A hydrogen and selenium-rich gas-containing mineral water drink and a preparation method thereof

Abstract

The present application belongs to the field of nutrition and food, and particularly relates to a hydrogen-rich and selenium-rich gas-containing mineral water drink and a preparation method thereof. The present application realizes synergistic enhancement of physiological activity by scientifically proportioning hydrogen and specific form organic selenium (L-selenium-methyl selenocysteine) in a gas-containing system. Hydrogen has selective antioxidant properties and can effectively neutralize harmful free radicals in cells; and L-selenium-methyl selenocysteine, as a core synthetic substrate of glutathione peroxidase (GPx) in the human body, can activate the activity of the key antioxidant enzyme. The two together in the carrier of gas-containing mineral water form a three-dimensional antioxidant defense network: hydrogen directly removes ·OH and other strong active oxygen, while selenium protein systematically decomposes peroxide to prevent lipid peroxidation chain reaction. This synergistic mechanism has been verified by experiments, and the comprehensive antioxidant index is increased by about 40%-60% compared with single-component products, realizing the health effect of "1+1>2".

Description

Technical Field

[0001] This invention belongs to the field of nutrition and food, specifically relating to a hydrogen-rich, selenium-rich carbonated mineral water beverage and its preparation method. Background Technology

[0002] Currently, there are different technical approaches for hydrogen-rich water, selenium-rich water, and carbonated water in the field of functional drinking water, but there is still a lack of products and methods that can organically combine them and solve their stability, safety, and taste compatibility issues.

[0003] 1. Hydrogen-rich water technology: Existing technologies mostly enrich hydrogen through physical injection or water electrolysis, but hydrogen has low solubility in water and is extremely easy to dissipate. To improve the dissolved hydrogen capacity and stability, related patents have adopted methods such as nanobubble technology, mechanical stirring to break up hydrogen bubbles, and ultrasonic vibration to break up hydrogen bubbles. However, these methods or equipment have complex structures or are difficult to maintain hydrogen concentration for a long time. For example, nanobubbles still quickly aggregate and merge, resulting in insufficient stability of hydrogen-rich water. It is best to prepare and drink it immediately, which limits the storage and transportation of the product.

[0004] 2. Selenium-enriched water technology: Selenium fortification mainly involves the direct addition of inorganic selenium (such as sodium selenite) or the acquisition of organic selenium through microbial conversion. Inorganic selenium (such as selenite and selenate) has low bioavailability and potentially high toxicity. Although some studies have explored the conversion of inorganic selenium into organic selenium (such as selenocysteine ​​and selenomethionine) through lactic acid bacteria fermentation to prepare selenium-enriched fermented beverages, and some patents have used sugars (such as D-mannose) to functionalize nano-selenium to enhance its stability and applications, these technologies primarily focus on the form and bioavailability of selenium and do not address the issue of its synergistic coexistence with hydrogen and carbon dioxide.

[0005] 3. Carbonated Water Technology: Carbonated water is usually produced by injecting carbon dioxide through a carbonation process. However, carbon dioxide dissolves in water and is acidic, which may affect the solubility and stability of hydrogen, and may also interact with selenium (especially certain forms of selenium), affecting the overall stability of the product.

[0006] 4. Challenges and Limitations of Technological Integration: The current market lacks products that effectively combine high-concentration dissolved hydrogen, stable and safe selenium, and carbon dioxide gas. Some existing technologies attempt to combine two of these elements, but these have significant shortcomings. The patent "A Functionalized Nano-Selenium Hydrogen-Rich Water and Its Preparation Method" (202110860724.3) stabilizes dissolved hydrogen in hydrogen-rich water by modifying nano-selenium with sugars, thus reducing hydrogen leakage. However, this patent does not address the gas-containing (carbon dioxide) characteristics, and therefore cannot solve the stability problem of hydrogen and selenium under carbonation conditions.

[0007] A hydrogen-rich water preparation device (202123324549.0) aims to increase the dissolved hydrogen capacity by improving the hydrogen bubble breaking method or by breaking the bubbles through ultrasonic vibration, but these technologies do not consider the introduction of selenium and compatibility in a gas-containing environment.

[0008] In summary, existing technologies fail to provide a complete solution to reconcile the stability, safety, and taste compatibility among hydrogen-rich, selenium-rich, and gaseous components. Specifically, maintaining the long-term stability of hydrogen and functional selenium forms in a gaseous (acidic) environment, ensuring the safety and bioavailability of selenium sources (especially safer organic selenium) in this complex system, and balancing the pungent taste of carbon dioxide with the overall flavor harmony of the beverage are all challenges that existing technologies have not yet overcome. Therefore, there is an urgent need for an innovative formulation and preparation method that integrates these three functions and resolves the technical contradictions arising from their coexistence. Summary of the Invention

[0009] The primary objective of this invention is to overcome the shortcomings of the prior art and provide a hydrogen-rich and selenium-rich carbonated mineral water beverage that has a good taste, good stability, high safety, and multiple health benefits such as anti-oxidation and supplementation of trace elements.

[0010] Another object of the present invention is to provide the above-mentioned hydrogen-rich and selenium-rich carbonated mineral water beverage.

[0011] Another object of the present invention is to provide the above-mentioned hydrogen-rich and selenium-rich carbonated mineral water beverage and its preparation method.

[0012] The objective of this invention is achieved through the following technical solution: A hydrogen- and selenium-enriched carbonated mineral water beverage comprises: a mineral water base, dissolved hydrogen, selenium, and carbon dioxide gas; wherein the selenium is derived from L-selenomethylselenocysteine ​​and has a concentration of 10 μg / L to 50 μg / L; the dissolved hydrogen concentration is 0.5 ppm to 2.0 ppm; and the carbon dioxide gas content is 2.0 to 5.0 times the volume, where the volume multiple refers to the ratio of the volume of carbon dioxide gas dissolved in water to the volume of water at standard temperature and pressure (0°C, 101.3 kPa).

[0013] Furthermore, the dissolved concentration of hydrogen is achieved through nanobubble technology, and the hydrogen bubbles generated by the nanobubble technology have a particle size of 200–500 nm.

[0014] Furthermore, the pH value of the beverage is in the range of 4.5 to 6.0.

[0015] Furthermore, the beverage is packaged in a high-barrier aluminum can or a high-barrier PET bottle.

[0016] Furthermore, a method for producing a hydrogen-rich, selenium-rich carbonated mineral water beverage includes the following steps: (1) Provide filtered and purified mineral water; (2) Add L-seleno-methylselenocysteine ​​to mineral water and stir to dissolve it at 10-25℃ to obtain selenium-enriched water; (3) Cool the selenium-enriched water to 2-8℃; (4) At a pressure of 0.3-0.6 MPa, hydrogen gas is injected into the cooled selenium-rich water and maintained for 10-20 minutes to obtain hydrogen-rich selenium-rich water; (5) Carbon dioxide gas is injected into the hydrogen-rich and selenium-rich water at a temperature of 2-8℃ and a pressure of 0.4-0.7 MPa to carry out carbonation; (6) Immediately perform aseptic filling and capping.

[0017] Furthermore, between steps (4) and (5), there is a step of secondary hydrogen compensation at a pressure of 0.2-0.4 MPa for 2-5 minutes.

[0018] Furthermore, the hydrogen injection described in step (4) is performed via a nanobubble generator.

[0019] Furthermore, the filling in step (6) adopts an isobaric filling method.

[0020] Furthermore, in step (2), before adding the L-seleno-methylselenocysteine, a step of adding a pH buffer to the mineral water is also included. The pH buffer is composed of sodium citrate and sodium bicarbonate in a mass ratio of 1:1 to 1:3, and the total amount added is 0.01%-0.05%.

[0021] Furthermore, after sealing in step (6), the process also includes laser marking the packaging container and recording the production batch and the initial value of dissolved hydrogen concentration.

[0022] Compared with the prior art, the present invention has the following innovations, advantages and effects: 1. This invention utilizes the synergistic effect of hydrogen and L-selenomethylselenocysteine ​​in carbonated mineral water to construct a dual antioxidant mechanism: hydrogen directly scavenges reactive oxygen species, while selenoproteins systematically decompose peroxides. Hydrogen possesses selective antioxidant properties, effectively neutralizing harmful free radicals within cells; while L-selenomethylselenocysteine, as a core substrate for the synthesis of glutathione peroxidase (GPx) in the human body, can activate the activity of this key antioxidant enzyme. Together, they form a three-dimensional antioxidant defense network in carbonated mineral water: hydrogen directly scavenges strong reactive oxygen species such as ·OH, while selenoproteins systematically decompose peroxides, preventing the chain reaction of lipid peroxidation. Experimental verification shows that this synergistic mechanism improves the overall antioxidant index by approximately 40%-60% compared to single-component products, achieving a health benefit of "1+1>2".

[0023] 2. The safety of this invention is reflected in three aspects. First, the core selenium source is L-seleno-methylselenocysteine, a food fortifier approved by domestic and international regulations. Its metabolic pathway in the human body is well-defined, and it carries no risk of cumulative toxicity from inorganic selenium (such as sodium selenite). Second, by precisely controlling the selenium concentration within the range of 10-50 μg / L, it meets the daily selenium requirements of the human body while remaining far below the safety upper limit, ensuring the safety of long-term consumption. Finally, the unique preparation process avoids harsh conditions such as high temperatures and strong acids and alkalis, preventing the formation of harmful byproducts. Acute oral toxicity tests show that its LD50 > 5000 mg / kg, which is practically non-toxic, fully demonstrating the high safety of the product.

[0024] 3. This invention addresses the technical bottlenecks of easily dissipated hydrogen, variable selenium form, and unstable carbonic acid environment through multiple technological innovations. It employs nanobubble technology combined with specific pressure parameters (0.3-0.6 MPa) to form stable hydrogen bubbles with a particle size of 200-500 nm, significantly extending their existence time in water. A secondary hydrogen compensation process effectively offsets hydrogen loss caused by subsequent carbonation processes. A sodium citrate-sodium bicarbonate composite buffer system precisely controls the pH at 4.5-6.0, satisfying the refreshing taste of carbonated beverages while providing an optimal stable environment for hydrogen and organic selenium. Accelerated testing shows that within a 6-month shelf life, the product exhibits a hydrogen retention rate >85%, a selenium retention rate >98%, and a carbon dioxide retention rate >90%, all significantly superior to the control product. Attached Figure Description

[0025] Figure 1 This is a process flow diagram of the preparation method of the present invention; Figure 2 This is a comparison chart of the changes in hydrogen concentration during the shelf life of Embodiment 1 and Comparative Example 1 of the present invention; Figure 3This is a comparison chart of the selenium speciation stability during storage between Example 1 and Comparative Example 2 of the present invention; Figure 4 This is a comparison chart of the stability test results (stored at 25°C for 180 days) of the present invention. Detailed Implementation

[0026] The embodiments of the present invention will be described in detail below with reference to the accompanying drawings. However, those skilled in the art will understand that the following embodiments and examples are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0027] Example 1: Formula: Mineral water base: 1L; L-Selenium-methylselenocysteine ​​(as selenium): 20 μg / L; M- Target concentration of dissolved hydrogen: 1.2 ppm; N-carbon dioxide volume ratio: 3.5 times; pH buffer: Sodium citrate and sodium bicarbonate are compounded in a mass ratio of 1:2, with an addition amount of 0.03%.

[0028] Preparation process: Water treatment: 1. Take natural mineral water and pass it through a three-stage filtration process: a 5μm precision filter, an activated carbon filter, and a 0.22μm microporous membrane. The water temperature is maintained at 15±2℃.

[0029] 2. Selenium fortification: Add precisely weighed pH buffer (0.01% sodium citrate, 0.02% sodium bicarbonate) to mineral water and stir until completely dissolved; Add precisely weighed L-seleno-methylselenocysteine ​​(corresponding to a selenium concentration of 20 μg / L); Stir at 120 rpm for 30 minutes at 15°C to ensure complete dissolution and obtain selenium-enriched water.

[0030] 3. Cooling treatment: The selenium-enriched water is cooled to 4±0.5℃ through a plate heat exchanger.

[0031] 4. Hydrogen injection: Using a nanobubble generator, food-grade hydrogen was injected into the cooled selenium-enriched water at a pressure of 0.4 MPa. The injection time was maintained for 15 minutes, and the dissolved hydrogen concentration was monitored in real time until it reached 1.2 ppm.

[0032] 5. Carbonation process: Food-grade carbon dioxide was injected into hydrogen-rich and selenium-rich water at 5±0.5℃ and 0.5MPa pressure, with the carbon dioxide volume ratio controlled at 3.5 times.

[0033] 6. Filling and sealing: Immediately fill the high-barrier aluminum cans (oxygen permeability <0.001cc / pkg·day) using an isobaric filling machine. Filling temperature is controlled below 5℃ and capping is performed instantly to ensure seal integrity.

[0034] 7. Quality control: Immediately after sealing, laser marking is used to record the production batch and the initial value of dissolved hydrogen concentration of 1.2 ppm.

[0035] Example 2: Low concentration formula: Mineral water base solution: 1L; L-Selenium-methylselenocysteine ​​(as selenium): 10 μg / L; M- Target concentration of dissolved hydrogen: 0.8 ppm; N-carbon dioxide volume ratio: 2.0 times; O-pH buffer: Sodium citrate and sodium bicarbonate are compounded in a 1:1 mass ratio, with an addition amount of 0.01%.

[0036] Preparation process: 1. Water treatment is the same as in Example 1; 2. Selenium fortification: After adding pH buffer, add L-seleno-methylselenocysteine ​​(corresponding to a selenium concentration of 10 μg / L) and stir at 10°C for 25 minutes; 3. Cooling treatment: Cool to 2℃; 4. Hydrogen injection: Inject hydrogen at a pressure of 0.3 MPa and maintain for 10 minutes to achieve a dissolved hydrogen concentration of 0.8 ppm; 5. Carbonation process: Carbon dioxide is injected at 2℃ and 0.4MPa pressure, with a volume ratio of 2.0 times; 6. Filling and sealing: High-barrier PET bottles are used for isobaric filling at a filling temperature of 2℃. 7. Quality monitoring: Record the initial value of dissolved hydrogen concentration as 0.8 ppm.

[0037] Example 3: High-concentration formula: Mineral water base solution: 1L L-Selenium-methylselenocysteine ​​(as selenium): 30 μg / L; M- Target concentration of dissolved hydrogen: 1.5 ppm; N-carbon dioxide volume ratio: 4.5 times; O-pH buffer: Sodium citrate and sodium bicarbonate are compounded in a mass ratio of 1:3, with an addition amount of 0.05%.

[0038] Preparation process: Water treatment is the same as in Example 1. Selenium fortification: After adding pH buffer, add L-seleno-methylselenocysteine ​​(corresponding to a selenium concentration of 30 μg / L) and stir at 25°C for 35 minutes; Cooling treatment: Cooling to 8℃, or cooling to 2–8℃, is to improve gas solubility and stability; Hydrogen injection: Inject hydrogen at a pressure of 0.6 MPa and maintain for 20 minutes to achieve a dissolved hydrogen concentration of 1.5 ppm; Secondary hydrogen compensation: Inject hydrogen at a pressure of 0.4 MPa for 3 minutes; Carbonation process: Carbon dioxide is injected at 8°C and 0.7 MPa pressure, with a volume ratio of 4.5 times; Filling and sealing: High-barrier aluminum cans are used for isobaric filling at a filling temperature of 8℃. Quality monitoring: Record the initial value of dissolved hydrogen concentration as 1.5 ppm.

[0039] Comparative Example 1: Comparison of Inorganic Selenium Sources formula: Sodium selenite was used as the selenium source (calculated as selenium): 20 μg / L; The rest of the formula is the same as in Example 1. Preparation process: The preparation process is exactly the same as in Example 1; Comparison results: Taste test: 8 out of 10 professional tasters detected a slight metallic taste; Stability: After 3 months of storage, the selenium precipitation increased by 15%, and the dissolved hydrogen concentration decreased to 0.6 ppm; Safety testing: Acute toxicity tests showed that the LD50 was reduced by 40% compared to Example 1.

[0040] Comparative Example 2: Comparison of Process Sequence formula: Same as Example 1 Changes in manufacturing process: Change the process sequence: first perform carbonation, then perform hydrogen injection; Water treatment is the same as in Example 1. Selenium fortification is the same as in Example 1 After cooling, carbonation is performed (under the same conditions as in Example 1); Then hydrogen gas was injected under the same conditions.

[0041] Comparison results: Acute oral toxicity testing was conducted according to GB 15193.3—2014, and the results showed LD50. 50 > 5000 mg / kg bw, which is practically non-toxic; Experiments have verified that selenium concentrations of 10, 20, 30, 40, and 50 μg / L can achieve good bioavailability and stability, and have significant synergistic effects with hydrogen and carbon dioxide. Hydrogen dissolution efficiency: The final dissolved hydrogen concentration was only 0.5 ppm, a 58% reduction compared to Example 1; Bubble stability: Nano hydrogen bubbles aggregate rapidly, increasing in size by 3 times within 1 hour; The synergistic antioxidant effect was determined by the DPPH free radical scavenging rate experiment. Compared with the single hydrogen group and the single selenium group, the comprehensive antioxidant index was increased by 40%–60%.

[0042] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A hydrogen-rich, selenium-rich carbonated mineral water beverage, characterized in that, It comprises: mineral water base liquid, dissolved hydrogen, selenium, and carbon dioxide gas; wherein the selenium is derived from L-selenomethylselenocysteine ​​and has a concentration of 10 μg / L to 50 μg / L; the dissolved concentration of hydrogen is 0.5 ppm to 2.0 ppm; and the content of carbon dioxide gas is 2.0 to 5.0 times the volume, where the volume multiple refers to the ratio of the volume of carbon dioxide gas dissolved in water to the volume of water at standard temperature and pressure (0°C, 101.3 kPa).

2. The hydrogen-rich and selenium-rich carbonated mineral water beverage according to claim 1, characterized in that: The dissolved concentration of hydrogen is achieved through nanobubble technology, and the hydrogen bubbles generated by the nanobubble technology have a particle size of 200–500 nm.

3. The hydrogen-rich and selenium-rich carbonated mineral water beverage according to claim 1, characterized in that: The pH value of the beverage is in the range of 4.5 to 6.

0.

4. The hydrogen-rich and selenium-rich carbonated mineral water beverage according to claim 1, characterized in that: The beverage is packaged in a high-barrier aluminum can or a high-barrier PET bottle.

5. The method for preparing the hydrogen-rich and selenium-rich carbonated mineral water beverage according to any one of claims 1 to 4, characterized in that: Includes the following steps: (1) Provide filtered and purified mineral water; (2) Add L-seleno-methylselenocysteine ​​to mineral water and stir to dissolve it at 10-25℃ to obtain selenium-enriched water; (3) Cool the selenium-enriched water to 2-8℃; (4) At a pressure of 0.3-0.6 MPa, hydrogen gas is injected into the cooled selenium-rich water and maintained for 10-20 minutes to obtain hydrogen-rich selenium-rich water; (5) Carbon dioxide gas is injected into the hydrogen-rich and selenium-rich water at a temperature of 2-8℃ and a pressure of 0.4-0.7 MPa to carry out carbonation; (6) Immediately perform aseptic filling and capping.

6. The method according to claim 5, characterized in that: Between steps (4) and (5), there is a step of secondary hydrogen compensation at a pressure of 0.2-0.4 MPa for 2-5 minutes.

7. The method according to claim 5, characterized in that: The hydrogen injection described in step (4) is performed via a nanobubble generator.

8. The method according to claim 5, characterized in that: The filling in step (6) adopts the isobaric filling method.

9. The method according to claim 5, characterized in that: In step (2), before adding the L-seleno-methylselenocysteine, a step of adding a pH buffer to the mineral water is also included. The pH buffer is composed of sodium citrate and sodium bicarbonate in a mass ratio of 1:1 to 1:3, and the total amount added is 0.01%-0.05%.

Images