Double Hydrogen Bottle (registered trademark)). Fine bubbles are preferred. A solution containing hydrogen ultrafine bubbles can be prepared by the double bottle hydrogen generator (see FIG. 2).

The carbon dioxide and hydrogen ultrafine bubble aqueous solution (prepared by blowing carbon dioxide in the order of hydrogen) allows carbon dioxide to pass through porous ceramics (the porous ceramics passing method) or a porous plastic film, and then passes through the porous plastic film. It can be prepared by blowing into the solution containing hydrogen ultrafine bubbles, or by causing the carbon dioxide ultrafine bubbles to generate hydrogen ultrafine bubbles by a double bottle hydrogen generator.

Further, the carbon dioxide and hydrogen ultrafine bubble aqueous solution can be prepared by at least one method selected from the group consisting of the pressure dissolution system and the spiral flow system. According to these methods, a large amount of carbon dioxide and hydrogen ultrafine bubble aqueous solution can be prepared.

(Measurement of characteristics of ultrafine bubble-containing aqueous solution)
The characteristics of ultrafine bubbles are measured by the Resonant Mass Method, Particle Trajectory Method, Laser Diffraction Method, and Dynamic Light Scattering Method (DLS Method). ), Interactive Force MFP Method (IFA Method), etc. are known.

The characteristics of the ultrafine bubble in the present invention can be measured by various methods. Among them, in the characteristic measurement of the ultrafine bubble of the present invention, it is possible to measure an ultrafine bubble having a small particle size equivalent to that of the dynamic light scattering method (DLS) method, and since it has high accuracy, the following mutual It is preferable to use a dynamic light scattering (IFA) measurement method.

The ultrafine bubble in the present invention can measure its particle size size distribution in an aqueous solution using the IFA measuring device shown in FIG. 3 (see FIGS. 4 and 5). According to this measuring device, "the particle size distribution of fine bubbles from several nm to several 100 μm can be measured with high accuracy, and the particle concentration, the light transmittance of the liquid, and the refractive index are not affected. "Measurable" (Patent No. 650265, p. 3, paragraph [0009]). An example of this measuring device is shown in FIG. The measured values are in good agreement with those measured by the Dynamic Light Scattering (DLS) method.

The method for measuring an interaction force device is disclosed in Japanese Patent Application Laid-Open No. 2016-109453 (Invention title "Fine bubble particle size distribution measuring method and measuring device", Japanese Patent No. 6502657).

(Characteristics of non-alcoholic aqueous solution containing ultrafine bubbles)
As measured by ultra-fine bubbles above interaction force device method the particle size of the particle size the ultra-fine bubbles in water, (50% average diameter of the bubble size) the carbon dioxide ultrafine bubble particle size was measured to 115 nm, The particle size of the hydrogen ultrafine bubble (50% average diameter of the bubble size) was measured to be 130 nm (see FIG. 4).

Stability of Ultra Fine Bubbles The change in particle size of the Ultra Fine Bubbles (in water) over time was measured by the above-mentioned interaction force device method, and its stability (sustainability) was evaluated. The carbon dioxide ultrafine bubbles existed in distilled water for several days and disappeared after 4 days. The stability of the carbon dioxide ultrafine bubble in distilled water was several days, and the stability due to the ultrafine bubble was confirmed. It was found that the hydrogen ultrafine bubble had a particle size of 25 nm after the lapse of 40 days, and the particle size became smaller with the lapse of time. It was found that the hydrogen ultrafine bubble was stably present even after 40 days (see FIG. 5). A comparison of these stability with the stability of other bubbles is shown in Table 1.

According to the particle size and density measurement, the contents of carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles in the ultrafine bubble-containing aqueous solution are 100 million / mL to 10 billion / mL and 100 million, respectively. It was in the range of / mL to 100 billion pieces / mL.

Table 1 summarizes the content, particle size, and stability of the ultrafine bubble hydrous solution. As is clear from Table 1, the ultrafine bubble according to the present invention has a sufficiently small particle size and an internal content thereof, and can exist stably for a long period of time.

(Characteristics of ultrafine bubble-containing alcoholic aqueous solution)
The approximate particle size of the particle size the ultra-fine bubbles of ultra-fine bubbles was measured by the interaction force system method in the alcoholic solution. One example of the particle size of the carbon dioxide ultrafine bubble (50% average diameter of the bubble size) is 250 nm, 280 nm, 300 nm, and 500 nm in 10%, 20%, 50%, and 100% ethanol aqueous solution or ethanol solution, respectively. One example of the particle size of the hydrogen ultrafine bubble (50% average diameter of the bubble size) measured is 230 nm, 540 nm, 830 nm, 1000 nm in 10%, 20%, 50%, 100% ethanol aqueous solution or ethanol solution. Was measured (see Table 2). Ultrafine bubbles of several hundred nm are present in the aqueous ethanol solution, and the larger the ethanol content in the aqueous solution, the larger the particle size of the ultrafine bubbles tends to be.

The approximate particle size of the carbon dioxide and hydrogen ultrafine bubbles (50% average diameter of the bubble size) is the particle size of carbon dioxide and hydrogen ultrafine bubbles prepared by blowing in the order of hydrogen to carbon dioxide and carbon dioxide to hydrogen. Was measured. In the injection of carbon dioxide from hydrogen, one example of the particle size in the 10%, 20%, and 50% ethanol aqueous solutions was 220 nm, 220 nm, and 104 nm, respectively, and was not observed in the 100% ethanol solution. In the preparation of hydrogen injection from carbon dioxide, one example of the particle size in the 10% and 20% ethanol aqueous solutions was measured to be 200 nm and 460 nm, respectively (see Table 2). Similar to the preparation by blowing carbon dioxide or hydrogen alone, ultrafine bubbles of several hundred nm are present in the aqueous ethanol solution, and the larger the ethanol content in the aqueous solution, the larger the particle size of the ultrafine bubbles tends to be. Be done.

(Measurement method of ROS scavenging action of ultrafine bubble-containing aqueous solution)
For the measurement of hydroxy radical (OH ·) and superoxide anion radical (O ₂ · ⁻ ) in an aqueous solution containing ultrafine bubbles, G-CYPMPO®: 2- (5,5-dimethyl-2-) was used as a spin trapping agent. oxo-2-l5- [1,3,2] dioxaphosphinan-2-yl) -2-methyl-3,4-dihydro-2H-pyrro- line N-oxide {2- (5,5-dimethyl-2-) ESR spectroscope (JES-TE25X manufactured by JEOL) using oxo-1,3,2-dioxaphosphinan-2-yl) -3,4-dihydro-2-methyl-2H-pyrrole N-oxide (chemical formula 1 below) Was done by recording the ESR spectrum of the spin trapping adduct.

In a hydrogen peroxide solution (0.1 w / v%) under UV irradiation, that is, an adduct of hydroxyl radical (OH ·) and G-CYPMPO®, and in a hypoxanthine / xanthine oxidase system, that is, superoxide. anion radicals (O ₂ · ^-) and showed ESR spectrum of the adduct of G-CYPMPO (registered trademark) in Fig. In the figure, the diamond mark (◆) indicates _{the peak of the superoxide anion radical (O 2} · ⁻ ) adduct, and the inverted triangle mark (▼) indicates the peak of the hydroxyl radical (OH ·) adduct. The peak-to-peak intensity of both peaks is used for measuring the amount of active oxygen.

The Kohri's ESR spin trap method, which is a typical method, was used for data analysis. The peak-to-peak intensity of the selected ESR line of the free radical adduct is followed in the presence and absence of antioxidants.

It is conceivable that a wrapping reaction with the following free radicals (R) occurs in the presence of a spin trapping agent (SP) and an antioxidant (AO).
R + SP → R adduct rate constant: tk _sp (1)
R + AO → Product rate constant: k _AO (2)
If I ₀ and I are the ESR peak heights in the presence of ST only and ST + AO, respectively, the amount of product in formula (2) is I _0- I. Therefore, I ₀ / I-1 is calculated to quantify the free radical capture capacity.

To quantify the free radical capture capacity, the oxidant species is mixed with the free radical generating system hours prior to ESR measurements. When I ₀ and I have ESR peak heights in the presence of ST alone and ST + oxidant, respectively, the amount of free radical generation system oxidized to the oxidant species is I _0- I. Therefore, I ₀ / I-1 is calculated to quantify the free radical capture capacity.

(ROS scavenging action of non-alcoholic aqueous solution containing ultrafine bubbles)
The ultrafine bubble-containing solution according to the present invention has an active oxygen (ROS) scavenging action. In particular, the carbon dioxide ultrafine bubble-containing solution is hydroxy radicals have the scavenging action of (OH ·) (see FIG. 7), a solution containing the ultra-fine bubble hydrogen superoxide anion radical - erasing (O 2 ^_·) The action is remarkable (see FIG. 8).

That is, the carbon dioxide ultrafine bubbles (hereinafter referred to as "porous ceramics carbon dioxide UFB") prepared by passing carbon dioxide from the pressurized tank through the porous ceramics (the above-mentioned porous ceramics passing method) are combined with hydrogen peroxide. It has a high scavenging effect on hydroxy radicals (OH ·) generated using an ultraviolet lamp. On the other hand, hydrogen ultrafine bubbles (hereinafter referred to as "hydrogen UFB") prepared by electrolysis (the above-mentioned electrolysis method for producing fine bubbles) using a double bottle hydrogen generator (Gas & Water Double Hydrogen Bottle (registered trademark)). Does not have an scavenging effect on the hydroxy radical (OH ·) (see FIG. 7 above).

Further, the hydrogen UFB has a high scavenging effect of _{superoxide anion radicals (O 2} · ^−). Hydrogen ultrafine bubbles showed the highest scavenging effect 24 hours after preparation. On the other hand, the porous ceramic carbon dioxide UFB has a weak or no scavenging action of _{superoxide anion radicals (O 2} · ^{−) (see FIG. 8).}

As described above, the non-alcoholic aqueous solution containing the ultrafine bubbles according to the present invention has a hydroxyl radical scavenging action, and from the viewpoint of the strength of the hydroxyl radical scavenging action, carbon dioxide ultrafine bubbles, or carbon dioxide and hydrogen. Ultrafine bubbles are preferred, and carbon dioxide ultrafine bubbles are even more preferred (see FIGS. 7 and 3).

Further, the non-alcoholic aqueous solution containing the ultrafine bubbles according to the present invention has a superoxide anion radical scavenging action, and from the viewpoint of the strength of the superoxide anion radical scavenging action, hydrogen ultrafine bubbles, carbon dioxide and carbon dioxide. Hydrogen ultrafine bubbles are preferred (see FIGS. 8 and 4).

Further, the non-alcoholic aqueous solution containing ultrafine bubbles according to the present invention has an scavenging action of both hydroxyl radicals and superoxide anion radicals, and from the viewpoint of the strength of the ROS scavenging action, carbon dioxide and hydrogen ultrafine bubbles are present. Preferred (see FIGS. 7 and 8, Tables 3 and 4).

(ROS scavenging action of alcoholic aqueous solution containing ultrafine bubbles)
The ultrafine bubble-containing alcohol aqueous solution according to the present invention is characterized in that the alcoholic aqueous solution containing ultrafine bubbles contains at least one ultrafine bubble selected from the group consisting of carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles. And. Since the alcohol aqueous solution contains the ultrafine bubbles, it can have an active oxygen scavenging action.

The alcohol aqueous solution containing the carbon dioxide ultrafine bubble has an action of scavenging active oxygen, particularly hydroxyl radical. The alcoholic aqueous solution containing the carbon dioxide ultrafine bubble has a strong hydroxyl radical scavenging effect at any alcohol content even if the alcohol content in the alcoholic aqueous solution fluctuates (Table 5 and FIGS. 9 to 12). ..

The alcohol aqueous solution containing the carbon dioxide ultrafine bubble has an action of scavenging active oxygen, but has a weak action of scavenging superoxide anions. The active oxygen scavenging action of the superoxide anion fluctuates due to the fluctuation of the alcohol content in the alcohol aqueous solution. When the alcohol content in the alcohol aqueous solution is high, the active oxygen scavenging action tends to be weak, and when the alcohol content is low, the active oxygen scavenging action tends to be strong. The alcohol aqueous solution containing carbon dioxide ultrafine bubbles has an alcohol content of 20% or less and has a superoxide anion scavenging action (Table 6 and FIGS. 13 to 16).

The hydroxyl radical scavenging action of the alcohol aqueous solution containing the hydrogen ultrafine bubble varies depending on the ethanol content in the alcohol aqueous solution. The hydroxyl radical scavenging action is not observed in the ethanol solution having a 100% content, and tends to become stronger as the ethanol content decreases. When the ethanol content in the alcohol aqueous solution is 10%, a hydroxyl radical scavenging action is observed (Table 5 and FIGS. 9 to 12).

The superoxide anion scavenging action of the alcohol aqueous solution containing the hydrogen ultrafine bubble also varies depending on the ethanol content in the alcohol aqueous solution. The superoxide anion scavenging action is not observed in an ethanol solution having a 100% content, and tends to become stronger as the ethanol content decreases. When the ethanol content in the alcohol aqueous solution is 10%, a hydroxyl radical scavenging action is observed (Table 6 and FIGS. 13 to 16).

The alcohol aqueous solution containing carbon dioxide and hydrogen ultrafine bubbles has a hydroxyl radical scavenging action. In particular, an alcohol aqueous solution containing carbon dioxide and hydrogen ultrafine bubbles prepared by blowing in the order of hydrogen to carbon dioxide has a strong hydroxyl radical scavenging action regardless of the ethanol content in the alcohol aqueous solution (Tables 5 and 9). ~ 12).

The alcohol aqueous solution containing carbon dioxide and hydrogen ultrafine bubbles has a superoxide anion scavenging action. The superoxide anion scavenging action tends to become stronger as the ethanol content decreases. When the ethanol content in the alcohol aqueous solution is 20% or less, a strong superoxide anion scavenging action is observed. In particular, an alcohol aqueous solution containing carbon dioxide and hydrogen ultrafine bubbles prepared by blowing in the order of hydrogen to carbon dioxide has a strong hydroxyl radical scavenging action when the ethanol content in the alcohol aqueous solution is 20% or less (Table). 6 and FIGS. 13 to 16).

Regarding the alcoholic aqueous solution containing ultrafine bubbles according to the present invention, the aqueous solution containing carbon dioxide ultrafine bubbles has a hydroxyl radical scavenging action, but the superoxide anion scavenging action is weak. In the hydrogen ultrafine bubble-containing aqueous solution, the hydroxyl radical scavenging action and the superoxide anion scavenging action are weak, but the lower the ethanol content in the ultrafine bubble-containing aqueous solution, the stronger the active oxygen scavenging action tends to be.

Regarding the alcoholic aqueous solution containing ultrafine bubbles according to the present invention, a relatively stable and strong active oxygen scavenging action is observed in the alcoholic aqueous solution containing carbon dioxide and hydrogen ultrafine bubbles. In particular, a strong active oxygen scavenging action is observed in an alcohol solution containing carbon oxide and hydrogen ultrafine bubbles prepared by blowing in the order of hydrogen to carbon dioxide.

As described above, as for the alcoholic aqueous solution containing ultrafine bubbles according to the present invention, the carbon dioxide ultrafine bubble-containing alcohol aqueous solution and the carbon dioxide and hydrogen ultrafine bubble-containing alcohol aqueous solutions are preferable for the hydroxyl radical scavenging action. Further, an aqueous alcohol solution containing carbon dioxide and hydrogen ultrafine bubbles is preferable for the action of scavenging active oxygen (hydroxy radicals and superoxide anions).

(Beverage containing ultra fine bubbles)
The ultrafine bubble-containing beverage according to the present invention is characterized by containing the ultrafine bubble-containing aqueous solution according to the present invention. Since the ultrafine bubble-containing aqueous solution contains at least one ultrafine bubble selected from the group consisting of carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles, it can have an action of scavenging active oxygen. Since the ultrafine bubble-containing beverage contains the ultrafine bubble-containing aqueous solution, it can have an action of scavenging active oxygen, particularly hydroxyl radicals and / or superoxide anions.

Since the ultrafine bubble-containing beverage contains carbon dioxide ultrafine bubbles, hydrogen ultrafine bubbles, or carbon dioxide and hydrogen ultrafine bubbles, it has an active oxygen scavenging effect, particularly, sustained hydroxyl radicals and / or superoxide anions. By having an erasing action, it is expected to maintain health, recover from fatigue, and prevent various diseases.

The beverage according to the present invention includes various beverages, but a soft drink as a non-alcoholic aqueous solution and an alcoholic beverage as an alcoholic aqueous solution are preferable.

(Soft drink containing ultra fine bubbles)
The ultrafine bubble-containing soft drink according to the present invention is characterized by containing at least one ultrafine bubble selected from the group consisting of carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles.

The soft drink according to the present invention is a non-alcoholic aqueous solution and does not contain ethanol, although there are differences in the inclusions other than water. Non-alcoholic beverages are aqueous solutions containing less than 1% by volume of alcohol (ethanol) and are contained in soft drinks (Food Sanitation Law). However, since it contains ethanol, it is not included in the soft drink according to the present invention.

Since the soft drink according to the present invention is an aqueous solution containing carbon dioxide ultrafine bubbles, hydrogen ultrafine bubbles, or carbon dioxide and hydrogen ultrafine bubbles, it has an active oxygen scavenging effect, particularly hydroxyl radicals and / or superoxide anions. By having a continuous scavenging action, it is expected to maintain health, recover from fatigue, and prevent various diseases.

The ultrafine bubble-containing soft drink refers to "all beverages except lactic acid bacteria beverages, milk, dairy products, and alcohol (1% by volume or more of alcohol)" (Food Sanitation Law). Examples of the soft drink include carbonated drinks such as ramune, cider and cola, fruit tree drinks, vegetable drinks such as tomato juice, coffee drinks, tea-based drinks, sports drinks, mineral water and soy milk. As described above, the alcoholic beverage according to the present invention is not included.

(Alcoholic beverage containing ultra fine bubbles)
The alcoholic beverage according to the present invention is characterized by containing at least one ultrafine bubble selected from the group consisting of carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles.

The alcoholic beverage is an ethanol-containing aqueous solution containing 1% by volume or more of alcoholic beverage. The non-alcoholic beverage is generally not included in the alcoholic beverage because it is an aqueous solution containing less than 1% by volume of alcohol (ethanol), but it is included in the alcoholic beverage according to the present invention.

Since the alcoholic beverage according to the present invention is an aqueous solution containing carbon dioxide ultrafine bubbles, hydrogen ultrafine bubbles, or carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles, it has an active oxygen scavenging effect, particularly hydroxyl radicals and / or super. By having a continuous scavenging action of oxide anions, it is expected to maintain health, recover from fatigue, and prevent various diseases.

In the alcoholic beverage according to the present invention, the alcoholic beverage is a beverage containing ethyl alcohol, and refers to sake, peel, wine, whiskey, and the like.

(Manufacturing of non-alcoholic aqueous solution containing ultrafine bubbles)
The method for producing a non-alcoholic aqueous solution containing the carbon dioxide ultrafine bubble and the hydrogen ultrafine bubble according to the present invention is the same as the aqueous solution containing the carbon dioxide ultrafine bubble and the hydrogen ultrafine bubble. It can be manufactured by changing the bubble preparation order (gas blowing order).

That is, as described above, the ultrafine bubble-containing non-alcoholic aqueous solution containing the carbon dioxide ultrafine bubbles and the hydrogen ultrafine bubbles is further added to the ultrafine bubble-containing non-alcoholic aqueous solution containing hydrogen ultrafine bubbles, and carbon dioxide is further added. It is possible to obtain an ultrafine bubble-containing non-alcoholic aqueous solution containing carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles.

Further, the ultrafine bubble-containing non-alcoholic aqueous solution containing the carbon dioxide ultrafine bubble and the hydrogen ultrafine bubble is further blown with hydrogen into the ultrafine bubble-containing aqueous solution containing the carbon dioxide ultrafine bubble as described above. It can be produced to obtain an ultrafine bubble-containing non-alcoholic aqueous solution containing carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles.

The soft drink according to the present invention can be produced in the same manner as the ultrafine bubble-containing non-alcoholic aqueous solution.

(Manufacturing of alcoholic aqueous solution containing ultrafine bubbles)
The method for producing an alcoholic aqueous solution containing the carbon dioxide ultrafine bubble and the hydrogen ultrafine bubble according to the present invention is the same as the aqueous solution containing the carbon dioxide ultrafine bubble and the hydrogen ultrafine bubble. And two ultrafine bubbles corresponding to hydrogen ultrafine bubbles are produced by changing the preparation order (gas blowing order).

That is, the ultrafine bubble-containing alcoholic aqueous solution containing the carbon dioxide ultrafine bubbles and the hydrogen ultrafine bubbles further blows carbon dioxide into the ultrafine bubble-containing alcoholic aqueous solution containing the hydrogen ultrafine bubbles as described above. It is possible to obtain an ultrafine bubble-containing alcoholic aqueous solution containing carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles.

Further, the ultrafine bubble-containing alcoholic aqueous solution containing the carbon dioxide ultrafine bubbles and the hydrogen ultrafine bubbles further blows hydrogen into the ultrafine bubble-containing alcoholic aqueous solution containing the carbon dioxide ultrafine bubbles as described above. It is possible to obtain an ultrafine bubble-containing alcoholic aqueous solution containing carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles.

The alcoholic beverage according to the present invention can be produced in the same manner as the ultrafine bubble-containing alcoholic aqueous solution.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

(1) Preparation of Ultrafine Bubble-Containing Aqueous Solution According to the Present Invention Experimental Example 1: Preparation of Carbon Dioxide Ultrafine Bubble-Containing Aqueous Solution According to the Present Invention The carbon dioxide ultrafine bubble-containing aqueous solution is magnetic as shown in FIG. _{Carbon dioxide (CO 2} , 99.5%) in argon gas from a pressurized tank in a beaker containing 200 mL of water for 30 minutes at a rate of 0.4 L / min while stirring using a stirrer. It was prepared by passing through porous ceramics (the above-mentioned porous ceramics passing method). The ultrafine bubble carbon dioxide in the aqueous solution is also hereinafter referred to as "UFB / CO ₂ ".

Experimental Example 2: Preparation of an aqueous solution containing a hydrogen ultrafine bubble according to the present invention As shown in FIG. 2, the hydrogen ultrafine bubble is used in a double bottle hydrogen generator (Gas & Water Double Hydrogen Bottle (registered trademark) manufactured by Woo). ) (Hereinafter, also referred to as _{“UFB / EH 2”).} The aqueous solution containing hydrogen ultrafine bubbles was prepared in 200 mL of water for 30 minutes. The concentration of hydrogen ultrafine bubbles by electrolysis was 0.15% by volume, and was quantified using a specific gravity bottle.

Experimental Example 3: Preparation of an aqueous solution containing carbon dioxide and hydrogen ultrafine bubbles according to the present invention The aqueous solution containing carbon dioxide and hydrogen ultrafine bubbles is used in the aqueous solution containing hydrogen ultrafine bubbles (prepared in the previous section (Experimental Example 2)). _{, Carbon dioxide (CO 2} , 99.) in argon gas from the pressurized tank for 30 minutes at a rate of 0.4 L / min while stirring using a magnetic stirrer as in the method of the previous section (Experimental Example 1). 5%) was prepared by blowing. Alternatively, the carbon dioxide and hydrogen ultrafine bubble aqueous solution is electrolyzed into the carbon dioxide ultrafine bubble-containing aqueous solution (created in the previous section (Experimental Example 1)) for 30 minutes according to the method in the previous section (Experimental Example 2). Was prepared by performing.

(2) Preparation of Ultrafine Bubble-Containing Alcohol Aqueous Solution According to the Present Invention Experimental Example 4: Preparation of Carbonated Carbonate Ultrafine Bubble-Containing Alcohol Solution According to the Present Invention , 50%, 20%, 10% ethanol) with a magnetic stirrer as shown in FIG. 1 at a rate of 0.4 L / min for 30 minutes in the alcohol gas from the pressurized tank. Passing through porous ceramics in a beaker containing 200 mL of alcohol aqueous solution or alcohol solution (100%, 50%, 20%, 10% ethanol) of carbon (CO _{2, 99.5%) (the porous ceramics passing method).} ) To prepare. The carbon dioxide ultrafine bubble in the aqueous solution is also hereinafter referred to as "UFB / CO ₂ ".

Experimental Example 5: Preparation of an aqueous solution of an alcohol containing a hydrogen ultrafine bubble according to the present invention As shown in FIG. 2, the hydrogen ultrafine bubble is subjected to a double bottle hydrogen generator (Gas & Water Double Hydrogen Bottle (registered trademark) manufactured by Woo). )) Was produced by electrolysis (the above-mentioned electrolysis method for producing fine bubbles). The hydrogen ultrafine bubble-containing alcohol aqueous solution or alcohol solution (100%, 50%, 20%, 10% ethanol) is added to 200 mL of the alcohol aqueous solution or alcohol solution (100%, 50%, 20%, 10% ethanol) 30 times. Prepared in minutes. The concentration of hydrogen ultrafine bubbles by electrolysis was 0.15% by volume, and was quantified using a specific gravity bottle.

Experimental Example 6: Preparation of carbon dioxide and hydrogen ultrafine bubble-containing alcohol aqueous solution according to the present invention The carbon dioxide and hydrogen ultrafine bubble-containing alcohol aqueous solution or alcohol solution is the hydrogen ultrafine bubble-containing alcohol aqueous solution or alcohol solution ( 100%, 50%, 20%, 10% ethanol) (prepared in the previous section (Experimental Example 2)), 0.4 L / L / while stirring using a magnetic stirrer as in the previous section (Experimental Example 1). It was prepared by blowing _{carbon dioxide (CO 2} , 99.5%) in argon gas from a pressurized tank for 30 minutes at a rate of minutes. Alternatively, the carbon dioxide and hydrogen ultrafine bubble-containing alcohol solution or alcohol solution is the carbon dioxide ultrafine bubble-containing alcohol aqueous solution or alcohol solution (100%, 50%, 20%, 10% ethanol) (previous item (experimental example). It was prepared by performing electrolysis for 30 minutes according to the method of the previous section (Experimental Example 2) in 1)).

(3) Measurement of Ultrafine Bubble-Containing Solution in the Present Invention by IFA Measuring Device The ultrafine bubble in the present invention is measured in water or an alcohol aqueous solution by using the IFA measuring device shown in FIG. The particle size distribution was measured by the IFA method shown in "Bubble particle size distribution measuring method and measuring device" (see FIGS. 4 and 5).

(4) ROS scavenging action of ultrafine bubble-containing solution in the present invention Experimental example 7: Generation of active oxygen (ROS) Hydroxyl radical (OH ·) is 5s ultraviolet radiation of a UV radiator (made by UV LIGHTSOURCE, SUPERCURE-203S). Below, it was produced by decomposition of 0.1 w / t% hydrogen peroxide (H ₂ O _2). A mixture of 90 μL of 0.2 w / t% hydrogen peroxide and 20 μL of 100 mM G-CYPMPO was transferred to a disposable borosilicate ESR cell, and the ESR spectrum of the adduct of hydroxyl radical and G-CYPMPO was analyzed.

Superoxide anion radicals _{(O 2} · ^-) were then produced in hypoxanthine / xanthine (HX / XO) system. A mixture of 10.970 units / mL XO, 20 mM HX 20 μL, and 100 mM G-CYPMPO 20 μL was transferred to a disposable borosilicate ESR cell and the ESR spectrum of the adduct of hydroxyl radicals and G-CYPMPO was analyzed.

Experimental Example 8: Measurement of active oxygen by ESR A novel radical trapper 2- (5,5-dimethyl-2-oxo-2-l5-[1,3,2] dioxaphosphinan-2-yl) -2- methyl-3,4-dihydro-2H-pyrro-line N-oxide {2-(5,5-dimethyl-2-oxo-1,3,2-dioxaphosphinan-2-yl) -3,4-dihydro-2 -Methyl-2H-pyrrole N-oxide, G-CYPMPO® was used to capture the free radicals of reactive oxygen species. 25 mg of G-CYPMPO® (100 mL) was dissolved in 2 mL of ultrapure water.

The ESR spectrum of the spin trapping adduct was recorded using an ESR spectrometer (JES-TE25X manufactured by JEOL). Typical ESR measurement conditions were as follows.
Microwave power: 4 mW, microwave frequency: 9.2 GHz, magnetic field: 328.0 mT, field sweep with: ± 7.5 mT, field modulation: 0.16 mT, sweep time: 1 minute, 0.003663 mT / Points, all 4096 points, ESR measurements were performed at room temperature.

The Kohri's ESR spin trap method, which is a typical method, was used for data analysis. The peak-to-peak intensity of the selected ESR line of the free radical adduct was followed in the presence and absence of antioxidants.

In the presence of the spin trapping agent (SP) and the antioxidant (AO), a wrapping reaction with the following free radicals (R) occurs.
R + SP → R adduct rate constant: tk _sp (1)
R + AO → Product rate constant: k _AO (2)
If I ₀ and I are the ESR peak heights in the presence of ST only and ST + AO, respectively, the amount of product in formula (2) is I _0- I. Therefore, I ₀ / I-1 was calculated to quantify the free radical capture capacity.

To quantify the free radical capture capacity, the oxidant species is mixed with the free radical generating system hours prior to ESR measurement. When I ₀ and I have ESR peak heights in the presence of ST alone and ST + oxidant, respectively, the amount of free radical generation system oxidized to the oxidant species is I _0- I. Therefore, I ₀ / I-1 was calculated to quantify the free radical capture capacity.

Examples 1 to 5: Hydroxyl radical (OH ·) scavenging action of ultrafine bubble-containing non-alcoholic aqueous solution according to the present invention Control Example 1: Ultrafine bubble-free, Example 2: Carbon dioxide ultrafine bubble-containing, reference Example 3: Hydrogen ultrafine bubble containing, Example 4: Carbon dioxide and hydrogen ultrafine bubble containing (prepared by blowing in the order of hydrogen to carbon dioxide), and Example 5: Carbon dioxide and hydrogen ultrafine bubble containing (from carbon dioxide) The hydroxyl radical (OH ·) scavenging action of each aqueous solution (prepared by injecting hydrogen in this order) was examined by ESR measurement. FIG. 7 shows _{I 0} / I-1 obtained from the ESR spectrum of the G-CYPMPO (registered trademark) adduct of the ultrafine bubble-containing solution.

Based on FIG. 7, Table 3 shows the strength of the erasing action as strong ⊚, moderate ◯, weak Δ, and x with little or no erasing action. A strong hydroxyl radical scavenging action was observed in the carbon dioxide ultrafine bubble-containing aqueous solution (Example 2). In the carbon dioxide and hydrogen ultrafine bubble-containing aqueous solutions (Examples 4 and 5), a hydroxyl radical scavenging action at mid-latitude was observed. In the hydrogen ultrafine bubble-containing aqueous solution (Reference Example 3), almost no hydroxyl radical scavenging action was observed.

As shown in FIGS. 7 and 3, regarding the hydroxyl radical scavenging action of the non-alcoholic aqueous solution containing ultrafine bubbles according to the present invention, from the viewpoint of its strength, carbon dioxide ultrafine bubbles or carbon dioxide and hydrogen ultra It was found that it is preferable to use fine bubbles, and it is more preferable to use carbon dioxide ultrafine bubbles.

_{Examples 6 to 10: Superoxide anion (O 2} · ^- ) scavenging action of the non-alcoholic aqueous solution containing ultrafine bubbles according to the present invention Control example 6: Does not contain ultrafine bubbles, Reference example 7: Contains carbon dioxide ultrafine bubbles , Example 8: Hydrogen ultrafine bubble containing, Example 9: Carbon dioxide and hydrogen ultrafine bubble containing (prepared by blowing in order from hydrogen to carbon dioxide), and Example 10: Carbon dioxide and hydrogen ultrafine bubble containing (carbon dioxide) each aqueous superoxide anion of blown preparation) in the order of hydrogen from carbon (· O ₂ ^-) was investigated by ESR measurement erasing action. FIG. 8 shows _{I 0} / I-1 obtained from the ESR spectrum of the G-CYPMPO® adduct of the ultrafine bubble-containing solution.

Based on FIG. 8, Table 4 shows the strength of the erasing effect as strong ⊚, moderate ◯, weak Δ, and × with little or no erasing effect. In the hydrogen ultrafine bubble-containing aqueous solution (Example 8) and the carbon dioxide and hydrogen ultrafine bubble-containing aqueous solutions (Examples 9 and 10), a superoxide anion scavenging action at mid-latitude was observed. On the other hand, in the carbon dioxide ultrafine bubble-containing aqueous solution (Reference Example 7), almost no superoxide anion scavenging action was observed.

As shown in FIGS. 8 and 4, regarding the superoxide anion scavenging action of the non-alcoholic aqueous solution containing the ultrafine bubble according to the present invention, from the viewpoint of its strength, hydrogen ultrafine bubble or carbon dioxide and hydrogen ultrafine. It turned out that it was preferable to use bubbles.

Based on Tables 3 and 4, regarding the active oxygen scavenging action of the non-alcoholic aqueous solution containing ultrafine bubbles according to the present invention, carbon dioxide and hydrogen ultra have a scavenging action on both hydroxyl radicals and superoxide anions. It was found that it is preferable to use fine bubbles.

Examples 11 to 15: Hydroxyl radical (OH ·) scavenging action of the ultrafine bubble-containing alcohol solution (100%) according to the present invention Control Example 11: Ultrafine bubble free, Example 12: Carbon dioxide ultrafine bubble content , Example 13: Hydrogen ultrafine bubble containing, Example 14: Carbon dioxide and hydrogen ultrafine bubble containing (prepared by blowing in order from hydrogen to carbon dioxide), and Example 15: Carbon dioxide and hydrogen ultrafine bubble containing (carbon dioxide) The hydroxy radical (OH ·) scavenging action of each 100% ethanol solution (prepared by blowing in the order of carbon to hydrogen) was examined by ESR measurement. FIG. 9 shows _{I 0} / I-1 obtained from the ESR spectrum of the G-CYPMPO (registered trademark) adduct of the ultrafine bubble-containing solution.

Based on FIG. 9, Table 5 shows the strength of the erasing action as strong ⊚, moderate ◯, weak Δ, and x with little or no erasing action. A strong hydroxyl radical scavenging effect was observed in the carbon dioxide ultrafine bubble-containing ethanol solution (Example 12). In the hydrogen ultrafine bubble-containing ethanol solution (Reference Example 13) and the carbon dioxide and hydrogen ultrafine bubble-containing ethanol solution (Examples 14 and 15), a hydroxyl radical scavenging effect at mid-latitude was observed.

Examples 16 to 20: Hydroxyl radical (OH ·) scavenging action of the ultrafine bubble-containing alcohol aqueous solution (50%) according to the present invention Control example 16: Ultrafine bubble free, Example 17: Carbon dioxide ultrafine bubble content , Example 18: hydrogen ultrafine bubble containing, Example 19: carbon dioxide and hydrogen ultrafine bubble containing (prepared by blowing in order from hydrogen to carbon dioxide), and Example 20: carbon dioxide and hydrogen ultrafine bubble containing (carbon dioxide). The hydroxy radical (OH ·) scavenging action of each 50% ethanol aqueous solution (prepared by blowing in the order of carbon to hydrogen) was examined by ESR measurement. FIG. 10 shows _{I 0} / I-1 obtained from the ESR spectrum of the G-CYPMPO (registered trademark) adduct of the ultrafine bubble-containing solution.

Based on FIG. 10, Table 5 shows the strength of the erasing action as strong ⊚, moderate ◯, weak Δ, and x with little or no erasing action. A strong hydroxyl radical scavenging action was observed in the carbon dioxide ultrafine bubble-containing ethanol aqueous solution (Example 17) and the carbon dioxide and hydrogen ultrafine bubble-containing alcohol aqueous solution (Example 19). In the carbon dioxide and hydrogen ultrafine bubble-containing alcohol aqueous solution (Example 20), a hydroxyl radical scavenging action at mid-latitude was observed. A weak hydroxyl radical scavenging action was observed in the hydrogen ultrafine bubble-containing alcohol aqueous solution (Example 18).

Examples 21 to 25: Hydroxyl radical (OH ·) scavenging action of the ultrafine bubble-containing alcohol aqueous solution (20%) according to the present invention Control example 21: Ultrafine bubble free, Example 22: Carbon dioxide ultrafine bubble content , Example 23: Hydrogen ultrafine bubble containing, Example 24: Carbon dioxide and hydrogen ultrafine bubble containing (prepared by blowing in order from hydrogen to carbon dioxide), and Example 25: Carbon dioxide and hydrogen ultrafine bubble containing (carbon dioxide) The hydroxy radical (OH ·) scavenging action of each 20% ethanol aqueous solution (prepared by blowing in the order of carbon to hydrogen) was examined by ESR measurement. FIG. 11 shows _{I 0} / I-1 obtained from the ESR spectrum of the G-CYPMPO® adduct of the ultrafine bubble-containing solution.

Based on FIG. 11, Table 5 shows the strength of the erasing action as strong ⊚, moderate ◯, weak Δ, and x with little or no erasing action. A strong hydroxyl radical scavenging action was observed in the carbon dioxide ultrafine bubble-containing alcohol aqueous solution (Example 22) and the carbon dioxide and hydrogen ultrafine bubble-containing alcohol aqueous solution (Example 24). In the carbon dioxide and hydrogen ultrafine bubble-containing alcohol aqueous solution (Example 25), a hydroxyl radical scavenging action at mid-latitude was observed. A weak hydroxyl radical scavenging effect was observed in the hydrogen ultrafine bubble-containing alcohol aqueous solution (Reference Example 23).

Examples 26 to 30: Hydroxyl radical (OH ·) scavenging action of the ultrafine bubble-containing alcohol aqueous solution (10%) according to the present invention Control example 26: Ultrafine bubble free, Example 27: Carbon dioxide ultrafine bubble content , Example 28: hydrogen ultrafine bubble containing, Example 29: carbon dioxide and hydrogen ultrafine bubble containing (prepared by blowing in order from hydrogen to carbon dioxide), and Example 30: carbon dioxide and hydrogen ultrafine bubble containing (carbon dioxide). The hydroxy radical (OH ·) scavenging action of each 10% ethanol aqueous solution (prepared by blowing in the order of carbon to hydrogen) was examined by ESR measurement. FIG. 12 shows _{I 0} / I-1 obtained from the ESR spectrum of the G-CYPMPO® adduct of the ultrafine bubble-containing solution.

Based on FIG. 12, Table 5 shows the strength of the erasing action as strong ⊚, moderate ◯, weak Δ, and x with little or no erasing action. A strong hydroxyl radical scavenging action was observed in the carbon dioxide ultrafine bubble-containing alcohol aqueous solution (Example 27) and the carbon dioxide and hydrogen ultrafine bubble-containing alcohol aqueous solution (Example 29). In the hydrogen ultrafine bubble-containing alcohol aqueous solution (Example 28) and the carbon dioxide and hydrogen ultrafine bubble-containing alcohol aqueous solution (Example 30), a hydroxyl radical scavenging action at mid-latitude was observed.

As shown in FIGS. 9 to 12 and Table 5, carbon dioxide ultrafine bubbles or carbon dioxide and hydrogen ultrafine bubbles may be used for the hydroxyl radical scavenging action of the ultrafine bubble-containing alcoholic aqueous solution according to the present invention. It has been found that it is preferable to use carbon dioxide and hydrogen ultrafine bubbles (prepared by blowing in the order of hydrogen to carbon dioxide) from the viewpoint of the strength of the hydroxyl radical scavenging action. It was also found that when the ethanol content of the ultrafine bubble-containing alcohol aqueous solution becomes low, hydrogen ultrafine bubbles also have a hydroxyl radical scavenging effect.

_{Examples 31 to 35: Superoxide anion (O 2} · ⁻ ) scavenging action of the ultrafine bubble-containing alcohol solution (100%) according to the present invention Control Example 31: Ultrafine bubble-free, Example 32: Carbon dioxide ultra Fine bubble containing, Reference Example 33: Hydrogen ultrafine bubble containing, Example 34: Carbon dioxide and hydrogen ultrafine bubble containing (prepared by blowing in the order of carbon dioxide to carbon dioxide), and Example 35: Carbon dioxide and hydrogen ultrafine bubble _{The superoxide anion (O 2} · ^- ) scavenging action of each 100% ethanol solution containing (prepared by blowing in the order of carbon dioxide to hydrogen) was examined by ESR measurement. FIG. 13 shows _{I 0} / I-1 obtained from the ESR spectrum of the G-CYPMPO® adduct of the ultrafine bubble-containing solution.

Based on FIG. 13, the strength of the erasing action is shown in Table 6 with strong ⊚, moderate ◯, weak Δ, and × with little or no erasing action. A weak superoxide anion scavenging effect was observed in the carbon dioxide ultrafine bubble-containing ethanol solution (Example 32) and the carbon dioxide and hydrogen ultrafine bubble-containing ethanol solution (Examples 34 and 35). In the hydrogen ultrafine bubble-containing ethanol solution (Reference Example 33), almost no superoxide anion scavenging action was observed.

_{Examples 36 to 40: Superoxide anion (O 2} · ⁻ ) scavenging action of ultrafine bubble-containing alcohol aqueous solution (50%) according to the present invention Control example 36: Ultrafine bubble-free, Reference example 37: Carbon dioxide ultra Fine bubble containing, Example 38: Hydrogen ultrafine bubble containing, Example 39: Carbon dioxide and hydrogen ultrafine bubble containing (prepared by blowing carbon dioxide in this order), and Example 40: Carbon dioxide and hydrogen ultrafine bubble _{The superoxide anion (O 2} · ^- ) scavenging action of each 50% ethanol aqueous solution of the content (prepared by blowing in the order of carbon dioxide to hydrogen) was examined by ESR measurement. FIG. 14 shows _{I 0} / I-1 obtained from the ESR spectrum of the G-CYPMPO® adduct of the ultrafine bubble-containing solution.

Based on FIG. 14, Table 6 shows the strength of the erasing action by strong ⊚, moderate ◯, weak Δ, and x with little or no erasing action. Hydrogen ultra-fine bubbles containing an aqueous alcohol solution (Example 38), the carbon dioxide and hydrogen ultra-fine bubbles containing an aqueous alcohol solution (Example 39), a weak superoxide anion (O ₂ · ^-) scavenging action was observed. In the carbon dioxide and hydrogen ultrafine bubble-containing alcohol aqueous solution (Example 40), a superoxide anion scavenging action at mid-latitude was observed. In the carbon dioxide ultrafine bubble-containing ethanol aqueous solution (Example 37), almost no superoxide anion scavenging action was observed.

_{Examples 41 to 45: Superoxide anion (O 2} · ⁻ ) scavenging action of the ultrafine bubble-containing alcohol aqueous solution (20%) according to the present invention Control Example 41: Ultrafine bubble-free, Example 42: Carbon dioxide ultra Fine Bubble Containing, Reference Example 43: Hydrogen Ultra Fine Bubble Containing, Example 44: Carbon Dioxide and Hydrogen Ultra Fine Bubble Containing (from Hydrogen to Carbon Dioxide), and Example 45: Carbon Dioxide and Hydrogen Ultra Fine Bubble Containing (From Carbon Dioxide) _{The superoxide anion (O 2} · ^- ) scavenging action of each 20% ethanol aqueous solution of hydrogen) was examined by ESR measurement. FIG. 15 shows _{I 0} / I-1 obtained from the ESR spectrum of the G-CYPMPO® adduct of the ultrafine bubble-containing solution.

Based on FIG. 15, Table 6 shows the strength of the erasing action as strong ⊚, moderate ◯, weak Δ, and x with little or no erasing action. Carbon dioxide ultrafine bubble-containing alcohol aqueous solution (Example 42), carbon dioxide and hydrogen Ultrafine bubble-containing alcohol aqueous solution (Examples 44 and 45) showed moderate to strong superoxide anion scavenging action, and in particular, carbon dioxide. In addition, a strong superoxide anion scavenging action was observed in the hydrogen ultrafine bubble-containing alcohol aqueous solution (Example 45). On the other hand, in the hydrogen ultrafine bubble-containing alcohol aqueous solution (Example 43), almost no superoxide anion scavenging action was observed.

_{Examples 46 to 50: Superoxide anion (O 2} · ⁻ ) scavenging action of ultrafine bubble-containing alcohol aqueous solution (10%) according to the present invention Control example 46: Ultrafine bubble-free, Example 47: Carbon dioxide ultra Fine bubble containing, Example 48: Hydrogen ultrafine bubble containing, Example 49: Carbon dioxide and hydrogen ultrafine bubble containing (prepared by blowing carbon dioxide in this order), and Example 50: Carbon dioxide and hydrogen ultrafine bubble _{The superoxide anion (O 2} · ^- ) scavenging action of each 10% ethanol aqueous solution of the content (prepared by blowing in the order of carbon dioxide to hydrogen) was examined by ESR measurement. FIG. 16 shows _{I 0} / I-1 obtained from the ESR spectrum of the G-CYPMPO® adduct of the ultrafine bubble-containing solution.

Based on FIG. 16, Table 6 shows the strength of the erasing action as strong ⊚, moderate ◯, weak Δ, and x with little or no erasing action. Any aqueous solution of carbon dioxide ultrafine bubble-containing alcohol aqueous solution (Example 47), hydrogen ultrafine bubble-containing alcohol aqueous solution (Example 48), carbon dioxide and hydrogen ultrafine bubble-containing alcohol aqueous solution (Examples 49 and 50) can be used. A weak to strong superoxide anion scavenging action was observed, and in particular, a strong superoxide anion scavenging action was observed in the carbon dioxide and hydrogen ultrafine bubble-containing alcohol aqueous solution (Example 49).

As shown in FIGS. 13 to 16 and Table 6, regarding the superoxide anion scavenging action of the ultrafine bubble-containing alcoholic aqueous solution according to the present invention, carbon dioxide ultrafine bubble-containing alcohol aqueous solution, hydrogen ultrafine bubble-containing alcohol aqueous solution, and hydrogen ultrafine bubble-containing alcohol aqueous solution. The superoxide anion scavenging action of both the carbon dioxide and hydrogen ultrafine bubble-containing alcohol aqueous solutions varied depending on the ethanol content. The lower the ethanol content, the stronger the superoxide anion scavenging effect. When the ethanol content of the alcohol aqueous solution is low (20% and 10%), the superoxide anion scavenging action of the carbon dioxide ultrafine bubble-containing alcohol aqueous solution and the carbon dioxide and hydrogen ultrafine bubble-containing alcohol aqueous solution becomes moderate or higher, and in particular, carbon dioxide. Strong superoxide anion scavenging action was observed in carbon and hydrogen ultrafine bubbles (prepared by blowing in the order of hydrogen to carbon dioxide).

Based on Tables 5 and 6, regarding the active oxygen scavenging action of the ultrafine bubble-containing alcoholic aqueous solution according to the present invention, carbon dioxide and hydrogen ultrafine bubbles are exhibited from the viewpoint of scavenging both hydroxyl radicals and superoxide anions. In particular, it was found that it is preferable to use carbon dioxide and hydrogen ultrafine bubbles (prepared by blowing in the order of hydrogen to carbon dioxide).

Although the present invention has been described above using the embodiments and examples, it goes without saying that the technical scope of the present invention is not limited to the scope described in the above embodiments. It will be apparent to those skilled in the art that various changes or improvements can be made to the above embodiments. Further, it is clear from the description of the scope of claims that the form to which such a modification or improvement is added may be included in the technical scope of the present invention.

310 Electric balance 320 Platinum 330 Sample solution 340 Particle behavior part 341 Hemisphere 342 Flat plate 343 Piezo stage

Claims (31)

1. An ultrafine bubble-containing aqueous solution containing at least one ultrafine bubble selected from the group consisting of carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles.
2. The ultrafine bubble-containing aqueous solution according to claim 1, which is an ethanol-free non-alcoholic aqueous solution containing at least one ultrafine bubble selected from the group consisting of carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles.
3. The ultrafine bubble-containing aqueous solution of claim 2, which contains carbon dioxide ultrafine bubbles.
4. The ultrafine bubble-containing aqueous solution according to claim 2, which contains hydrogen ultrafine bubbles.
5. The ultrafine bubble-containing aqueous solution of claim 2, which contains carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles.
6. The ultrafine bubble-containing aqueous solution according to any one of claims 3 to 5, which has a hydroxyl radical scavenging action.
7. The ultrafine bubble-containing soft drink according to any one of claims 3 to 5, which has a superoxide anion scavenging effect.
8. The ultrafine bubble-containing aqueous solution according to any one of claims 3 to 5, which has an action of scavenging hydroxyl radicals and superoxide anions.
9. The ultrafine bubble-containing aqueous solution according to claim 2, which contains carbon dioxide ultrafine bubbles and has a hydroxyl radical scavenging action.
10. The ultrafine bubble-containing aqueous solution according to claim 2, which contains carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles and has a hydroxyl radical scavenging action.
11. The ultrafine bubble-containing aqueous solution according to claim 2, which contains hydrogen ultrafine bubbles and has a superoxide anion scavenging action.
12. The ultrafine bubble-containing aqueous solution according to claim 2, which contains carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles and has a superoxide anion scavenging action.
13. A soft drink containing the ultrafine bubble-containing aqueous solution according to any one of claims 2 to 12.
14. The soft drink according to claim 13, which is any soft drink selected from the group consisting of carbonated drinks, fruit tree drinks, vegetable drinks, coffee drinks, tea-based drinks, sports drinks, and mineral water.
15. The method for producing an ultrafine bubble-containing aqueous solution according to claim 5, 10 or 12, which comprises carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles, wherein carbon dioxide is further added to the ultrafine bubble-containing aqueous solution containing hydrogen ultrafine bubbles. A method for producing an ultrafine bubble-containing aqueous solution, which comprises blowing in to produce an ultrafine bubble-containing aqueous solution containing carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles.
16. The method for producing an ultrafine bubble-containing aqueous solution according to claim 5, 10 or 12, which comprises carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles, wherein hydrogen is further added to the ultrafine bubble-containing aqueous solution containing carbon dioxide ultrafine bubbles. A method for producing an ultrafine bubble-containing aqueous solution, which comprises blowing in to produce an ultrafine bubble-containing aqueous solution containing carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles.
17. The ultrafine bubble-containing alcohol aqueous solution according to claim 1, which is an ethanol-containing alcoholic aqueous solution containing at least one ultrafine bubble selected from the group consisting of carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles.
18. The ultrafine bubble-containing alcohol aqueous solution according to claim 17, which contains carbon dioxide ultrafine bubbles.
19. The ultrafine bubble-containing alcohol aqueous solution according to claim 17, which contains hydrogen ultrafine bubbles.
20. The ultrafine bubble-containing alcohol aqueous solution according to claim 17, which contains carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles.
21. The ultrafine bubble-containing alcohol aqueous solution according to claim 20, which has a hydroxyl radical scavenging action.
22. The ultrafine bubble-containing alcohol aqueous solution according to claim 20, which has a superoxide anion scavenging action.
23. The ultrafine bubble-containing alcohol aqueous solution according to claim 20, which has an action of scavenging hydroxyl radicals and superoxide anions.
24. The ultrafine bubble-containing alcohol aqueous solution according to claim 17, which contains carbon dioxide ultrafine bubbles and has a hydroxyl radical scavenging action.
25. The ultrafine bubble-containing alcohol aqueous solution according to claim 17, which contains hydrogen ultrafine bubbles and has a hydroxyl radical scavenging action.
26. The ultrafine bubble-containing alcohol aqueous solution according to claim 17, which contains carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles and has an action of scavenging hydroxyl radicals and superoxide anions.
27. The ultrafine bubble-containing alcohol aqueous solution according to claim 17, which contains carbon dioxide ultrafine bubbles and has a superoxide anion scavenging action.
28. The ultrafine bubble-containing alcohol aqueous solution according to claim 17, which contains carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles and has an action of scavenging hydroxyl radicals and superoxide anions.
29. An alcoholic beverage containing the ultrafine bubble-containing alcohol aqueous solution according to any one of claims 17 to 28.
30. The alcoholic beverage according to claim 29, which is any alcoholic beverage selected from the group consisting of sake, peel, wine, and whiskey.
31. The method for producing an ultrafine bubble-containing alcohol aqueous solution according to claim 23, 26, or 28, which comprises carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles, and is further added to an ultrafine bubble-containing aqueous solution containing hydrogen ultrafine bubbles. A method for producing an ultrafine bubble-containing alcohol aqueous solution, which comprises blowing carbon into an ultrafine bubble-containing aqueous solution containing carbon dioxide ultrafine bubbles and hydrogen ultrafine bubbles.
    
    

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