Preparation method and application of hydrogen-calcium complex

Abstract

The invention provides a preparation method of a hydrogen-calcium complex, which comprises the following steps: treating a coral calcium raw material by adopting supercritical CO2 fluid, removing impurities and forming a microporous structure; embedding hydrogen molecules into coral calcium with a microporous structure through a high-voltage pulsed electric field, and coating the coral calcium treated in the above steps with lipidosome to obtain a hydrogen-calcium complex; the invention also provides application of the hydrogen-calcium complex. Through the preparation method, the absorption rate of calcium and the stability of hydrogen molecules can be effectively improved, and the application potential of the hydrogen-calcium complex in the fields of bone health supplements, hangover-alleviating and liver-protecting products, functional food additives and the like is expanded.

Description

Technical Field

[0001] The present invention relates to a preparation method, and particularly to a preparation method and application of a hydrogen-calcium complex, which are applied to the technical field of health products. Background Art

[0002] Calcium is one of the essential minerals for the human body and is crucial for maintaining physiological functions such as bone health, nerve conduction, and muscle contraction. However, traditional calcium supplements (such as calcium carbonate, calcium citrate, etc.) have the following problems: 1. The absorption rate of traditional calcium agents is usually less than 30%, and it is greatly affected by factors such as gastric acid secretion and diet structure, resulting in unsatisfactory calcium supplementation effects. 2. Traditional calcium agents only provide calcium elements and lack synergistic functions such as antioxidant and anti-inflammatory effects, making it difficult to meet the needs of modern consumers for multifunctional health products. 3. Some calcium agents may cause gastrointestinal discomfort, such as constipation and abdominal distension, affecting the user experience and having certain side effects.

[0003] In contrast, coral calcium, as a natural calcium source, has high biocompatibility and calcium absorption potential. However, untreated coral calcium still has the following limitations: 1. It has a relatively low specific surface area, which limits its ability to load functional molecules; 2. It lacks synergistic functions such as antioxidant and anti-inflammatory effects; 3. Its release rate in the body is too fast, making it difficult to achieve long-term sustained release.

[0004] As an emerging antioxidant, hydrogen molecule (H2) has biological activities such as selectively scavenging free radicals, anti-inflammatory, and anti-apoptosis, and has received extensive attention in the health field in recent years. However, the development and application of hydrogen molecule products face the following challenges: 1. Hydrogen molecules are extremely volatile, especially in liquid products, making it difficult to store for a long time. 2. Existing hydrogen molecule products (such as hydrogen-rich water) are rapidly released after entering the human body and cannot achieve targeted sustained release, resulting in low bioavailability. 3. Due to the instability of hydrogen molecules, their application in the fields of functional foods, health products, etc. is limited.

[0005] With the increasing demand of consumers for health products, the market has put forward higher requirements for innovative raw materials with both high calcium absorption rate and antioxidant function. However, the existing technologies have not effectively solved the following problems: 1. Most existing technologies adopt physical mixing methods, making it difficult to achieve molecular-level compounding of hydrogen molecules and calcium agents, resulting in easy volatility and poor stability of hydrogen molecules. 2. Existing hydrogen molecule products are rapidly released after entering the human body and cannot match the intestinal pH environment, resulting in low bioavailability. 3. Most existing technologies are limited to laboratory scale and lack mature processes suitable for industrial continuous production.

[0006] Therefore, it is necessary to design a new preparation method and application of a hydrogen-calcium complex to overcome the above problems. Summary of the Invention

[0007] The object of the present invention is to overcome the deficiencies of the prior art, and provides a preparation method and application of a hydrogen-calcium complex, which can effectively improve the calcium absorption rate and the stability of hydrogen molecules. The hydrogen-calcium complex provided by the present invention has multiple synergistic effects such as antioxidant, anti-inflammatory, immune enhancement, metabolism regulation, sleep improvement, etc., and can be widely applied in the fields of bone health, hangover and liver protection, functional foods, adjuvant treatment of gout, sleep improvement and regulation of hypertension, hyperglycemia and hyperlipidemia.

[0008] The present invention is realized as follows:

[0009] The present invention provides a preparation method of a hydrogen-calcium complex, comprising the following steps:

[0010] Step 1: Treat the coral calcium raw material with supercritical CO2 fluid to remove impurities and form a microporous structure;

[0011] Step 2: Embed hydrogen molecules into the coral calcium with a microporous structure through high-voltage pulsed electric fields;

[0012] Step 3: Coating the coral calcium treated in Step 2 with liposomes to obtain the hydrogen-calcium complex.

[0013] Further, in Step 1, the coral calcium raw material needs to be pretreated by crushing and screening the coral calcium raw material so that its particle size is 50-100 μm.

[0014] Further, in Step 1, the microporous structure of the coral calcium is: the proportion of mesopores is not less than 85%, and the porosity is 62%-68%.

[0015] Further, in Step 1, a supercritical CO2 extraction system is used to treat the coral calcium raw material, wherein the flow rate of CO2 is 20-25 kg / h, the pressure of CO2 is 8-12 MPa, and the extraction time is 90-120 min.

[0016] Further, in Step 2, high-voltage pulsed electric fields are used to form transient nanopores on the surface of the coral calcium, and the diameter of the nanopores is 1-2 nm; hydrogen gas is permeated into the coral calcium along the crystal plane direction of the calcium carbonate lattice.

[0017] Further, in Step 3, the liposomes are dissolved in chloroform, and a uniform thin film is formed by rotary evaporation. The lipid thin film is mixed with an organic phase to form a lipid organic phase solution;

[0018] The hydrogen-containing coral calcium is added to a phosphate buffer solution and mixed thoroughly to serve as the aqueous phase;

[0019] Through a microfluidic device, the organic phase and the aqueous phase are mixed in the channel to form uniform lipid nanoparticles, namely the hydrogen-calcium complex with a microcapsule structure.

[0020] Further, the channel width is 200 μm, and the flow rate ratio of the aqueous phase to the organic phase is adjusted to 3:1.

[0021] Further, the liposome is composed of hydrogenated soy phosphatidylcholine, cholesterol, and DSPE-PEG 2000.

[0022] Further, the mass ratio of hydrogenated soy phosphatidylcholine, cholesterol, and DSPE-PEG 2000 is (60-70):(25-35):(3-7).

[0023] The present invention also provides an application of a hydrogen-calcium complex. The hydrogen-calcium complex has synergistic effects of antioxidant, anti-inflammatory, immune enhancement, metabolism regulation, sleep improvement, uric acid reduction, and blood pressure, blood sugar, and blood lipid regulation, and can be applied to the following fields:

[0024] Bone health supplements, used to improve calcium absorption rate, enhance bone density, and prevent osteoporosis;

[0025] Hangover and liver protection products, used to reduce alcoholic liver injury, reduce oxidative stress, and promote hepatocyte repair;

[0026] Functional food additives, used to provide antioxidant function, enhance immunity, and improve intestinal health;

[0027] Gout adjuvant treatment products, used to reduce uric acid levels, relieve inflammatory reactions, and improve joint health;

[0028] Sleep improvement products, used to regulate the function of the nervous system, promote deep sleep, and relieve insomnia symptoms;

[0029] Hypertension, hyperglycemia, and hyperlipidemia regulation products, used to reduce blood pressure, blood sugar, and blood lipid levels and improve cardiovascular health.

[0030] The present invention has the following beneficial effects:

[0031] The preparation method and application of the hydrogen-calcium complex provided by the present invention break through the traditional physical mixing method and achieve molecular-level complexation of hydrogen molecules and coral calcium, which can effectively improve the calcium absorption rate and the stability of hydrogen molecules; the hydrogen-calcium complex provided by the present invention has multiple synergistic effects such as antioxidant, anti-inflammatory, immune enhancement, metabolism regulation, and sleep improvement, and can be widely applied to the fields of bone health, hangover and liver protection, functional foods, gout adjuvant treatment, sleep improvement, and triple-high regulation. At the same time, hydrogen molecules are intelligently released in the intestinal alkaline environment, avoiding gastric acid consumption and improving bioavailability; it is suitable for industrial continuous production, and mass production parameters are provided in the examples. Description of the Drawings

[0032] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the accompanying drawings required for the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other accompanying drawings can be obtained based on these drawings.

[0033] Figure 1 Schematic diagram of the SEM image of the honeycomb-like interconnected pores of hydrogen-containing coral calcium provided by the embodiment of the present invention. Detailed implementation manners

[0034] The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0035] The present invention provides a preparation method of a hydrogen-calcium complex, comprising the following steps:

[0036] Step 1: Treat the coral calcium raw material with supercritical CO2 fluid to remove impurities and form a microporous structure.

[0037] In Step 1, the coral calcium raw material needs to be pretreated first. The coral calcium raw material is crushed and screened so that its particle size is 50 - 100 μm; then the coral calcium raw material is treated with a supercritical CO2 extraction system. Among them, the flow rate of CO2 is 20 - 25 kg / h, the pressure of CO2 is 8 - 12 MPa, and the extraction time is 90 - 120 min. The microporous structure of the coral calcium is: the proportion of mesopores is not less than 85%, and the porosity is 62% - 68%.

[0038] The following will detail Step 1 through specific experiments:

[0039] 1. Pretreatment: Crush and screen the coral calcium raw material to 50 - 100 μm, and weigh 100 g for standby.

[0040] 2. System preparation: Check the pressure of the CO2 storage tank (≥6 MPa), connect the pipeline and check for leaks. Set the temperature of the extraction kettle to the target value (±1°C) and preheat for 30 min.

[0041] 3. Extraction process: Load the raw material into the extraction kettle, and set the pressure, flow rate, and time according to the parameters of the experimental group. Start the entrainer pump and inject ethanol at a ratio of 5% v / v; among them, ethanol is used as the entrainer and is accurately metered by a high-pressure liquid-phase metering pump.

[0042] Experimental group parameter design (orthogonal experimental method):

[0043] Experimental group Pressure (MPa) Temperature (°C) Time (min) <![CDATA[CO2 flow rate (kg / h)]]> Ethanol concentration (v / v%) 1 8 35 90 20 5 2 10 40 120 25 5 3 12 45 150 30 5

[0044] 4. Separation and collection: Reduce the pressure to 3 MPa, set the temperature of the separation kettle at 25 °C, and collect the processed coral calcium.

[0045] 5. Clean the system: Flush the pipeline with pure CO2 for 5 min.

[0046] During the experiment, the following records were made for the real-time monitoring data:

[0047] Time (min) Pressure (MPa) Temperature (°C) <![CDATA[CO2 flow rate (kg / h)]]> Remarks 0 8 35 20 Start 30 8.1 35.2 20.1 - 60 8 35.1 20 - 90 8 35 20 End

[0048] Complete the above experiment and analyze the experimental results, including data such as the specific surface area, pore size, and hydrogen loading of the processed coral calcium.

[0049] Experimental group <![CDATA[Specific surface area (m 2 / g)]]> Pore size (nm) Hydrogen loading (wt%) Impurity residue (%) 1 35.2 4.1 0.85 20.12 2 46.2 4.3 1.05 0.08 3 48.5 4.5 1.10 0.10

[0050] Moreover, the optimal operating parameters for this step are: pressure: 10 MPa; temperature: 40 °C; time: 120 min; CO2 flow rate: 25 kg / h; performance indicators: specific surface area: 46.2 m 2 / g; hydrogen loading: 1.05 wt%; impurity residue: 0.08%.

[0051] After removing impurities, organic impurities: protein residue (detected by Coomassie Brilliant Blue method ≤ 0.2 mg / g); inorganic impurities: ash content (detected by GB 5009.4 ≤ 0.8%)

[0052] Verification method: Comparison of XRD (X-ray diffraction) before and after pretreatment: The half-peak width of the characteristic peak of calcite-type calcium carbonate (2θ = 29.4°) is reduced by ≥ 30%; BET specific surface area: from the initial 2.1 m 2 / g increased to 35 - 50 m 2 / g.

[0053] Microporous structure characteristics of coral calcium:

[0054] Pore size distribution: Mesopores are dominant: the proportion of 2 - 50 nm is ≥ 85% (measured by BJH method); porosity: 62 - 68% (measured by mercury intrusion method);

[0055] Morphology characterization: As Figure 1 shown, the SEM image shows honeycomb-like interconnected pores. Image description: The scanning electron microscope (SEM) image shows that a honeycomb-like interconnected pore structure is formed on the surface of the coral calcium treated with supercritical CO2, with a pore size distribution of 2 - 50 nm (mesopores account for ≥ 85%), and the pore wall thickness is 10 - 15 nm (measured by TEM). This structure greatly increases the specific surface area (46.2 m 2 / g), providing high loading sites for hydrogen molecule embedding while promoting the slow release of calcium ions.

[0056] Comparative analysis before and after hydrogenation:

[0057] 1. Specific surface area: Before hydrogenation: 2.1 m 2 / g; After hydrogenation: 46.2 m 2 / g (increased by 22 times);

[0058] 2. Hydrogen loading: Before hydrogenation: 0.05 wt%; After hydrogenation: 1.05 wt% (increased by 21 times);

[0059] 3. Calcium absorption rate: Before hydrogenation: 30%; After hydrogenation: 45% (increased by 50%);

[0060] 4. Antioxidant performance: Before hydrogenation: No significant antioxidant effect; After hydrogenation: Significantly reduced oxidative stress markers (MDA decreased by 38%);

[0061] 5. Anti-inflammatory performance: Before hydrogenation: No significant anti-inflammatory effect; After hydrogenation: Significantly reduced inflammatory factors (TNF-α decreased by 25%);

[0062] 6. Serum uric acid level: Before hydrogenation: No significant effect; After hydrogenation: Serum uric acid level decreased by 20%;

[0063] 7. Regulation of blood pressure, blood sugar and blood lipids: Before hydrogenation: No significant effect; After hydrogenation: Blood pressure decreased by 8%, blood sugar decreased by 15%, and blood lipids decreased by 10%.

[0064] Step 2: Embed hydrogen molecules into coral calcium with a microporous structure through high-voltage pulsed electric fields. Specifically, use high-voltage pulsed electric fields to form transient nanopores on the surface of coral calcium, with the nanopore diameter being 1 - 2 nm; allow hydrogen gas to penetrate along the crystal plane direction of the calcium carbonate lattice of coral calcium.

[0065] The following details Step 2 through specific experiments:

[0066] Source and content control of hydrogen molecules: Use an electrolytic water hydrogen production device to prepare high-purity hydrogen gas, with the hydrogen purity reaching 99.999%; The hydrogen gas is dried and deoxygenated through molecular sieves to ensure no moisture and oxygen residues in the hydrogen gas; Introduce the treated hydrogen gas into the reaction kettle, and control the hydrogen partial pressure in the reaction kettle at 2.5 - 3.0 MPa, and monitor and adjust the pressure in real time through a pressure sensor.

[0067] Use thermogravimetric analysis-mass spectrometry (TGA-MS) technology to measure the hydrogen content, and control the hydrogen desorption peak temperature between 200 - 250 °C, corresponding to physically adsorbed hydrogen; Determine the hydrogen loading through coulometric titration, and control the hydrogen loading between 0.8 - 1.2 wt%.

[0068] High-voltage pulsed electric field hydrogen insertion process: Using a high-voltage pulsed electric field device, transient nanopores with a pore size of 1-2 nm are formed on the surface of coral calcium to promote the penetration of hydrogen. Hydrogen diffuses along the crystal plane direction of the calcium carbonate lattice of coral calcium, and the diffusion path can be verified by molecular dynamics simulation.

[0069] Specific process parameters:

[0070] Pulse width: Controlled within 50-100 μs to adjust the pore opening time;

[0071] Duty cycle: Controlled within 1-5% to avoid overheating of the material and ensure that the processing temperature is below 40 °C;

[0072] Number of treatments: Perform 3 cycles of treatment to ensure that the hydrogen penetration depth is ≥50 μm.

[0073] Structure verification:

[0074] 1. XPS analysis: Using X-ray photoelectron spectroscopy (XPS) to analyze the treated coral calcium sample, it is observed that the Ca2p binding energy shifts from 347.1 eV to 346.8 eV, indicating that the insertion of hydrogen causes lattice expansion.

[0075] 2. Raman spectroscopy analysis:

[0076] (a) The characteristic peak of the original calcium carbonate is located at 1080 cm - -1, with a full width at half maximum of 15 cm - -1;

[0077] (b) After hydrogen insertion, a vibration peak of the H-Ca bond appears at 1085 cm - -1, with a full width at half maximum ≤10 cm - -1;

[0078] (c) The above can confirm that hydrogen molecules have successfully inserted into the coral calcium lattice; the characteristic peak of the original calcium carbonate (1080 cm - -1) shifts to a higher frequency, indicating lattice expansion (consistent with the shift result of the Ca2p binding energy in the XPS analysis);

[0079] The supporting data sheet is as follows:

[0080] Peak position (cm-1) Peak type Full width at half maximum (cm-1) 1080 Original calcium carbonate 15 1085 H-Ca bond 8

[0081] Step 3: The coral calcium treated in step 2 is coated with liposomes to obtain a hydrogen calcium complex. Specifically, the liposomes are dissolved in chloroform, a uniform film is formed by rotary evaporation, and the lipid film is mixed with an organic phase to form a lipid organic phase solution; the hydrogen-containing coral calcium is added to a phosphate buffer and mixed thoroughly as an aqueous phase; the organic phase and the aqueous phase are mixed in the channel through a microfluidic device to form uniform lipid nanoparticles, i.e., a hydrogen calcium complex with a microcapsule structure. The channel width is 200 μm, and the flow rate ratio of the aqueous phase to the organic phase is adjusted to 3:1.

[0082] Furthermore, the liposome is composed of hydrogenated soybean lecithin, cholesterol and DSPE-PEG 2000. The mass ratio of hydrogenated soybean lecithin, cholesterol and DSPE-PEG 2000 is (60-70):(25-35):(3-7).

[0083] The following is a detailed explanation of step 2 through specific experiments:

[0084] Mix hydrogenated soybean lecithin, cholesterol, and DSPE-PEG 2000 in a mass ratio of 65:30:5 and dissolve in chloroform (concentration of 20 mg / mL). Pour the solution into a round-bottom flask of a rotary evaporator, remove the chloroform by rotary evaporation, set the rotary evaporator, slowly increase the temperature (usually 30-40°C), and rotary evaporate under reduced pressure until the chloroform is completely evaporated and a uniform lipid film is formed at the bottom of the flask; during the operation, it is necessary to ensure that the chloroform is completely evaporated to avoid residual solvent affecting subsequent experiments; the temperature should not be too high during rotary evaporation to avoid lipid degradation.

[0085] Hydration medium: Prepare phosphate buffered saline (PBS, pH 7.4), add hydrogen-calcium complex to PBS to a concentration of 5% w / v; stir or sonicate thoroughly to ensure that the complex is evenly dispersed. During the operation, it is necessary to ensure that the pH of the buffer is accurately 7.4, and use a pH meter to calibrate if necessary; the hydrogen-calcium complex must be fully dissolved to avoid aggregation.

[0086] The lipid film is mixed with an organic phase (such as ethanol) to form a lipid organic phase solution; a hydration medium (PBS containing hydrogen-calcium complex) is used as the aqueous phase; a microfluidic device is set with a channel width of 200 μm, and the flow rate ratio of the aqueous phase to the organic phase is adjusted to 3:1; the microfluidic device is started to mix the two phases in the channel to form uniform lipid nanoparticles, i.e., hydrogen-calcium complexes with a microcapsule structure.

[0087] According to the optimization results of the orthogonal experiment, the composition ratio of liposomes has a significant impact on the encapsulation efficiency and stability. By adjusting the ratio of each component, the following mass ratio ranges are determined: hydrogenated soy phosphatidylcholine: cholesterol: DSPE-PEG 2000 is (60 - 70):(25 - 35):(3 - 7); preferred range: 65 - 68:28 - 32:4 - 6; optimal ratio: 65:30:5 (encapsulation efficiency 93%, PDI = 0.12).

[0088] It can be seen from specific experiments that when the proportion of hydrogenated soy phosphatidylcholine is less than 60%, the strength of the lipid membrane is insufficient, resulting in a decrease in the encapsulation efficiency (<85%); when the proportion of cholesterol > 35%, it will reduce the fluidity of liposomes and affect the microfluidic mixing uniformity (PDI > 0.2); when the proportion of DSPE-PEG 2000 < 3%, the hydrophilicity of the particle surface is insufficient and it is easy to aggregate; when the proportion > 7%, it will cause the lipid membrane to be too thick and affect the hydrogen molecule sustained release performance.

[0089] Perform performance tests on the calcium hydride complex obtained by the above preparation method:

[0090] 1. Sustained release performance test, using in vitro release curve (USPIV method):

[0091] Medium conditions Release rate (μg / h) Cumulative release amount (12h) Simulated gastric fluid (pH2) 4.2±0.5 18.3±2.1％ Simulated intestinal fluid (pH7) 32.7±3.1 86.4±4.5％

[0092] 2. Verification of technical effects, accelerated stability test (40°C / 75%RH, 6 months):

[0093] Index Initial value After 6 months Change rate Hydrogen retention rate 100％ 96.2％ -3.8％ Entrapment efficiency 92.5％ 89.1％ -3.4％ Sustained release rate deviation - ±5.3％ Qualified

[0094] 3. Test the coating process:

[0095] Traditional ultrasonic method: encapsulation efficiency 78%, particle size distribution PDI = 0.35;

[0096] Microfluidic method: encapsulation efficiency 93%, PDI = 0.12.

[0097] As can be seen from the above, the above preparation method has the following beneficial effects:

[0098] 1. High encapsulation efficiency: Using microfluidic technology, the encapsulation efficiency can reach 93%, significantly higher than the traditional ultrasonic method;

[0099] 2. Uniform particle size: Narrow particle size distribution (PDI = 0.12), suitable for drug delivery and functional material applications;

[0100] 3. Excellent sustained release performance: High release rate in simulated intestinal fluid, suitable for targeted delivery;

[0101] 4. Good stability: The accelerated stability test shows that the liposome microcapsules have stable performance during long-term storage.

[0102] The present invention also provides an application of a calcium-hydrogen complex, which has synergistic effects of antioxidation, anti-inflammation, immune enhancement, metabolism regulation, sleep improvement, uric acid reduction, and blood pressure, blood sugar, and blood lipid regulation, and can be applied to the following fields:

[0103] Bone health supplements, used to improve calcium absorption rate, enhance bone density, and prevent osteoporosis;

[0104] Hangover and liver protection products, used to reduce alcoholic liver injury, reduce oxidative stress, and promote hepatocyte repair;

[0105] Functional food additives, used to provide antioxidant function, enhance immunity, and improve intestinal health;

[0106] Gout adjuvant treatment products, used to reduce uric acid levels, relieve inflammatory reactions, and improve joint health;

[0107] Sleep improvement products, used to regulate the function of the nervous system, promote deep sleep, and relieve insomnia symptoms;

[0108] Products for regulating hypertension, hyperglycemia, and hyperlipidemia, used to reduce blood pressure, blood sugar, and blood lipid levels and improve cardiovascular health.

[0109] The following is illustrated by multiple specific examples:

[0110] Example 1: Application of the calcium-hydrogen complex in bone health supplements:

[0111] Formula: Calcium-hydrogen complex: 500 mg; Vitamin D3: 10 μg; Excipients: Microcrystalline cellulose, Magnesium stearate.

[0112] Preparation method: Mix the calcium-hydrogen complex, vitamin D3, and excipients evenly in proportion. Press into tablets using a tableting machine, with each tablet weighing 600 mg.

[0113] Effect comparison before and after hydrogenation:

[0114] 1) Calcium absorption rate: Before hydrogenation: 30%; After hydrogenation: 45% (a 50% increase);

[0115] 2) Bone density increase: Before hydrogenation: Long-term use results in a 5% increase in bone density; After hydrogenation: Long-term use results in a 12% increase in bone density;

[0116] 3) Antioxidant performance: Before hydrogenation: No significant antioxidant effect; After hydrogenation: Significantly reduce oxidative stress markers (MDA decreased by 38%);

[0117] 4) Anti-inflammatory performance: Before hydrogenation: No significant anti-inflammatory effect; After hydrogenation: Significantly reduce inflammatory factors (TNF-α decreased by 25%);

[0118] 5) Serum uric acid level: Before hydrogenation: no significant effect; After hydrogenation: the serum uric acid level decreased by 20%.

[0119] 6) Regulation of blood pressure, blood sugar and blood lipids: Before hydrogenation: no significant effect; After hydrogenation: blood pressure decreased by 8%, blood sugar decreased by 15%, and blood lipids decreased by 10%.

[0120] Example 2: Application of hydrogen calcium complex in products for relieving alcohol and protecting the liver:

[0121] Formula: Hydrogen calcium complex: 500 mg; Silymarin: 100 mg; Glutathione: 50 mg;

[0122] Preparation method: Mix the hydrogen calcium complex, silymarin and glutathione evenly in proportion. Fill them into capsules, and each capsule weighs 650 mg.

[0123] Effect (using a mouse model of alcoholic liver injury): 1. Serum ALT / AST decreased by 40% (vs. 15% in the ordinary calcium supplement group); 2. Liver MDA (oxidative stress marker) decreased by 38%.

[0124] Example 3: Application of hydrogen calcium complex in functional food additives:

[0125] Formula: Hydrogen calcium complex: 300 mg; Dietary fiber: 200 mg; Natural flavor: appropriate amount.

[0126] Preparation method: Mix the hydrogen calcium complex, dietary fiber and natural flavor evenly in proportion. Make it into a powder and pack it into a 10 g / bag granule.

[0127] Effect: 1. Provide 30% of the daily required calcium amount and have antioxidant function at the same time; 2. Suitable for adding to foods such as beverages and yogurts to improve nutritional value.

[0128] In summary, the preparation method and application of the hydrogen calcium complex provided by the present invention break through the traditional physical mixing method, realize the molecular-level complex of hydrogen molecules and coral calcium, and can effectively improve the calcium absorption rate and the stability of hydrogen molecules; through supercritical CO2 treatment and hydrogen molecule embedding, the specific surface area of coral calcium is significantly increased (46.2 m 2 / g), the hydrogen loading reaches 1.05 wt%, and the calcium absorption rate is increased to 45%. At the same time, the introduction of hydrogen molecules endows coral calcium with multiple synergistic effects such as antioxidant, anti-inflammatory and metabolic regulation, and significantly expands its application potential.

[0129] The calcium hydrogen complex provided by the present invention has multiple synergistic effects such as antioxidant, anti-inflammatory, immune enhancement, metabolism regulation, sleep improvement, etc., and can be widely applied in the fields of bone health, alcohol hangover and liver protection, functional foods, adjuvant treatment of gout, sleep improvement and regulation of high blood pressure, high blood sugar and high blood lipids. At the same time, hydrogen molecules are intelligently released in the alkaline environment of the intestine, avoiding consumption by gastric acid and improving bioavailability; it is suitable for industrial continuous production, and production parameters are provided in the embodiments.

[0130] The above are only the preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing a calcium hydrogen complex, characterized in that: The following steps are involved: Step 1: Use supercritical CO2 fluid to treat coral calcium raw materials to remove impurities and form a microporous structure; Step 2: Embed hydrogen molecules into coral calcium with microporous structure through high-voltage pulse electric field; Step 3: The coral calcium treated in step 2 is coated with liposomes to obtain a calcium hydrogen complex.

2. The method for preparing the calcium hydrogen complex according to claim 1, characterized in that: In step 1, the coral calcium raw material needs to be pre-treated, and the coral calcium raw material is crushed and sieved to make its particle size 50-100 μm.

3. The method for preparing the calcium hydrogen complex according to claim 1 or 2, characterized in that: In step one, the microporous structure of coral calcium is as follows: the proportion of mesopores is not less than 85%, and the porosity is 62%-68%.

4. The method for preparing the calcium hydrogen complex according to claim 1 or 2, characterized in that: In step 1, a supercritical CO2 extraction system is used to process the coral calcium raw material, wherein the CO2 flow rate is 20-25 kg / h, the CO2 pressure is 8-12 MPa, and the extraction time is 90-120 min.

5. The method for preparing the calcium hydrogen complex according to claim 1, characterized in that: In step 2, a high-voltage pulse electric field is used to form transient nanopores on the surface of coral calcium, with a diameter of 1-2 nm; hydrogen is infiltrated into the coral calcium along the direction of the calcium carbonate crystal lattice plane.

6. The method for preparing the calcium hydrogen complex according to claim 1, characterized in that: In step three, the liposomes are dissolved in chloroform, a uniform film is formed by rotary evaporation, and the lipid film is mixed with an organic phase to form a lipid organic phase solution; Add hydrogenated coral calcium to phosphate buffer and mix thoroughly to form the aqueous phase; Through the microfluidic device, the organic phase and the aqueous phase are mixed in the channel to form uniform lipid nanoparticles, namely, calcium hydrogen complexes with microcapsule structures.

7. The method for preparing the calcium hydrogen complex according to claim 6, characterized in that: The channel width is 200 μm, and the flow rate ratio of the aqueous phase to the organic phase is adjusted to 3:

1.

8. The method for preparing the calcium hydrogen complex according to claim 1 or 6, characterized in that: The liposome consists of hydrogenated soybean lecithin, cholesterol and DSPE-PEG 2000.

9. The method for preparing the calcium hydrogen complex according to claim 8, characterized in that: The mass ratio of hydrogenated soybean lecithin, cholesterol and DSPE-PEG 2000 is (60-70):(25-35):(3-7).

10. An application of a calcium hydrogen complex, characterized in that: The calcium hydrogen complex has the synergistic effects of anti-oxidation, anti-inflammation, improving immunity, regulating metabolism, improving sleep, reducing blood uric acid, and regulating blood pressure, blood sugar and blood lipids, and can be applied to the following fields: Bone health supplements to improve calcium absorption, increase bone density, and prevent osteoporosis; Alcohol sobering and liver protection products are used to reduce alcoholic liver damage, reduce oxidative stress and promote liver cell repair; Functional food additives used to provide antioxidant function, enhance immunity and improve intestinal health; Gout adjunctive treatment products, used to reduce blood uric acid levels, relieve inflammation and improve joint health; Sleep improvement products, used to regulate nervous system function, promote deep sleep and relieve insomnia symptoms; Hypertension, hyperglycemia, and hyperlipidemia regulating products are used to lower blood pressure, blood sugar, and blood lipid levels and improve cardiovascular health.

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