Glycine chelated magnesium with high magnesium content and high bioavailability and preparation method thereof

Abstract

The invention discloses glycine chelated magnesium with high magnesium content and high bioavailability and a preparation method of the glycine chelated magnesium. The preparation method comprises the following steps: firstly, adding water into a reaction kettle, stirring and heating, then adding glycine for dissolving, then adding magnesite powder, continuously heating for reaction, filtering reaction liquid after the reaction is completed, and then carrying out spray drying to obtain the glycine magnesium. Glycine and pure natural magnesite powder are used as raw materials to react, unreacted filter residues are filtered after the reaction is completed to obtain the reaction liquid, the reaction liquid is subjected to spray drying to obtain anhydrous magnesium glycinate with the magnesium content larger than or equal to 14.0%, the magnesium content is remarkably increased, the source of the magnesite powder is low in price and easy to obtain, and the production cost is effectively reduced. The preparation method disclosed by the invention is green and environment-friendly, high in production efficiency and easy for industrial production, and has remarkable economic benefits and social benefits. By comparing in-vitro simulated digestion tests of various magnesium glycinate, magnesium glycinate with the content of 14% has higher bioavailability.

Description

Technical Field

[0001] The present invention relates to the technical field of amino acid chelation, and more particularly to a glycine chelated magnesium with high magnesium content and high bioavailability and a preparation method thereof. Background Art

[0002] Magnesium is one of the indispensable minerals for the human body. The human body cannot produce magnesium and must be ingested from the outside. In recent years, most people have focused on the nutrient calcium, and rarely on the supplementation of "magnesium". The "Dietary Reference Intake of Nutrients for Chinese Residents (2023 Edition)" recommends that the recommended daily intake of magnesium for adults is 330 mg, which is second only to calcium supplementation. Magnesium deficiency is associated with a wide range of health problems, from cardiovascular disease to dementia to osteoporosis.

[0003] Traditional magnesium supplements are mostly first-generation preparations in the form of inorganic salts such as magnesium sulfate and magnesium oxide. However, such preparations are easy to absorb moisture, have high irritation to the gastrointestinal tract, and have low bioavailability. At the same time, a large amount of inorganic trace elements will be excreted with urine, resulting in a waste of trace elements. Subsequently, second-generation magnesium supplements represented by magnesium citrate and magnesium malate appeared. Compared with inorganic salts, they have better solubility and less irritation to the gastrointestinal tract. The disadvantage is that the magnesium content is low. The third-generation preparation of amino acid chelated magnesium with good stability, which is centered on magnesium atoms and amino acids as ligands, has high magnesium content, good absorption efficiency, high biological efficacy, low toxicity, and good palatability. Magnesium glycinate, as the smallest molecular weight and most easily absorbed chelate among amino acid magnesium, has broad application prospects.

[0004] As people's living standards improve, they are paying more and more attention to the natural sources of magnesium. The magnesium source in China's public patent CN109608349A is processed, and the magnesium content of the obtained magnesium glycinate is 11.4%; the magnesium content of the magnesium glycinate in China's public patent CN106478438A ranges from 10.8% to 12.5%, and the content deviation is relatively large. The standard molecular formula of 2:1 type magnesium glycinate should be Mg(C2H4NO2)2, and the magnesium content is 14.0%, and there is no relevant report. Similarly, the bioavailability of magnesium glycinate has not been well verified, so it is urgent to develop a high magnesium content and high bioavailability glycinate chelated magnesium. Summary of the invention

[0005] In view of this, the present invention provides a glycine chelated magnesium with high magnesium content and high bioavailability and a preparation method thereof, which is simple, environmentally friendly, and suitable for industrial production.

[0006] To achieve the above object, the present invention adopts the following technical solution:

[0007] First, the present invention provides a method for preparing glycine chelated magnesium with high magnesium content and high bioavailability, comprising the following steps:

[0008] (1) Add water to a reaction kettle, start stirring and increase the temperature, and add glycine to the kettle to dissolve;

[0009] (2) adding magnesite powder to the solution after the complete dissolution in step (1), and continuing to heat the reaction;

[0010] (3) After the reaction is completed, the reaction solution is filtered and then spray-dried to obtain magnesium glycinate with a magnesium content of ≥14%.

[0011] Preferably, the heating temperature in step (1) is 40-60°C.

[0012] Preferably, the amount of water added in step (1) is 150-300 L per 1,000 mol of glycine.

[0013] Preferably, the heating temperature in step (2) is 90-105° C., and the reaction time is 0.5-2 h.

[0014] Preferably, the mass ratio of glycine to magnesite powder is 1:(0.8-1.2).

[0015] Preferably, the filtration in step (3) is performed using a 1 μm filter.

[0016] Preferably, in step (3), the spray drying has an inlet air temperature of 260-300°C, an outlet air temperature of 130-150°C, and a rotation speed of 8000-20000 r / min.

[0017] In addition, the present invention also provides a magnesium glycine chelate prepared by the method described in the above technical solution.

[0018] It can be seen from the above technical solution that, compared with the prior art, the present invention discloses a magnesium glycine chelate with high magnesium content and high bioavailability and a preparation method thereof, which has the following beneficial effects:

[0019] The magnesium content of the magnesium glycinate chelate prepared by the present invention is 14.0%, which is anhydrous magnesium glycinate, and the magnesium content is significantly improved. When supplementing metal elements, glycine is also supplemented, which plays a double supplement role. The source of dolomite powder is cheap and easy to obtain, which effectively reduces the production cost. The reaction process of the preparation method of the present invention is green and environmentally friendly. Through spray drying, the production efficiency is greatly improved, and it is easy to industrialize production, with significant economic and social benefits. By comparing the in vitro simulated digestion test of various types of magnesium glycinate, the magnesium glycinate with a content of 14% of the present invention has higher bioavailability. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying creative work.

[0021] Figure 1 XRD of magnesium glycinate and 11.4% magnesium glycinate prepared in Example 1 of the present invention;

[0022] Figure 2 This is a thermogravimetric diagram of magnesium glycinate prepared in Example 1 of the present invention;

[0023] Figure 3 is the concentration of magnesium glycinate prepared in Example 1 of the present invention after gastric digestion;

[0024] Figure 4 The concentration of magnesium glycinate after intestinal digestion prepared in Example 1 of the present invention;

[0025] Figure 5 This is the concentration of magnesium glycinate Caco-2 prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0026] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] Example 1

[0028] (1) Add 450.0 L of water into an enameled reactor, start stirring, raise the temperature to 55° C., add 150.0 kg of food-grade glycine into the reactor for dissolution, and dissolve completely within 12 minutes;

[0029] (2) Add 150 kg of magnesite powder to the solution of step (1), raise the temperature to 95° C., and continue the reaction for 0.5 h;

[0030] (3) After the reaction is completed, the reaction solution to be sprayed is filtered through a 1 μm filter, and then the reaction solution is spray-dried. The inlet air temperature of the spray drying is 280° C., the outlet air temperature is 140° C., and the rotation speed is 11000 r / min, thereby obtaining 170.2 kg of magnesium glycinate product.

[0031] The yield was 97.7% and the magnesium content was 14.02%.

[0032] The XRD pattern of the prepared magnesium glycinate is as follows: Figure 1 As shown, it can be seen from the XRD spectrum that the water peak of 14% magnesium glycinate disappears, the background of the XRD graph is small, and the diffraction peak is high and sharp, indicating that it has a good crystal form and high purity.

[0033] The thermogravimetric diagram of the prepared magnesium glycinate chelate is shown in Figure 2 As shown, it can be seen from the thermogravimetric diagram that magnesium glycinate starts to lose weight at around 300°C, and the ash content of the final product is 23.26%, which is consistent with the content of MgO. No weight loss of crystal water is found, and the molecular formula of the product should be Mg(C2H5NO2)2.

[0034] Example 2

[0035] (1) Add 350.0 L of water into an enameled reactor, start stirring, raise the temperature to 55° C., add 150.0 kg of food-grade glycine into the reactor for dissolution, and dissolve completely within 15 minutes;

[0036] (2) adding 125 kg of magnesite powder to the solution of step (1), heating to 70° C., and continuing the reaction for 0.5 h to obtain a reaction solution;

[0037] (3) After the reaction is completed, the reaction liquid to be sprayed is filtered through a 1 μm filter, and then the reaction liquid is spray-dried. The inlet air temperature of the spray drying is 260° C., the outlet air temperature is 135° C., and the rotation speed is 8000 r / min, and 173.4 kg of magnesium glycinate product is obtained.

[0038] The yield was 99.6% and the magnesium content was 14.00%.

[0039] Example 3

[0040] (1) Add 3000 L of water into the enameled reactor, start stirring, raise the temperature to 55° C., add 300.0 kg of food-grade glycine into the reactor for dissolution, and dissolve completely within 10 minutes;

[0041] (2) adding 250 kg of magnesite powder to the solution of step (1), heating to 90° C., and continuing the reaction for 1 h to obtain a reaction solution;

[0042] (3) After the reaction is completed, the reaction liquid to be sprayed is filtered with a 1 μm filter, and then the reaction liquid is spray-dried. The inlet air temperature of the spray drying is 300° C., the outlet air temperature is 150° C., and the rotation speed is 15000 r / min, thereby obtaining 340.1 kg of magnesium glycinate product.

[0043] The yield was 98.8% and the magnesium content was 14.08%.

[0044] Experimental Example 1

[0045] In vitro simulated digestion was carried out using the magnesium glycinate in Example 1 and commercially available magnesium glycinate with magnesium contents of 11.4% and 20%.

[0046] Pepsin solution: Prepare pepsin into a 7 g / L solution with 0.1 mol / L hydrochloric acid. The enzyme solution should be prepared within 1 hour before the experiment.

[0047] Pancreatic enzyme and bile mixture: Mix pancreatin and bile salts, and use 0.1 mol / L sodium bicarbonate to prepare a mixed solution of 7 g / L pancreatic juice and 7.4 g / L bile. The enzyme solution should be prepared within 1 hour before the experiment.

[0048] The same concentration of magnesium glycinate solution in Example 1 and commercially available magnesium glycinate solutions with magnesium contents of 11.4% and 20% were adjusted to a pH value of 1.9 similar to gastric juice using 1 mol / L hydrochloric acid. The acidified samples were placed in a 37°C constant temperature water bath and shaken for 10 minutes. After taking out the samples, pepsin solution was added, nitrogen was filled in, the brown bottle was tightly covered, and the bottles were shaken in a 37°C constant temperature water bath for 2 hours. After the gastric digestion of the samples, they were cooled on ice for 10 minutes to stop the gastric digestion. The digestive fluid was centrifuged at constant volume with 0.9% saline, and the supernatant was taken for ICP-OES analysis. The magnesium ion absorption rate of magnesium glycinate after gastric digestion is shown in Figure 2. Figure 3 .

[0049] Intestinal digestion simulation: After the gastric digestion stage is completed, the magnesium glycinate gastric digestion solution is adjusted to pH 6.5 (this value is close to the value of the small intestine under physiological conditions) with 1 mol / L sodium hydroxide solution, and a mixed enzyme solution of pancreatic juice and bile is added, nitrogen is filled, the brown bottle is tightly covered, and the bottle is shaken in a constant temperature water bath at 37°C for 2 hours. After the end, it is cooled on ice for 10 minutes, centrifuged at constant volume with physiological saline, and the supernatant is analyzed by ICP-OES. The magnesium ion absorption rate of magnesium glycinate after intestinal digestion is shown in Figure 4 .

[0050] Experimental Example 2

[0051] Magnesium Glycinate Caco-2 Cell Transport:

[0052] The morphology and functional characteristics of the Caco-2 cell monolayer are similar to those of human intestinal epithelial cells. By establishing a Caco-2 cell model, the transport of magnesium glycinate in the digestive fluid across the cell monolayer was detected, providing a basis for exploring the factors affecting the absorption of magnesium glycinate in vivo.

[0053] Caco-2 cells were cultured in cell culture medium and placed in a constant temperature incubator at 37°C, 5% CO2 and 95% humidity, and grown in T75 cell culture flasks. When 70-90% of the cells covered the culture flask, the cell culture medium was discarded. After washing the cells with PBS, trypsin-EDTA was added to digest the cells for 5 minutes to separate the Caco-2 cells from the cell wall. Then, cell culture medium was added to terminate trypsin digestion, and the cells were blown to form single cells, and the cells were passaged at a ratio of 1:10. The cell solution was changed every two days on average until a dense cell membrane was formed after 21 days, and then relevant transport experiments could be performed.

[0054] The cell transport test was carried out at 37°C, 5% CO2, and 150 rpm shaking. After 120 min, the magnesium content was detected by ICP-OES. Figure 5 Absorption rate of magnesium glycinate after transport in Caco-2 cells.

[0055] Depend on Figure 3-5 The experimental results show that the dissolution rate of magnesium ions in the magnesium glycinate prepared by the method of the present invention after gastric digestion is 97.73%, and the dissolution rate of magnesium ions after intestinal digestion is 57.81%; the concentrations of magnesium ions in 11.4% after gastric and intestinal digestion are 98.11% and 53.24%, respectively; the dissolution rates of magnesium ions in 20% after gastric and intestinal digestion are 97.61% and 47.58%, respectively. The absorption rates of the present invention, the commercially available 11.4 and 20% magnesium glycinate after Caco-2 cell transport are 53.76%, 47.91% and 42.82%, respectively. The concentration of magnesium glycinate prepared by the method of the present invention is significantly higher than that of the other two commercially available products. Therefore, the magnesium ions in the present invention are more easily digested and absorbed in the intestinal environment, which indicates that the 14% magnesium glycinate in the present invention has higher bioavailability.

[0056] In this specification, each embodiment is described in a progressive manner, and each embodiment focuses on the differences from other embodiments, and the same and similar parts between the embodiments can be referred to each other. The above description of the disclosed embodiments enables professionals and technicians in this field to implement or use the present invention. Various modifications to these embodiments will be obvious to professionals and technicians in this field, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to these embodiments shown in this article, but will comply with the widest range consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing glycine chelated magnesium with high magnesium content and high bioavailability, characterized in that: The following steps are involved: (1) Add water to a reaction kettle, start stirring and increase the temperature, and add glycine to the kettle to dissolve; (2) adding magnesite powder to the solution after the complete dissolution in step (1), and continuing to heat the reaction; (3) After the reaction is completed, the reaction solution is filtered and then spray-dried to obtain magnesium glycinate with a magnesium content of ≥14%.

2. The method for preparing a glycine chelated magnesium with high magnesium content and high bioavailability according to claim 1, characterized in that: The heating temperature in step (1) is 40-60°C.

3. The method for preparing a glycine chelated magnesium with high magnesium content and high bioavailability according to claim 1, characterized in that: The amount of water added in step (1) is 150-300 L per 1,000 mol of glycine.

4. The method for preparing a glycine chelated magnesium with high magnesium content and high bioavailability according to claim 1, characterized in that: The heating temperature in step (2) is 90-105° C., and the reaction time is 0.5-2 h.

5. The method for preparing a glycine chelated magnesium with high magnesium content and high bioavailability according to claim 1, characterized in that: The mass ratio of the glycine to the magnesite powder is 1:(0.8-1.2).

6. The method for preparing a glycine chelated magnesium with high magnesium content and high bioavailability according to claim 1, characterized in that: The filtration in step (3) is performed using a 1 μm filter.

7. The method for preparing a glycine chelated magnesium with high magnesium content and high bioavailability according to claim 1, characterized in that: The spray drying in step (3) has an air inlet temperature of 260-300°C, an air outlet temperature of 130-150°C, and a rotation speed of 8000-20000 r / min.

8. Magnesium glycine chelate prepared by the method according to any one of claims 1 to 7.

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