A HydroMg microsphere composition for intracellular antioxidant and repair of oxidative damage

Abstract

A HydroMg microsphere composition for intracellular antioxidant and oxidative damage repair, comprising HydroMg composite hydrogen storage microspheres and functional ingredients; the functional ingredients comprise at least one of dietary fiber, edible organic acid and composite lactic acid bacteria; the HydroMg composite hydrogen storage microspheres comprise mixed core materials and wall materials; the wall materials comprise resistant dextrin; the mixed core materials comprise: magnesium-based hydrogen storage materials, core material ingredients; the magnesium-based hydrogen storage materials are prepared by hydrogenation of medical-grade or food-grade magnesium oxide with hydrogen; the core material ingredients comprise chitosan oligosaccharide, and optionally calcium carbonate, oyster powder and porous dextrin; the HydroMg composite hydrogen storage microspheres are prepared by a rotary evaporation method. The HydroMg composite hydrogen storage microspheres are combined with beneficial ingredients such as chitosan oligosaccharide to obtain an optimal energy negative hydrogen ion slow-release microsphere composition, which can enter cells to play the functions of antioxidant, anti-aging and molecular-level and bottom-layer repair of oxidative damage.

Description

Technical Field

[0001] This invention belongs to the field of hydrogen storage magnesium-based compound materials, and particularly relates to a HydroMg microsphere composition for intracellular antioxidant and oxidative damage repair, its preparation method and application. Background Technology

[0002] As the outermost organ, the skin is most vulnerable to damage due to exposure to harmful environmental factors such as UV rays, air pollutants, pathogens, and physical and chemical irritants. Air pollution and photoaging, in particular, accelerate skin aging primarily through oxidative stress mechanisms, posing a major threat to skin health. For many years, numerous research teams have dedicated themselves to developing various products, including chemical compositions and therapeutic devices, that combat oxidation and repair oxidative damage. Patent CN112716839B discloses an antioxidant and oxidative damage repair composition and its application. The composition comprises the following components in weight percentages: water 5-50%, 1,3-propanediol 20-50%, camellia leaf extract 0.5-20%, camellia flower extract 0.5-20%, panthenol 2-20%, uric acid 2-20%, epigallocatechin gallate 0.1-5%, niacinamide 0.2-5%, curcumin 0.1-5%, paeonol 0.1-5%, caffeine 0.1-5%, dipotassium glycyrrhizate 0.2-5%, and silymarin 0.1-5%. This invention's formulation contains antioxidant components that scavenge reactive oxygen species, and is combined with synergistic components to further increase autophagy components, reduce reactive oxygen species damage to the skin, improve the skin's own antioxidant capacity, and accelerate the skin's ability to repair oxidative damage. However, the composition provided by this invention is mainly used in cosmetics, acting on the skin surface and unable to penetrate deep into human cells, thus having limited effectiveness in repairing oxidative damage to cells.

[0003] Research indicates that the true cause of aging is the decrease in ATP production due to the reduction in the number of cells in the body. Since fewer cells can regenerate, negative hydrogen ions, which work with NAD+ to produce ATP, are generated in the inner mitochondrial membrane. Under the action of enzymes, these negative hydrogen ions tightly bind with the coenzyme NAD+ (nicotinamide adenine dinucleotide), generating NADH. NADH, as a coenzyme, releases and transfers electrons when it regenerates to NAD+, ultimately leading to the production of adenosine triphosphate (ATP) from ADP (adenosine diphosphate) and inorganic phosphate (Pi) under the action of ATP synthase. This provides energy to the body and slows down aging. Negative hydrogen ions have strong reducing properties; they not only reduce toxic free radicals but also work with NAD+ to generate ATP. They can be used in various products such as food, pharmaceuticals, and cosmetics. Cells can absorb this nanoscale substance. Therefore, hydrogen gas, as the only molecule that can enter mitochondria and scavenge oxygen free radicals, can play a role in the body, preventing disease, restoring health, and slowing aging.

[0004] HydroMg is a novel, edible physical antioxidant. As a magnesium hydrogen compound, its effects encompass the functions of both hydrogen and magnesium. However, HydroMg has a high thermal dehydrogenation temperature and high hydrolytic activity, making it difficult to control the rate and duration of hydrogen release, thus limiting its practical application. Patent application CN115428945A discloses a sustained-release antioxidant composition containing HydroMg and its application. This composition includes HydroMg microspheres, γ-aminobutyric acid (GABA), and nicotinamide. The HydroMg microspheres are prepared by spray drying of a core material composed of HydroMg and malic acid, and a wall material composed of sodium hyaluronate. HydroMg is prepared from magnesium oxide through a high-temperature vaporization reaction with a hydrogen-argon mixture. This composition, through the special structure of the HydroMg microspheres combined with the driving force of magnesium-based micromotors, achieves artificial and effective control of the targeted sustained-release function of HydroMg. It can effectively reduce cellular oxidative stress and inflammation caused by air pollution and photoaging, providing effective protection for the skin and achieving antioxidant effects. However, the antioxidant and oxidative damage repair components of this invention are relatively simple, and the protection of effective components such as HydroMg during the preparation process is insufficient, which can easily lead to a decrease in the effectiveness of the final product.

[0005] Therefore, how to obtain methods and products that have excellent antioxidant and oxidative damage repair properties, can act on human cells, and can achieve targeted sustained and controlled release of hydrogen to improve the utilization rate of effective components such as HydroMg has become an important technical problem that urgently needs to be solved in this field. Summary of the Invention

[0006] To address the deficiencies in the existing technologies, the present invention aims to provide a HydroMg microsphere composition for intracellular anti-oxidation and repair of oxidative damage, its preparation method, and its applications. This invention utilizes micro / nano magnesium-based solid hydrogen storage materials and various beneficial components such as chitosan oligosaccharides to obtain a high-energy negative hydrogen ion sustained-release composition, and promotes this composition to various application fields such as food, pharmaceuticals, and skincare products.

[0007] Specifically, the present invention provides a HydroMg microsphere composition for intracellular antioxidant and oxidative damage repair, comprising HydroMg composite hydrogen storage microspheres and functional ingredients;

[0008] The functional ingredients include at least one of dietary fiber, edible organic acids, and compound lactic acid bacteria; the HydroMg composite hydrogen storage microspheres include a mixed core material and a wall material, with a mass ratio of the mixed core material to the wall material of 1:(1-3);

[0009] The wall material includes resistant dextrin;

[0010] The mixed core material comprises the following components in parts by weight:

[0011] 40-70 parts of magnesium-based hydrogen storage material

[0012] Core material ingredients: 30-60 parts;

[0013] The magnesium-based hydrogen storage material is prepared by hydrogenation of magnesium oxide and hydrogen gas; the core material ingredients include chitosan oligosaccharide, and optionally calcium carbonate, oyster powder, and porous dextrin.

[0014] The HydroMg composite hydrogen storage microspheres were prepared by rotary evaporation.

[0015] In view of the uses and safety of the composition products of the present invention, the magnesium oxide of the present invention is pharmaceutical grade or food grade, such as food grade magnesium oxide, which meets GB14880.2012 "National Food Safety Standard for the Use of Food Fortifiers" and GB2760-2014 "National Food Safety Standard for the Use of Food Additives".

[0016] Preferably, the mass ratio of HydroMg composite hydrogen storage microspheres to functional ingredients is (65-80):(20-35); the functional ingredients are composite lactic acid bacteria particles coated with water-soluble dietary fiber and edible organic acid, and the mass ratio of water-soluble dietary fiber, edible organic acid and composite lactic acid bacteria is (5-10):(1-5):(10-20).

[0017] Preferably, the water-soluble dietary fiber is selected from at least one of fruit and vegetable water-soluble dietary fiber, cereal water-soluble dietary fiber, and legume water-soluble dietary fiber. Dietary fiber, known as the seventh essential nutrient, can form a gel-like layer in the intestine, thickening the non-turbulent layer and directly hindering the diffusion of dietary cholesterol and the emulsification of cholesterol with bile, thus reducing cholesterol absorption. Insoluble dietary fiber can be converted into small-molecule soluble dietary fiber through fermentation (e.g., using commonly used Lactobacillus bulgaricus). Simultaneously, the abundant calcium can also reduce cholesterol absorption, making it suitable for people with high blood lipids.

[0018] The compound lactic acid bacteria comprises Lactobacillus paracasei, Streptococcus thermophilus, and Lactobacillus bulgaricus in a mass ratio of (1-2):(1-2):(1-2), with the viable count of Lactobacillus paracasei, Streptococcus thermophilus, and Lactobacillus bulgaricus ≥1×10⁻⁶. 9 CFU / g; the edible organic acid is selected from one or more combinations of sialic acid, citric acid, tartaric acid, malic acid, and lactic acid.

[0019] Preferably, the functional ingredient is prepared by the following steps:

[0020] (1) Dissolve water-soluble dietary fiber and edible organic acid in deionized water to obtain a spray solution; mix compound lactic acid bacteria evenly to obtain compound bacterial powder;

[0021] (2) Spray the spray liquid onto the compound bacterial powder and stir evenly at the same time;

[0022] (3) Drying is carried out by passing in dry gas at 20-40℃ to obtain compound lactic acid bacteria particles coated with water-soluble dietary fiber and edible organic acid.

[0023] Preferably, the hybrid core material is prepared by the following steps:

[0024] S1. Preparation of magnesium-based hydrogen storage materials

[0025] S1.1 Magnesium oxide with a purity greater than 99% is mixed evenly with oyster calcium and sodium hyaluronate, and ball-milled for 1-2 hours to obtain a sodium magnesium ion composition;

[0026] S1.2 Disperse the sodium magnesium ion composition and mesoporous silica in water and mix them evenly;

[0027] Under the action of electric field S1.3, water is electrolyzed to produce hydrogen gas, resulting in a suspension of white crystals that adsorb and store hydrogen gas.

[0028] S1.3 The suspension is filtered and dried by passing hydrogen gas to obtain magnesium-based hydrogen storage material;

[0029] S1.4 The magnesium-based hydrogen storage material is dispersed in liquid polyethylene glycol with a molecular weight of 400-600, and filtered to obtain the pre-coated magnesium-based hydrogen storage material;

[0030] S2. Mix the core material ingredients with the pre-coated magnesium-based hydrogen storage material evenly to form an electrostatic adsorption hydrogen storage layer on the outside of the pre-coated magnesium-based hydrogen storage material, and then vacuum dry to obtain the mixed core material.

[0031] Mixing micro / nano-sized magnesium oxide with oyster calcium and sodium hyaluronate and then ball-milling it facilitates the construction of a heterostructure, increases the specific surface area of ​​magnesium oxide, and increases the number of reaction sites. Furthermore, the resulting sodium-magnesium ion composition enhances the hydrolysis kinetics of the subsequently obtained micro / nano HydroMg, promoting its in-situ decomposition into magnesium ions and negative hydrogen ions in water. Since micro / nano HydroMg is generated in situ, the formation of a Mg(OH)2 coating layer during hydrolysis can be avoided, thereby promoting the hydrolysis kinetics.

[0032] Mesoporous silica, with particle sizes ranging from 2-50 nm, possesses many unique properties, such as a large specific surface area and good biocompatibility. Furthermore, depending on the preparation method, particles with adjustable particle size, pore size, and specific surface area can be obtained, making it a highly promising carrier material. This invention disperses mesoporous silica with the aforementioned sodium-magnesium ion composition in water for electrolytic hydrogen production. The high specific surface area of ​​mesoporous silica also provides some stability for hydrogen gas and negative hydrogen ions, making it a favorable supporting component for magnesium-based hydrogen storage materials. Overall, the core magnesium-based hydrogen storage material of this invention possesses a micro / nano structure. Utilizing this structure and composite components, an intelligent micro / nano assembly is constructed. Due to its small size effect and ease of functionalization design, the composition efficiently adsorbs and stores hydrogen through the interaction between adsorbate and adsorbent molecules and the changing state of the adsorbate, based on its ultra-high specific surface area. The aforementioned structure and composition can also achieve the effect of locally controlled hydrogen release, forming a hydrogen motor, with kinetic energy reaching and acting on the lesion.

[0033] Preferably, the mesoporous silica undergoes a certain surface modification treatment to improve its surface activity; for example, plasma surface activation treatment can be selected, with the vacuum degree controlled at 1×10⁻⁶. -2 Up to 10×10 -2 Pa, heat to 80-120℃, and activate the surface of mesoporous silica using hydrogen or oxygen plasma under vacuum for 1-5 minutes.

[0034] Preferably, in the core material ingredients, the mass ratio of chitosan oligosaccharide, calcium carbonate, oyster powder and porous dextrin is (5-10):(1-3):(1-3):(1-3).

[0035] Preferably, the wall material further includes wall material ingredients selected from at least one of gelatin, chitosan, sodium alginate, and glyceryl monolaurate, and the total mass of the wall material ingredients to the mass ratio of resistant dextrin is (1-4):5.

[0036] This invention improves the physicochemical properties of microspheres, such as water activity, flowability, hygroscopicity, and particle size distribution, by further adding wall material ingredients to the wall material and adjusting the total mass of the wall material ingredients to the mass ratio of resistant dextrin. The microspheres have excellent encapsulation rate and yield.

[0037] Through the above structural design, the HydroMg composite hydrogen storage microspheres of the present invention actually include at least a magnesium-based hydrogen storage material at the core, a polyethylene glycol pre-coating layer, an electrostatic adsorption hydrogen storage layer formed by the core material formulation, and an outer wall material. Furthermore, the wall material can be designed to have a density gradient to further control the stability and sustained-release performance of the microspheres. For example, different compositions and / or different concentrations of wall material solutions can be used to obtain different mixed suspensions, which are then distributed to form a composite wall material via rotary evaporation. Preferably, the outer wall material has a higher density than the inner wall material, effectively improving the water-blocking stability of the microspheres.

[0038] Secondly, the present invention also provides a method for preparing the HydroMg microsphere composition for intracellular antioxidant and oxidative damage repair, comprising the following steps:

[0039] Step 1: Magnesium-based hydrogen storage material is prepared by hydrogen charging with magnesium oxide and hydrogen gas; and the magnesium-based hydrogen storage material is blended with chitosan oligosaccharide, as well as optional calcium carbonate, oyster powder and porous dextrin to obtain a mixed core material;

[0040] Step 2: Add the wall material raw material to deionized water at 60-80℃ and stir to obtain a wall material solution;

[0041] Step 3: Disperse the mixed core material in the wall material solution, and homogenize under pressure to obtain a mixed suspension;

[0042] Step 4: The mixed suspension is used to prepare HydroMg composite hydrogen storage microspheres by rotary evaporation;

[0043] Step 5: Mix the HydroMg composite hydrogen storage microspheres with the functional ingredients evenly.

[0044] The HydroMg composite hydrogen storage microspheres and functional ingredients of the present invention (preferably composite lactic acid bacteria particles coated with water-soluble dietary fiber and edible organic acids) can be used in various proportions according to different application scenarios, thereby expanding the product's applicable scope and target population.

[0045] Preferably, in step four, the rotary evaporation method includes drying to a moisture content of less than 4% using a centrifugal pump under conditions of vacuum degree less than 150 Pa and temperature of 20-40°C.

[0046] Thirdly, the present invention further provides the application of the aforementioned HydroMg microsphere composition for intracellular antioxidant and oxidative damage repair in food, pharmaceuticals, or skin care products.

[0047] The advantages of this invention compared to the prior art are as follows:

[0048] (1) This invention utilizes pharmaceutical-grade micro / nano magnesium-based solid hydrogen storage high-energy negative hydrogen ion sustained-release composition technology to form a microsphere structure with both protective and sustained-release functions. Firstly, the negative hydrogen ions (which only exist in mitochondria, lightning, or as transient intermediates in reaction processes in nature) exist stably in the form of metallic bonds and adsorb more hydrogen atoms, making them possible as drugs, nutrients, and energy sources. Secondly, when the microsphere structure comes into contact with water or gastric acid, the structure gradually disintegrates and slowly releases the hydrogen ions. Thirdly, with magnesium-based hydrogen storage material as the core (negative ions), the nanoscale size provides better permeability and activity, such as entering cells to exert antioxidant and oxidative damage repair functions, and also distributing more widely in damaged and abnormal tissue areas through damaged blood vessels to achieve targeted repair effects.

[0049] (2) Combining beneficial components such as chitosan oligosaccharide with micro / nano magnesium-based solid hydrogen storage materials. Chitosan oligosaccharide, as a positively charged cationic basic amino oligosaccharide, has excellent adsorption properties. It can adsorb negatively charged substances such as lipids, sugars, and chloride ions, and has the ability to chelate heavy metals. Chitosan oligosaccharide exhibited extremely high thermal and pH stability during the experiment, which significantly improved the hydrogen storage effect of magnesium-based hydrogen storage materials.

[0050] (3) In conjunction with HydroMg composite hydrogen storage microspheres, this invention also provides composite lactic acid bacteria particles coated with water-soluble dietary fiber and edible organic acids to form functional ingredients, which provide more nutrition and repair components while resisting oxidation and repairing oxidative damage, thus expanding the applicable population.

[0051] (4) In the process of core material preparation, microsphere preparation and functional ingredient preparation, the present invention adopts relatively mild process methods to ensure the safety of raw materials and processes, while minimizing the damage to the function of materials and giving full play to the comprehensive properties of the composition such as anti-oxidation, repair of oxidative damage and anti-aging. Attached Figure Description

[0052] The above and other objects, features, and advantages of exemplary embodiments of this disclosure will become readily understood by reading the following detailed description with reference to the accompanying drawings. Wherein:

[0053] Figure 1 This is a schematic diagram of the structure of the HydroMg microsphere composition of the present invention;

[0054] Figure 2 This is a comparison of the scavenging rates of different samples against superoxide anion free radicals;

[0055] Figure 3 It compares the scavenging rates of hydroxyl radicals of different samples;

[0056] Figure 4The anti-aging performance of human umbilical vein endothelial cells (HUVECs) under different concentrations of HydroMg or NMN pretreatment;

[0057] Figure 5 The proportion of senescent cells after cell staining analysis using ImageJ software;

[0058] Figure 6 This is a bar chart showing the mRNA expression levels of pro-inflammatory factors TNF-α, IL-6, and IL-10 in macrophage cell line RAW264.7 after 2 hours of HydroMg treatment;

[0059] Figure 7 This is a bar chart showing the mRNA expression levels of anti-inflammatory factors TNF-α, IL-6, and IL-10 in macrophage cell line RAW264.7 HydroMg after 6 hours of treatment.

[0060] Figure 8 The results show the growth of mouse macrophage cell line RAW264.7 after the addition of HydroMg at concentrations of 0.2 mg / L (a) and 0.04 mg / L (b).

[0061] Figure reference numerals: 1. Mixed core material, 2. Wall material, 11. Magnesium-based hydrogen storage material, 12. Polyethylene glycol pre-coating layer, 13. Electrostatic adsorption hydrogen storage layer, 20. Functional shell layer, 21. Functional core, 100. HydroMg composite hydrogen storage microspheres, 200. Functional ingredients. Detailed Implementation

[0062] The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0063] This invention provides a HydroMg microsphere composition for intracellular antioxidant and oxidative damage repair, comprising HydroMg composite hydrogen storage microspheres 100 and functional ingredients 200 in a mass ratio of (65-80):(20-35); specifically:

[0064] 1. HydroMg composite hydrogen storage microspheres 100, comprising a mixed core material 1 and a wall material 2, wherein the mass ratio of the mixed core material 1 to the wall material 2 is 1:(1-3);

[0065] 1.1 The wall material 2 includes resistant dextrin and optional wall material ingredients, wherein the wall material ingredients are selected from at least one of gelatin, chitosan, sodium alginate, and glyceryl monolaurate, and the total mass of the wall material ingredients to the mass ratio of resistant dextrin is (1-4):5; specifically, the resistant dextrin, gelatin and sodium alginate are provided in a mass ratio of 10:(2-6):(2-6), or the resistant dextrin, gelatin, chitosan and glyceryl monolaurate are compounded in a mass ratio of 10:(2-6):(1-2):(2-5) to provide the wall material 2;

[0066] 1.2. By weight, the mixed core material 1 comprises the following components:

[0067] 40-70 parts of magnesium-based hydrogen storage material

[0068] Core material ingredients: 30-60 parts;

[0069] Magnesium-based hydrogen storage material is prepared by hydrogenation of pharmaceutical-grade or food-grade magnesium oxide with hydrogen gas; the core material ingredients include chitosan oligosaccharide, and optionally calcium carbonate, oyster powder, and porous dextrin.

[0070] Specifically, the mixed core material 1 is prepared through the following steps:

[0071] S1. Preparation of magnesium-based hydrogen storage materials

[0072] S1.1 Mix pharmaceutical-grade or food-grade magnesium oxide with a purity greater than 99% with oyster calcium and sodium hyaluronate evenly, and ball mill for 1-2 hours to obtain a sodium-magnesium ion composition; wherein, the amount of oyster calcium and sodium hyaluronate is 1-3% of the mass of magnesium oxide; the magnesium oxide mentioned above is, for example, food-grade magnesium oxide, which meets GB14880.2012 "National Food Safety Standard for the Use of Food Fortifiers" and GB2760-2014 "National Food Safety Standard for the Use of Food Additives";

[0073] S1.2 Disperse the sodium magnesium ion composition and mesoporous silica in water and mix them evenly; the amount of mesoporous silica is 10-20% of the mass of magnesium oxide;

[0074] Under the action of electric field S1.3, water is electrolyzed to produce hydrogen gas, resulting in a suspension of white crystals that adsorb and store hydrogen gas.

[0075] S1.3 The suspension is filtered and dried by passing hydrogen gas to obtain magnesium-based hydrogen storage material 11;

[0076] S1.4 The magnesium-based hydrogen storage material 11 is dispersed in liquid polyethylene glycol with a molecular weight of 400-600, and filtered to obtain the pre-coated magnesium-based hydrogen storage material;

[0077] S2. Mix the core material ingredients with the pre-coated magnesium-based hydrogen storage material evenly to form an electrostatic adsorption hydrogen storage layer 13 on the outside of the pre-coated magnesium-based hydrogen storage material, and then vacuum dry to obtain the mixed core material 1.

[0078] The mesoporous silica undergoes certain surface modification treatments to improve its surface activity; for example, plasma surface activation treatment can be selected, with the vacuum degree controlled at 1×10⁻⁶. -2 Up to 10×10 -2 Pa, heat to 80-120℃, and activate the surface of mesoporous silica using hydrogen or oxygen plasma under vacuum for 1-5 minutes.

[0079] In the core material ingredients, the mass ratio of chitosan oligosaccharide, calcium carbonate, oyster powder and porous dextrin is (5-10):(1-3):(1-3):(1-3).

[0080] 1.3 HydroMg composite hydrogen storage microspheres were prepared by rotary evaporation, specifically including the following steps:

[0081] Step 1: A magnesium-based hydrogen storage material is prepared by hydrogen charging with pharmaceutical-grade or food-grade magnesium oxide; and the magnesium-based hydrogen storage material is blended with chitosan oligosaccharide, as well as optional calcium carbonate, oyster powder and porous dextrin to obtain a mixed core material 1.

[0082] Step 2: Add the wall material raw material to deionized water at 60-80℃ and stir to obtain a wall material solution;

[0083] Step 3: Disperse the mixed core material in the wall material solution, and homogenize under pressure to obtain a mixed suspension; the pressure homogenization can be carried out at a speed of 10000-15000 r / min and a pressure of 30-50 MPa for 1-3 times;

[0084] Step 4: The mixed suspension was used to prepare HydroMg composite hydrogen storage microspheres 100 by rotary evaporation.

[0085] This invention can produce HydroMg composite hydrogen storage microspheres using a pharmaceutical-grade solid hydrogen storage sustained-release material preparation device. The structure and composition of this device can be found in the applicant's prior application 202310913221.7 (A pharmaceutical-grade solid hydrogen storage sustained-release material preparation device and method for anti-aging), which is incorporated herein by reference in its entirety. The specific implementation method can be adjusted according to the composition of this invention.

[0086] 2. Functional ingredient 200 includes at least one of dietary fiber, edible organic acid, and compound lactic acid bacteria; preferably, functional ingredient 200 is compound lactic acid bacteria particles coated with water-soluble dietary fiber and edible organic acid, and the mass ratio of water-soluble dietary fiber, edible organic acid and compound lactic acid bacteria is (5-10):(1-5):(10-20); that is, a functional shell 20 is formed by a mixture of water-soluble dietary fiber and edible organic acid, and a functional core 21 is formed by coating compound lactic acid bacteria;

[0087] The water-soluble dietary fiber is selected from at least one of the following: water-soluble dietary fiber from fruits and vegetables, water-soluble dietary fiber from cereals, and water-soluble dietary fiber from legumes.

[0088] The compound lactic acid bacteria comprises Lactobacillus paracasei, Streptococcus thermophilus, and Lactobacillus bulgaricus in a mass ratio of (1-2):(1-2):(1-2), with the viable count of Lactobacillus paracasei, Streptococcus thermophilus, and Lactobacillus bulgaricus ≥1×10⁻⁶. 9 CFU / g;

[0089] The edible organic acid is selected from one or more combinations of sialic acid, citric acid, tartaric acid, malic acid, and lactic acid;

[0090] The functional ingredients are prepared through the following steps:

[0091] (1) Dissolve water-soluble dietary fiber and edible organic acid in deionized water to obtain a spray solution; mix compound lactic acid bacteria evenly to obtain compound bacterial powder;

[0092] (2) Spray the spray liquid onto the compound bacterial powder and stir evenly at the same time;

[0093] (3) Drying is carried out by passing in dry gas at 20-40℃ to obtain compound lactic acid bacteria particles coated with water-soluble dietary fiber and edible organic acid.

[0094] After preparing the HydroMg composite hydrogen storage microspheres and functional ingredients separately, the two are mixed evenly in proportion to obtain the microsphere composition of the present invention.

[0095] Through the above structural design, the HydroMg composite hydrogen storage microspheres of the present invention actually include at least a magnesium-based hydrogen storage material 11 at the core, a polyethylene glycol pre-coating layer 12, an electrostatic adsorption hydrogen storage layer 13 formed by the core material formulation, and an outer wall material 2. Furthermore, the wall material 2 can also be designed to have a density gradient to further control the stability and sustained-release performance of the microspheres. For example, different compositions and / or different concentrations of wall material solutions can be used to obtain different mixed suspensions, which are then distributed to form composite wall materials via rotary evaporation. Preferably, the outer wall material has a higher density than the inner wall material, effectively improving the water-blocking stability of the microspheres.

[0096] The microsphere composition of the present invention has a particle size of less than 50 μm, preferably less than 30 μm; an overall average moisture content of less than 3.8 wt%, preferably less than 3.5 wt%; a water activity of less than 0.4 aw, preferably less than 0.35 aw; and a microsphere encapsulation rate of greater than 90%. Moisture content and water activity have a significant impact on the viscosity, microbial stability, oxidation degree, and storage stability of the composition. The present invention has low moisture content and water activity, ensuring storage stability and safety in use.

[0097] Regarding this microsphere composition, the present invention specifically points out that it can be used in food, pharmaceuticals or skin care products. Its specific dosage form and dosage can be selected and adjusted according to actual application, which is highly designable and has great promotional value.

[0098] Example 1

[0099] The HydroMg microsphere composition sample for intracellular antioxidant and oxidative damage repair in this embodiment includes HydroMg composite hydrogen storage microspheres and functional ingredients in a mass ratio of 70:30; specifically:

[0100] 1. HydroMg composite hydrogen storage microspheres consist of a mixed core material and a wall material, with a mass ratio of the mixed core material to the wall material of 1:1.5;

[0101] 1.1 The wall material should be resistant dextrin;

[0102] 1.2 The mixed core material, by weight, includes: 70 parts magnesium-based hydrogen storage material and 30 parts chitosan oligosaccharide.

[0103] Magnesium-based hydrogen storage materials are prepared by hydrogenation of pharmaceutical-grade or food-grade magnesium oxide with hydrogen gas, followed by combination with chitosan oligosaccharides. The core material is prepared through the following steps:

[0104] S1. Preparation of magnesium-based hydrogen storage materials

[0105] S1.1 Disperse food-grade magnesium oxide with a purity greater than 99% (meeting GB14880.2012 "National Food Safety Standard for the Use of Food Fortifiers" and GB2760-2014 "National Food Safety Standard for the Use of Food Additives") in water;

[0106] Under the influence of electric field S1.2, water is electrolyzed to produce hydrogen gas;

[0107] S1.3 Hydrogen gas is adsorbed and stored by magnesium oxide, resulting in a suspension containing white crystals;

[0108] S1.4 The suspension is filtered and dried by passing hydrogen gas to obtain magnesium-based hydrogen storage material;

[0109] S2. Chitosan oligosaccharide is mixed evenly with magnesium-based hydrogen storage material to form an electrostatic adsorption hydrogen storage layer on the outside of magnesium-based hydrogen storage material, and vacuum drying is performed to obtain the mixed core material.

[0110] 1.3 HydroMg composite hydrogen storage microspheres were prepared by rotary evaporation, specifically including the following steps:

[0111] Step 1: Prepare the hybrid core material;

[0112] Step 2: Add the wall material raw material to 70℃ deionized water and stir to obtain a wall material solution;

[0113] Step 3: Disperse the mixed core material in the wall material solution and homogenize under pressure (homogenization twice at 40 MPa and a rotation speed of 15000 r / min) to obtain a mixed suspension;

[0114] Step 4: The mixed suspension is used to prepare HydroMg composite hydrogen storage microspheres by rotary evaporation.

[0115] 2. Functional ingredients are compound lactic acid bacteria granules coated with water-soluble dietary fiber and edible organic acids. The mass ratio of water-soluble dietary fiber, edible organic acids and compound lactic acid bacteria is 10:5:15.

[0116] The water-soluble dietary fiber is selected as a complex of water-soluble dietary fiber from fruits and vegetables, water-soluble dietary fiber from cereals, and water-soluble dietary fiber from legumes, with a mass ratio of approximately 2:1:1.

[0117] The compound lactic acid bacteria comprises Lactobacillus paracasei, Streptococcus thermophilus, and Lactobacillus bulgaricus in a mass ratio of 1:1:2, with a viable count of ≥2×10⁻⁶ for each of the Lactobacillus paracasei, Streptococcus thermophilus, and Lactobacillus bulgaricus. 9 CFU / g;

[0118] The edible organic acids include sialic acid;

[0119] The functional ingredients are prepared through the following steps:

[0120] (1) Dissolve water-soluble dietary fiber and edible organic acid in deionized water to obtain a spray solution; mix compound lactic acid bacteria evenly to obtain compound bacterial powder;

[0121] (2) Spray the spray liquid onto the compound bacterial powder and stir evenly at the same time;

[0122] (3) Drying is carried out by passing in dry gas at about 35°C to obtain compound lactic acid bacteria particles coated with water-soluble dietary fiber and edible organic acids.

[0123] After preparing the HydroMg composite hydrogen storage microspheres and functional ingredients separately, the two are mixed evenly.

[0124] Example 2

[0125] The HydroMg microsphere composition sample for intracellular antioxidant and oxidative damage repair in this embodiment includes HydroMg composite hydrogen storage microspheres and functional ingredients in a mass ratio of 75:25; specifically:

[0126] 1. HydroMg composite hydrogen storage microspheres consist of a mixed core material and a wall material, with a mass ratio of the mixed core material to the wall material of 1:1.5;

[0127] 1.1 The wall material should be resistant dextrin;

[0128] 1.2 The mixed core material, by weight, includes: 60 parts magnesium-based hydrogen storage material, 25 parts chitosan oligosaccharide, 4 parts calcium carbonate, 6 parts oyster powder, and 5 parts porous dextrin.

[0129] The core material is prepared through the following steps:

[0130] S1. Preparation of magnesium-based hydrogen storage materials

[0131] S1.1 Pharmaceutical-grade or food-grade magnesium oxide with a purity greater than 99% (e.g., food-grade magnesium oxide meeting GB14880.2012 "National Food Safety Standard for the Use of Food Fortifiers" and GB2760-2014 "National Food Safety Standard for the Use of Food Additives") is mixed evenly with oyster calcium and sodium hyaluronate, and ball-milled for 1 hour to obtain a sodium-magnesium ion composition; wherein, the amount of oyster calcium is 2% of the mass of magnesium oxide, and the amount of sodium hyaluronate is 3% of the mass of magnesium oxide;

[0132] S1.2 The sodium-magnesium ion composition and mesoporous silica are dispersed in water and mixed evenly; the amount of mesoporous silica is 15% of the mass of magnesium oxide, and it undergoes plasma surface activation treatment while controlling the vacuum degree to approximately 3 × 10⁻⁶. -2 Pa, heated to 90℃, and activated on the surface of mesoporous silica using oxygen plasma under vacuum for 1-5 minutes.

[0133] Under the action of electric field S1.3, water is electrolyzed to produce hydrogen gas, resulting in a suspension of white crystals that adsorb and store hydrogen gas.

[0134] S1.3 The suspension is filtered and dried by passing hydrogen gas to obtain magnesium-based hydrogen storage material;

[0135] S1.4 The magnesium-based hydrogen storage material is dispersed in liquid polyethylene glycol with a molecular weight of 400-600, and filtered to obtain the pre-coated magnesium-based hydrogen storage material;

[0136] S2. Mix the core material ingredients with the pre-coated magnesium-based hydrogen storage material evenly to form an electrostatic adsorption hydrogen storage layer on the outside of the pre-coated magnesium-based hydrogen storage material, and then vacuum dry to obtain the mixed core material.

[0137] 1.3 HydroMg composite hydrogen storage microspheres were prepared by rotary evaporation, specifically including the following steps:

[0138] Step 1: Preparation of the hybrid core material (repeated parts will not be described again);

[0139] Step 2: Add the wall material raw material to 70℃ deionized water, stir to obtain a wall material solution, and then cool it down to below 40℃;

[0140] Step 3: Disperse the mixed core material in the wall material solution and homogenize under pressure (homogenization twice at 40 MPa and a rotation speed of 15000 r / min) to obtain a mixed suspension;

[0141] Step 4: The mixed suspension is used to prepare HydroMg composite hydrogen storage microspheres by rotary evaporation.

[0142] 2. The functional ingredients and their composite hydrogen storage microspheres with HydroMg are the same as in Example 1.

[0143] Example 3

[0144] This embodiment is basically the same as Embodiment 2, except that the wall material includes the following components:

[0145] (1.1) 10 parts of resistant dextrin

[0146] (1.2) 5 parts gelatin

[0147] (1.3) 5 parts sodium alginate.

[0148] Example 4

[0149] The preparation method in this embodiment is basically the same as that in Example 2, except that the wall material includes the following components:

[0150]

[0151] Example 5

[0152] The preparation method in this embodiment is basically the same as that in Example 4, except that the mass ratio of the core material to the wall material is 1:2.

[0153] Performance testing and methods:

[0154] 1. Average particle size: The particle size of the sample was measured using a laser particle size analyzer. The particle refractive index was set to 1.414 and the particle absorption rate to 0.001. Pure water was used as the dispersant.

[0155] 2. Moisture Content: The moisture content of the sample was determined using a moisture analyzer. 0.50g of sample was weighed and placed in the sample pan of the instrument. The instrument temperature was set to 105℃, and the time was set automatically (until constant weight was achieved). The reading was recorded. Each sample was measured three times, and the average value was used for comparison. The moisture content was calculated using the following formula: Moisture content (%) = (M - M1) ÷ M × 100%; Where: M is the original mass of the sample (g); M1 is the mass of the sample dried to constant weight at 105℃ (g).

[0156] 3. Water activity: The water activity of the sample was measured at 25℃ using a water activity meter. The measurement was performed in parallel for 3 times and the average value was taken.

[0157] 4. HydroMg Effective Encapsulation Rate: After measuring the hydrogen concentration of the microspheres using a hydrogen concentration analyzer and converting the hydrogen mass, the HydroMg effective encapsulation rate is estimated using the following formula:

[0158]

[0159] In the formula, M H2 To measure the mass of hydrogen, M HydroMg This represents the initial mass of the magnesium-based hydrogen storage material.

[0160] The test results are shown in Table 1:

[0161] Table 1 Test results of Examples 1-5

[0162]

[0163]

[0164] The following tests were performed on the magnesium-based hydrogen storage material HydroMg in the example samples:

[0165] (1) Ability to scavenge superoxide anion free radicals

[0166] 1.1 Experimental Samples: 5 mg / mL of magnesium-based hydrogen storage material HydroMg, 2.5 mg / mL of magnesium-based hydrogen storage material HydroMg, 1.25 mg / mL of magnesium-based hydrogen storage material HydroMg, 0.625 mg / mL of magnesium-based hydrogen storage material HydroMg, SOD, β-nicotinamide mononucleotide (NMN), decarboxylated carnosine powder, glutathione, anthocyanins, and quercetin.

[0167] 1.2 Test Principle: Under weakly alkaline conditions, pyrogallol undergoes an auto-oxidation reaction, generating superoxide anions and a colored intermediate product. This intermediate product exhibits a characteristic absorption peak at 320 nm. In the initial testing phase, the amount of the intermediate product shows a linear relationship with time. When a superoxide anion scavenger is added, it reacts rapidly with the superoxide anions, thereby preventing the accumulation of the intermediate product and reducing the light absorption at 320 nm. Therefore, the scavenging effect of the scavenger on superoxide anions can be evaluated by measuring the A320 value.

[0168] 1.3 Instruments and Reagents

[0169] Instruments: UV-Vis spectrophotometer (PhotoLab 6600), electric thermostatic water bath (HH.S11-2-S);

[0170] Reagents: 3 mmol / L pyrogallol, 0.05 mol / L Tris-HCl buffer (pH = 8.2), 0.01 mol / L HCl.

[0171] 1.4 Test Results

[0172] Take 5 mL of 0.05 mol / L Tris-HCl buffer (pH = 8.2), preheat in a 25°C water bath for 20 min, add 4 mL of different sample solutions, preheat in a 25°C water bath for 20 min, then add 1 mL of 3 mmol / L pyrogallol (preheated in a 25°C water bath for 20 min), mix well, and react accurately in a 25°C water bath for 15 min. Measure the absorbance at 320 nm. For the blank control group, use the same volume of distilled water instead of the sample. Perform three parallel samples for each test group and take the average value. Simultaneously, set up a background control group for each group, replacing the pyrogallol solution with 1 mL of 0.01 mol / L HCl (the solvent for the pyrogallol solution), with the remaining procedures the same as the test group.

[0173] Calculation formula:

[0174] Among them: A o The absorbance of the blank control solution (subtracted from the blank background) is A. x A represents the absorbance after adding the sample solution. xo The absorbance of the extract background is shown in the figure. Figure 2 .

[0175] Different concentrations of the magnesium-based hydrogen storage material HydroMg showed good scavenging effects on superoxide anion free radicals, and the higher the concentration, the better the scavenging effect; anthocyanins and quercetin (pentahydroxyflavone) had no scavenging effect.

[0176] (2) Ability to scavenge hydroxyl radicals

[0177] 1.1 Experimental Samples: Samples used for testing the ability to scavenge superoxide anion free radicals.

[0178] 1.2 Test Principle: Hydrogen peroxide (H₂O₂) reacts with ferrous sulfate (FeSO₄) to generate hydroxyl radicals (·OH). Salicylic acid then reacts with these hydroxyl radicals (·OH) to generate 2,3-dihydroxybenzoic acid, which has a maximum absorption wavelength at 510 nm. Adding a substance with free radical scavenging capabilities can inhibit the formation of 2,3-dihydroxybenzoic acid, thus reducing the absorbance at 510 nm.

[0179] 1.3 Instruments and Reagents

[0180] Instruments: UV-Vis spectrophotometer (PhotoLab 6600), electric thermostatic water bath (HH.S11-2-S)

[0181] Reagents: 8.8 mmol / L hydrogen peroxide, 9 mmol / L ferrous sulfate, 9 mmol / L salicylic acid-ethanol

[0182] 1.4 Test Results

[0183] Add 2 mL of different sample solutions, 2 mL of 9 mmol / L salicylic acid-ethanol, and 2 mL of 9 mmol / L FeSO4 to test tubes respectively. Finally, add 2 mL of 8.8 mmol / L H2O2 to start the reaction. React at 37℃ for 15 min, using distilled water as a blank control. Measure the absorbance of each test solution at 510 nm. Considering the absorbance of the samples themselves, use 2 mL of 9 mmol / L salicylic acid-ethanol, 2 mL of 9 mmol / L FeSO4, 2 mL of distilled water, and 2 mL of sample solutions of different concentrations as background control groups, with reaction conditions the same as the test group.

[0184] Calculation formula:

[0185] Among them: A o The absorbance of the blank control solution (subtracted from the blank background) is A. x A represents the absorbance after adding the sample solution. xo The absorbance of the extract background is shown in the test results. Figure 3 .

[0186] Different concentrations of the magnesium-based hydrogen storage material HydroMg all exhibit good scavenging effects on hydroxyl radicals, with higher concentrations showing better scavenging effects.

[0187] (3) Permeability test

[0188] 1.1 Experimental samples: 5 mg / mL magnesium-based hydrogen storage material HydroMg, SOD, β-nicotinamide mononucleotide (NMN), and decarboxylated carnosine powder.

[0189] 1.2 Test Principle

[0190] The "hydrogen-water concentration titration method" is adopted, which belongs to the redox titration method. Colloidal platinum (nanoplatinum) catalyzes the reduction of methylene blue (MB) by hydrogen gas.

[0191] 1.3 Instruments and Reagents:

[0192] Instruments and consumables: electronic balance, stopwatch, wide-mouth glass bottle, resealable food storage bags (polyethylene (PE) resin);

[0193] Reagents: 0.4 mg / mL citric acid solution, reagent for determining dissolved hydrogen concentration.

[0194] 1.4 Experimental Method: Different sample solutions, namely HydroMg, SOD, β-nicotinamide mononucleotide (NMN), and 0.1g of skin-peeling powder, were added to wide-mouth glass bottles containing 500mL of 0.4mg / mL citric acid solution. 50L of dissolved hydrogen concentration assay reagent was added to a resealable plastic bag and placed in the wide-mouth glass bottle, ensuring the bag was in full contact with the solution surface. A 0.4mg / mL citric acid solution was used as a blank control group. The color change of the dissolved hydrogen concentration assay reagent in the resealable plastic bags of each group was observed over time.

[0195] 1.5 Test Results

[0196] After 6 minutes and 20 seconds, the color of the resealable bag containing the 5 mg / mL magnesium-based hydrogen storage material HydroMg changed from blue to colorless, while the colors of other groups remained unchanged. This indicates that HydroMg can release hydrogen gas, which permeates into the resealable bag, causing the hydrogen concentration assay reagent to turn colorless.

[0197] As can be seen from tests (1)-(3), the magnesium-based hydrogen storage material HydroMg can release hydrogen gas, has penetrability, and has a strong ability to scavenge superoxide anion free radicals and hydroxyl free radicals.

[0198] (4) Anti-cellular aging effect

[0199] Human umbilical vein endothelial cells (HUVECs) were pretreated for 15 minutes with different concentrations of the magnesium-based hydrogen storage material HydroMg (0.02 mg / ml, 0.04 mg / ml, 0.1 mg / ml, 0.2 mg / ml, and 0.4 mg / ml) or β-nicotinamide mononucleotide (NMN) (0.02 mg / ml, 0.04 mg / ml, 0.1 mg / ml, 0.2 mg / ml, and 0.4 mg / ml), followed by treatment with oxidized low-density lipoprotein (OX-LDL) (100 μg / ml) for 24 hours to induce endothelial cell senescence. When cells senescent, β-galactosidase in endogenous lysosomes is specifically expressed and accumulates in large quantities in the cytoplasm, resulting in significantly higher levels in senescent cells than in normal cells. Due to its ease of detection, β-galactosidase serves as a biomarker for cellular senescence. The degree of cellular senescence was detected using a β-galactosidase staining kit. Analysis of cell staining images using ImageJ software revealed that HydroMg concentration-dependently reduced the proportion of cells stained dark green, suggesting a significant decrease in the level of the aging marker β-galactosidase in cells. HydroMg's anti-cellular aging effect is superior to that of NMN (see appendix). Figure 4 ,5). In summary, HydroMg has a significant effect in alleviating vascular endothelial cell aging.

[0200] (5) Anti-inflammatory effect

[0201] Different concentrations (0.04 mg / ml and 0.2 mg / ml) of the magnesium-based hydrogen storage material HydroMg and dexamethasone (DEX, 2.5*10⁻⁶) were added to the mouse macrophage line RAW264.7. -7 After pretreatment with 100 ng / ml endotoxin LPS for 15 minutes, cells were stimulated for 2 h or 6 h with 100 ng / ml endotoxin LPS. Cells were then washed with phosphate-buffered saline (PBS), and total RNA was extracted from the cells with TRIZOL. After measuring the concentration, 0.5 μg of RNA was reverse transcribed into cDNA. The expression levels of inflammatory factors TNF-α, IL-6, and IL-10 were detected by real-time quantitative PCR, and their relative expression levels were calculated using 36b4 as an internal reference.

[0202] The results are as follows Figure 6-8 As shown, in macrophages, pretreatment with the magnesium-based hydrogen storage material HydroMg significantly reduced the mRNA expression levels of LPS-induced pro-inflammatory cytokines TNF-α and IL-6, with the inhibitory effect of 0.2 mg / ml HydroMg even stronger than that of dexamethasone. Simultaneously, HydroMg pretreatment increased the mRNA expression level of the anti-inflammatory cytokine IL-10. In conclusion, HydroMg exhibits significant anti-inflammatory effects.

[0203] The preferred embodiments of the present invention have been described above to make the spirit of the present invention clearer and easier to understand, and are not intended to limit the present invention. All modifications, substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope summarized by the appended claims.

Claims

1. A method for preparing a HydroMg microsphere composition for intracellular antioxidant and oxidative damage repair, characterized in that, The HydroMg microsphere composition includes HydroMg composite hydrogen storage microspheres and functional ingredients; The functional ingredients include at least one of water-soluble dietary fiber, edible organic acids, and compound lactic acid bacteria; The HydroMg composite hydrogen storage microspheres include a mixed core material and a wall material, with a mass ratio of the mixed core material to the wall material of 1:(1-3). The wall material includes resistant dextrin; The mixed core material comprises the following components in parts by weight: 40-70 parts of magnesium-based hydrogen storage material Core material ingredients: 30-60 parts; The core material ingredients include chitosan oligosaccharide, and optionally calcium carbonate, oyster powder, and porous dextrin; The preparation method includes the following steps: Step 1: Preparation of the hybrid core material: S1. Preparation of magnesium-based hydrogen storage materials using magnesium oxide and hydrogen charging. S1.1 Magnesium oxide with a purity greater than 99% is mixed evenly with oyster calcium and sodium hyaluronate, and ball-milled for 1-2 hours to obtain a sodium magnesium ion composition; S1.2 Disperse the sodium magnesium ion composition and mesoporous silica in water and mix them evenly; Under the action of electric field S1.3, water is electrolyzed to produce hydrogen gas, resulting in a suspension of white crystals that adsorb and store hydrogen gas. S1.4 The suspension is filtered and dried by passing hydrogen gas to obtain magnesium-based hydrogen storage material; S1.5 The magnesium-based hydrogen storage material is dispersed in liquid polyethylene glycol with a molecular weight of 400-600, and filtered to obtain the pre-coated magnesium-based hydrogen storage material; S2. Mix the core material ingredients with the pre-coated magnesium-based hydrogen storage material evenly to form an electrostatic adsorption hydrogen storage layer on the outside of the pre-coated magnesium-based hydrogen storage material, and then vacuum dry to obtain the mixed core material. Step 2: Add the wall material raw material to deionized water at 60-80℃ and stir to obtain a wall material solution; Step 3: Disperse the mixed core material in the wall material solution, and homogenize under pressure to obtain a mixed suspension; Step 4: The mixed suspension is used to prepare HydroMg composite hydrogen storage microspheres by rotary evaporation at a temperature of 30-60℃; Step 5: Mix the HydroMg composite hydrogen storage microspheres with the functional ingredients evenly.

2. The preparation method according to claim 1, characterized in that, In step four, the rotary evaporation method includes drying the product to a moisture content of less than 4% using a centrifugal pump under conditions of vacuum less than 150 Pa and temperature of 30-60 °C.

3. The preparation method according to claim 1, characterized in that, The mass ratio of HydroMg composite hydrogen storage microspheres to functional ingredients is (65-80):(20-35).

4. The preparation method according to claim 3, characterized in that, The functional ingredient is a compound lactic acid bacteria granule coated with water-soluble dietary fiber and edible organic acid, and the mass ratio of water-soluble dietary fiber, edible organic acid and compound lactic acid bacteria is (5-10):(1-5):(10-20).

5. The preparation method according to claim 4, characterized in that, The water-soluble dietary fiber is selected from at least one of the following: fruit and vegetable water-soluble dietary fiber, cereal water-soluble dietary fiber, legume water-soluble dietary fiber, and small molecule water-soluble dietary fiber. The compound lactic acid bacteria comprises Lactobacillus casei, Bifidobacterium lactis, Lactobacillus paracasei, Streptococcus thermophilus, and Lactobacillus bulgaricus in a mass ratio of (1-2):(1-2):(1-2), with the viable counts of Lactobacillus paracasei, Streptococcus thermophilus, and Lactobacillus bulgaricus ≥1×10⁻⁶. 9 CFU / g; The edible organic acid is selected from one or more combinations of sialic acid, citric acid, tartaric acid, malic acid, and lactic acid.

6. The preparation method according to claim 5, characterized in that, The functional ingredients are prepared through the following steps: (1) Dissolve water-soluble dietary fiber and edible organic acid in deionized water to obtain a spray solution; mix compound lactic acid bacteria evenly to obtain compound bacterial powder; (2) Spray the spray solution onto the compound bacterial powder while stirring evenly; (3) Drying is carried out by passing in dry gas at 20-40℃ to obtain compound lactic acid bacteria particles coated with water-soluble dietary fiber and edible organic acid.

7. The preparation method according to any one of claims 1-6, characterized in that, In the core material ingredients, the mass ratio of chitosan oligosaccharide, calcium carbonate, oyster powder and porous dextrin is (5-10): (1-3): (1-3): (1-3).

8. The preparation method according to any one of claims 1-6, characterized in that, The wall material also includes wall material ingredients selected from at least one of gelatin, chitosan, sodium alginate, and glyceryl monolaurate, and the total mass of the wall material ingredients to the mass ratio of resistant dextrin is (1-4):

5.

9. The use of a HydroMg microsphere composition for intracellular antioxidant and oxidative damage repair obtained by any one of claims 1-8 in the preparation of food, pharmaceutical or skin care products.

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