A nanoscale calcium-magnesium-malate composite product and a method for preparing the same

Abstract

The application discloses a kind of nanoscale calcium magnesium malate composite product and preparation method thereof.The method of the application is rich in magnesium element alga as magnesium source and calcium hydroxide compound, using high pressure pulse electric field treatment reduces and malic acid reaction energy consumption, improves reaction efficiency, by ultrasonic oscillation treatment promotes crystal rapid formation and controls crystal particle size.Nanoscale calcium magnesium malate composite product formed absorption rate and absorption speed are significantly improved, and can supplement calcium and magnesium simultaneously, can promote the balanced absorption of trace elements.The product prepared by the method of the application not only realizes the high value-added utilization of alga, green low carbon, and improves the chelation efficiency, is suitable for industrial production.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic trace element chelate processing, in particular to a preparation method of a nanoscale calcium-magnesium-malic acid composite product. BACKGROUND

[0002] Calcium is not only an important component of human bones, but also maintains normal functions of human nerves, bones, muscles, etc., and is an indispensable element in human life activities. Calcium malate is an organic trace element additive with stable chemical properties, which can avoid the precipitation effect of Ca 2+ in the digestive tract, so that the body can fully absorb and utilize metal ions; there is no compatibility contraindication with antibiotics; organic trace elements have no special odor, the median lethal dose is much larger than inorganic salts, the toxic side effects are small, the palatability is good, and the feeding is easy; after the absorption of organic trace elements, the integrated trace elements can be directly transported to specific target tissues and enzyme systems, so as to improve the enzyme activity in the human body, improve the utilization rate of protein, fat and vitamins, and enhance the immune response of the human body.

[0003] The common preparation method of calcium malate is to prepare calcium malate by neutralization reaction of calcium oxide and malic acid. However, the disadvantage of this method is that the calcium malate particles are large and not easy to be absorbed by the human body; and the functions of the human body, such as the balance mechanism, the metabolic process, etc., are affected, for example, the control and regulation of heartbeat, muscle contraction and relaxation, and nerve conduction, all of which require the joint action of calcium and magnesium to complete, and calcium supplementation alone may inhibit the absorption of magnesium elements. SUMMARY

[0004] The technical problem to be solved by the present application is to provide a preparation method of a nanoscale calcium-magnesium-malic acid composite product. The nanoscale calcium-magnesium-malic acid composite product prepared by the present application has the advantages of high conversion rate, high solubility and short reaction time, and the operation process is simple, and the raw materials have environmental protection performance.

[0005] The technical solution adopted by the present application to solve the above technical problems is:

[0006] A method for preparing nanoscale calcium-magnesium-malic acid, comprising the following steps:

[0007] (1) edible seaweed pretreatment: after the edible seaweed is washed and dried, it is crushed and sieved to obtain seaweed powder;

[0008] (2) preparation of calcium-magnesium-malic acid:

[0009] Deionized water is added to the seaweed powder and stirred to obtain solution a;

[0010] An excess of calcium hydroxide is added to the solution a of step (2), and is placed in a high-pressure pulse electric field treatment chamber for reaction to obtain solution b;

[0011] adding ethanol solution to the solution b in step (2) to perform alcohol precipitation treatment, centrifuging to obtain the precipitate, and freeze-drying to obtain the precipitate a as the magnesium hydroxide / calcium hydroxide composite;

[0012] adding malic acid to the precipitate a in step (2) to perform high-voltage pulse treatment to obtain the calcium magnesium malate composite;

[0013] (3) Preparation of nano calcium magnesium malate:

[0014] adjusting the pH of the solution containing the calcium magnesium malate prepared in step (2), ice-bathing, adding surfactant, mixing, then placing into an ultrasonic instrument to perform oscillation to promote the precipitation of nanocrystals;

[0015] (4) Separation of nano calcium magnesium malate:

[0016] after the crystal prepared in step (3) is extracted and dried, the nano calcium magnesium malate composite product powder is obtained.

[0017] Further, the seaweed in step (1) is selected from one of the magnesium-rich algal species including Undaria pinnatifida, Porphyra, Laminaria, sea lettuce, Eucheuma, Gracilaria, Sargassum, and Gelidium.

[0018] Further, the pulverization in step (1) is to pulverize the seaweed into a powder that can pass through an 80-150 mesh sieve.

[0019] Further, in step (2), the mass ratio of the calcium content of calcium hydroxide to the magnesium content of solution a is 2:1-4:1; the solid-liquid ratio of the mixture of seaweed powder and calcium hydroxide to water is 1:0.5-1:2 g / mL; and the mass ratio of malic acid to calcium hydroxide is 3.42:1.

[0020] Further, in steps (2) and (3), the pulse electric field intensity for high-voltage pulse treatment is 10.0-25.0 kV / cm, the pulse number is 10-25 times, the pulse width is 100-200 μs, and the pulse electric field treatment time is 10-40 s.

[0021] Further, in step (3), the pH is adjusted to 6-7.5, the mass percentage content of the surfactant is 0.05-0.2%, the sodium alginate and soybean phospholipid are mixed in a mass ratio of 1-2:0.05-2, the ultrasonic power is 100-300 W, and the ultrasonic time is 5-15 min.

[0022] Compared with the prior art, the method for preparing nanoscale calcium-magnesium malate has the advantages that the seaweed is used as a magnesium source, and the crude calcium-magnesium malate is obtained through high-voltage pulse electric field treatment; and the ultrasonic vibration is used in the saturated solution precipitation process to assist the action of the surfactant, so that the particle agglomeration is prevented and the particle size and the crystal growth rate are controlled. Not only the high-value utilization, green and low carbon of the seaweed are realized, but also the chelation efficiency is improved, so that the calcium-magnesium malate is prepared quickly and efficiently, the raw material, energy and time input are reduced, the cost is lowered, and the industrial production is suitable. The nanoscale calcium-magnesium malate has the advantages of high absorption rate and high absorption speed, and can supplement calcium and magnesium to promote the balanced absorption of trace elements, so as to make up for the shortcomings of the existing calcium-magnesium preparation.

[0023] Based on the defects of the prior art, the nanoscale calcium-magnesium malate composite product is developed. The edible seaweed is used as a raw material, and the crude calcium-magnesium malate is obtained through high-voltage pulse electric field treatment; and the ultrasonic vibration is used in the saturated solution precipitation process to prevent the particle agglomeration and control the particle size and the crystal growth rate, so that the nanoscale calcium-magnesium malate composite particles can be obtained after separation and drying.

[0024] The seaweed drifts to the nearshore water area or is accumulated on the beach, and if not treated in time, it will rot soon. The resource utilization of green tide algae biomass is a difficult problem in the coastal area. Therefore, if the seaweed biomass in the offshore area of China can be fully utilized, it has important practical significance.

[0025] The seaweed contains more magnesium elements than other foods (up to 100-500 mg / 100 g), and the magnesium is organic magnesium, which is more easily absorbed by the human body. The edible seaweed is used for high-value utilization, green and low carbon. The emerging physical field technology not only can avoid the harmful changes of energy consumption and physical and sensory characteristics caused by high-temperature treatment, but also can increase the contact sites between substances, promote the formation of covalent bonds, improve the chelation efficiency, quickly and efficiently prepare the malate chelate, reduce the raw material, energy and time input, reduce the cost, and be suitable for industrial production. The nanoscale calcium-magnesium malate has the advantages of high absorption rate and high absorption speed, and can supplement calcium and magnesium to promote the balanced absorption of trace elements, so as to make up for the shortcomings of the existing calcium-magnesium preparation. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 is the influence of different treatment methods on the average particle size of the reaction product;

[0027] Figure 2 is the influence of different treatment methods on the agglomeration coefficient AF (50) of the reaction product;

[0028] Figure 3 is the influence of different treatment methods on the magnesium chelation rate of the reaction product;

[0029] Figure 4 Effect of different processing methods on calcium chelation rate of reaction products;

[0030] Figure 5 Effect of different processing methods on magnesium digestion and absorption rate of reaction products;

[0031] Figure 6 Effect of different processing methods on calcium digestion and absorption rate of reaction products; DETAILED DESCRIPTION

[0032] In order to make the objectives, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the described embodiments of the present application, all other embodiments obtained by those of ordinary skill in the art without any creative effort fall within the protection scope of the present application.

[0033] As used herein, the terms "comprises", "comprising", "includes", "including", "has", "having", "contains", "containing", or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, a step, a method, an article, or an apparatus that comprises a list of elements is not necessarily limited to only those elements but can include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.

[0034] When expressing an equivalent, a concentration, or other value or parameter in a range, a preferred range, or a range defined by a series of upper preferred values and lower preferred values, it should be understood that all ranges formed by any pairing of an upper range limit or preferred value with a lower range limit or preferred value, whether or not the range is expressly disclosed, are specifically disclosed. For example, when a range "1 to 5" is disclosed, the described range should be interpreted to include ranges "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When numerical ranges are described herein, unless otherwise stated, the range is intended to include the end values and all integers and fractions within that range.

[0035] In addition, the technical features involved in each embodiment of the present application can be combined with each other as long as there is no conflict between them.

[0036] In the following examples, the seaweed used is commercially available;

[0037] The malic acid, calcium hydroxide, sodium alginate, and soybean phospholipid used are food grade and are purchased from Shanghai Aladdin Biochem Technology Co., Ltd. Example 1

[0038] (1) Algae pretreatment: After the Undaria pinnatifida was washed and dried, it was crushed and passed through an 80-mesh sieve to obtain seaweed powder (the magnesium content in the seaweed powder was 100-500 mg / 100 g).

[0039] (2) Preparation of calcium magnesium malate: After 2.5 kg of seaweed powder was uniformly stirred with 1.27 L of deionized water, 36.91 g of calcium hydroxide was added and placed in a high-voltage pulse electric field treatment chamber. The electric field intensity was 25.0 kV / cm, the pulse number was 10, the pulse width was 100 μs, and the treatment time was 10 s. After the pulse, centrifugation (5000 rpm, 10 min) was performed, and 4 times the volume of 95% ethanol solution (v / v) was added to the white precipitate, which was then alcohol precipitated at 4°C for 8 h, followed by centrifugation (5000 rpm, 10 min) to obtain the precipitate, which was then freeze-dried to obtain precipitate a, which was a magnesium hydroxide / calcium hydroxide composite. After 126.23 g of malic acid was added to the precipitate a and high-voltage pulse treatment was performed, the electric field intensity of the high-voltage pulse treatment was 10.0-25.0 kV / cm, the pulse number was 10-25, the pulse width was 100-200 μs, and the electric field treatment time was 10-40 s. A solution containing calcium magnesium malate was obtained.

[0040] (3) Preparation of nano calcium magnesium malate: The solution containing calcium magnesium malate prepared in step (2) was adjusted to pH 6 and placed in an ice bath. After 1.27 g of sodium alginate and 0.06 g of soybean phospholipid were added and mixed, the mixture was placed in an ultrasonic instrument and shaken for 15 min at an ultrasonic power of 100 W to promote the precipitation of nanocrystals.

[0041] (4) Separation of nano calcium magnesium malate: The crystals obtained in step (3) were filtered and dried to obtain nano calcium magnesium malate powder. Example 2

[0042] (1) Algae pretreatment: After the Undaria pinnatifida was washed and dried, it was crushed and passed through an 80-mesh sieve to obtain seaweed powder (the magnesium content in the seaweed powder was 100-500 mg / 100 g).

[0043] (2) Preparation of calcium magnesium malate: 2.5 kg of seaweed powder was mixed with 2.56 L of deionized water, and 55.36 g of calcium hydroxide was added. The mixture was placed in a high-voltage pulsed electric field treatment chamber and treated at an electric field strength of 15.0 kV / cm, a pulse number of 18, a pulse width of 150 μs, and a treatment time of 25 s. After the pulse, the mixture was centrifuged (5000 rpm, 10 min) and 4 times the volume of 95% ethanol solution (v / v) was added to the white precipitate. The mixture was alcohol precipitated at 4°C for 8 h, followed by centrifugation (5000 rpm, 10 min) to obtain a precipitate. The precipitate was freeze-dried to obtain a magnesium hydroxide / calcium hydroxide complex. 189.33 g of malic acid was added to the precipitate, and the mixture was treated by high-voltage pulse. The treatment was performed at an electric field strength of 10.0-25.0 kV / cm, a pulse number of 10-25, a pulse width of 100-200 μs, and a treatment time of 10-40 s. A calcium magnesium malate complex was obtained.

[0044] (3) Preparation of nano calcium magnesium malate: The solution containing calcium magnesium malate prepared in step (2) was adjusted to pH 7 and ice-bathed. 1.65 g of sodium alginate and 1.10 g of soybean phospholipid were added and mixed. The mixture was then placed in an ultrasonic instrument and shaken at an ultrasonic power of 200 W for 10 min to promote the precipitation of nanocrystals.

[0045] (4) Separation of nano calcium magnesium malate: The crystals obtained in step (3) were filtered and dried to obtain nano calcium magnesium malate powder. Example 3

[0046] (1) Algae pretreatment: The kelp was washed, dried, and ground to pass through a 150-mesh sieve to obtain seaweed powder (the magnesium content in the seaweed powder was 100-500 mg / 100 g).

[0047] (2) Preparation of calcium magnesium malate: 73.82 g of calcium hydroxide was added into 2.5 kg of seaweed powder after stirring uniformly in 5.15 L of deionized water, and was put into a high-voltage pulse electric field treatment chamber to react at an electric field intensity of 10.0 kV / cm, a pulse number of 25 times, a pulse width of 200 μs, and a treatment time of 40 s. After the pulse, centrifugation (5000 rpm, 10 min) was performed, and 4 times the volume of 95% ethanol solution (v / v) was added into the white precipitate to perform alcohol precipitation at 4°C for 8 h. Subsequently, centrifugation (5000 rpm, 10 min) was performed to take the precipitate to perform freeze-drying, and the precipitate a was obtained as a magnesium hydroxide / calcium hydroxide compound. 252.46 g of malic acid was added into the precipitate a to perform high-voltage pulse treatment at an electric field intensity of 10.0 ~ 25.0 kV / cm, a pulse number of 10 ~ 25 times, a pulse width of 100 ~ 200 μs, and a pulse electric field treatment time of 10-40 s. The calcium magnesium malate compound was obtained.

[0048] (3) Preparation of nano calcium magnesium malate: the solution containing calcium magnesium malate prepared in step (2) was adjusted to pH 7.5 to perform ice bath, 2.83 g of sodium alginate and 2.83 g of soybean phospholipid were added to mix uniformly, and then were put into an ultrasonic instrument to perform oscillation at an ultrasonic power of 300 W and an ultrasonic time of 5 min to promote the precipitation of nanocrystals.

[0049] (4) Separation of nano calcium magnesium malate: the crystals prepared in step (3) were suction filtered and dried to obtain nano calcium magnesium malate powder.

[0050] Comparative Example 1:

[0051] After 27.55 g of malic acid was dissolved in 51.72 mL of water, 24.17 g of magnesium hydroxide was added to react at 85°C for 3 h. After standing for 12 hours to wait for the precipitation of crystals, suction filtration was performed, and magnesium malate was obtained after drying.

[0052] Comparative Example 2:

[0053] After 84.15 g of malic acid was dissolved in 121.06 mL of water, 36.91 g of calcium hydroxide was added to react at 85°C for 3 h. After standing for 12 hours to wait for the precipitation of crystals, suction filtration was performed, and calcium malate was obtained after drying.

[0054] Comparative Example 3:

[0055] After 189.33 g of malic acid was dissolved in 269.10 mL of water, 24.17 g of magnesium hydroxide and 55.36 g of calcium hydroxide were added to react at 85°C for 3 h. After standing for 12 hours to wait for the precipitation of crystals, suction filtration was performed, and calcium magnesium malate compound was obtained after drying.

[0056] Comparative Example 4:

[0057] (1) Edible algae pretreatment: After the laver was washed and dried, it was crushed and passed through a 110-mesh sieve to obtain seaweed powder.

[0058] (2) Preparation of calcium magnesium malate: After 2.5 kg of seaweed powder was stirred uniformly with 2.56 L of deionized water, 55.36 g of calcium hydroxide was added and reacted at 85°C for 1 h. After the reaction, centrifugation (5000 rpm, 10 min) was performed and 4 volumes of 95% ethanol solution (v / v) was added to the white precipitate, which was then alcohol precipitated at 4°C for 8 h. Subsequently, centrifugation (5000 rpm, 10 min) was performed and the precipitate was freeze-dried to obtain precipitate a as a magnesium hydroxide / calcium hydroxide complex. After 189.33 g of malic acid was added to precipitate a and reacted at 85°C for 3 h, the crystals were allowed to precipitate for 12 h, and then filtration was performed. After drying, calcium malate / calcium malate complex was obtained.

[0059] Comparative Example 5:

[0060] (1) Edible algae pretreatment: After the laver was washed and dried, it was crushed and passed through a 110-mesh sieve to obtain seaweed powder.

[0061] (2) Preparation of calcium magnesium malate: After 2.5 kg of seaweed powder was stirred uniformly with 2.56 L of deionized water, 55.36 g of calcium hydroxide was added and placed in a high-voltage pulse electric field treatment chamber. The electric field strength was 15.0 kV / cm, the pulse number was 18, the pulse width was 150 μs, and the treatment time was 25 s. After the pulse, centrifugation (5000 rpm, 10 min) was performed and 4 volumes of 95% ethanol solution (v / v) was added to the white precipitate, which was then alcohol precipitated at 4°C for 8 h. Subsequently, centrifugation (5000 rpm, 10 min) was performed and the precipitate was freeze-dried to obtain precipitate a as a magnesium hydroxide / calcium hydroxide complex. After 189.33 g of malic acid was added to precipitate a and subjected to high-voltage pulse treatment, the electric field strength of the high-voltage pulse treatment was 10.0 ~ 25.0 kV / cm, the pulse number was 10 ~ 25, the pulse width was 100 ~ 200 μs, and the electric field treatment time was 10-40 s. Subsequently, filtration was performed and, after drying, calcium magnesium malate complex was obtained.

[0062] Comparative Example 6:

[0063] (1) Preparation of calcium magnesium malate: 24.17 g of magnesium hydroxide and 55.36 g of calcium hydroxide were added to 269.10 mL of water and put into a high-voltage pulse electric field treatment chamber, and the reaction electric field intensity was 15.0 kV / cm, the pulse number was 18, the pulse width was 150 μs, and the treatment time was 25 s; after the pulse, centrifugation (5000 rpm, 10 min) was performed and 4 times the volume of a 95% ethanol solution (v / v) was added to the white precipitate, which was alcohol precipitated at 4°C for 8 h, followed by centrifugation (5000 rpm, 10 min) to obtain a precipitate, which was freeze-dried to obtain a magnesium hydroxide / calcium hydroxide complex. After adding 189.33 g of malic acid to the precipitate a, high-voltage pulse treatment was performed, and the pulse electric field intensity was 10.0-25.0 kV / cm, the pulse number was 10-25, the pulse width was 100-200 μs, and the pulse electric field treatment time was 10-40 s; and a calcium magnesium malate complex was obtained.

[0064] (2) Preparation of nano calcium magnesium malate: the solution containing calcium magnesium malate prepared in step (1) was adjusted to pH 7 and then ice-bathed, 1.65 g of sodium alginate and 1.10 g of soybean phospholipid were added and mixed, and then put into an ultrasonic instrument for oscillation, the ultrasonic power was 200 W, and the ultrasonic time was 10 min, so as to promote the precipitation of nanocrystals.

[0065] (3) Separation of nano calcium magnesium malate: the crystals prepared in step (2) were filtered and dried to obtain nano calcium magnesium malate powder.

[0066] The above examples are only preferred embodiments of the present application, and are used to explain the present application, but not to limit the present application, and the changes, replacements, modifications, etc. made by those skilled in the art without departing from the spirit and essence of the present application shall all belong to the protection scope of the present application.

[0067] Determination method

[0068] Determination of particle size

[0069] The sample was diluted to 0.01 mg / mL with deionized water, and the particle size of the sample was determined at 25°C by a laser particle size analyzer. The degree of particle agglomeration can be represented by the agglomeration coefficient AF(50):

[0070] AF(50)=diameter of medium size agglomerate / average equivalent diameter of microparticles

[0071] In the formula, the diameter of the medium size agglomerate is the diameter of 50% cumulative mass in particle size analysis.

[0072] 2. Determination of Ca, Mg chelation rate

[0073] Calcium / magnesium content determination method: EDTA titration method. Take the sample to be tested, add 5 mL of ammonia chloride buffer solution (p H = 10.0), 5 drops of 0.5% chrome black T solution, immediately titrate with 0.05 mol / L EDTA-Na2 until the solution changes from purple red to sky blue, titrate for 3 times, and record the volume of titrant used.

[0074] Chelation rate calculation formula:

[0075] Chelation rate (%) = (M-m) / M x 100%

[0076] In the formula, M is the total amount of calcium / magnesium, and m is the amount of free calcium / magnesium.

[0077] 3. Determination of Ca and Mg digestion and absorption rate

[0078] (1) Preparation of simulated digestive juice

[0079] Artificial saliva, purchased from Shanghai Yuan Ye Biological Technology Co., Ltd.

[0080] Artificial gastric juice: 5 g / L NaCl, pH adjusted to 2.0 with 1 mol / L HCl solution.

[0081] Artificial intestinal juice: 0.5 mol / L NaHCO3, 5 g / L bovine bile salt, pH adjusted to 8.0 with 1 mol / L NaOH solution.

[0082] (2) In vitro digestion model of emulsified intestine

[0083] Simulated oral digestion: Mix 10 g of sample with 1 mL of simulated saliva at a ratio of 10:1, and place in a 37℃ constant temperature water bath for 2 min.

[0084] Simulated gastric digestion: Mix the sample after oral digestion with artificial gastric juice at a ratio of 1:1, and adjust the pH of the mixed system to 2.0 with 1 mol / L HCl solution, add pepsin (to a final concentration of 3 g / L) and mix, and place the sample mixture in a 37℃ constant temperature shaker for 2 h.

[0085] Simulated intestinal digestion: Mix the sample after gastric digestion with artificial intestinal juice at a ratio of 1:1, and adjust the pH of the mixed system to 8.0 with 1 mol / L NaOH solution, add trypsin (to a final concentration of 5 g / L) and mix, and continue to place the system in a 37℃ constant temperature condition for 3 h. After the above process, immediately place the digestion solution in a high temperature of 99.9℃ to inactivate the enzyme for 10 min, then centrifuge at 8000 x g for 15 min, and take the supernatant for subsequent calcium and magnesium content determination.

[0086] The calculation methods for the digestibility and absorption rates of Ca and Mg are as follows:

[0087] ×100%

[0088] In the formula, C is the digestion and absorption rate of Ca and Mg; C1 is the content of Ca and Mg in the sample after digestion; and C0 is the content of Ca and Mg in the sample before digestion.

[0089] Results Analysis

[0090] Figure 1 The particle size results show that the product obtained by high-voltage pulsed electric field treatment has a smaller particle size than that obtained by traditional water bath heating reaction. The product further treated with ultrasound has an average particle size of 530 nm, indicating that using ultrasound to promote the crystal precipitation process helps prevent particle agglomeration and control particle size and crystal growth rate, resulting in a high specific surface area and high reactivity. This provides more reaction sites, promotes the chelation of trace elements and amino acids, shortens the reaction time, and also improves the calcium / magnesium chelation rate, thus increasing reaction efficiency. Furthermore, under the same high-voltage pulsed and ultrasonic treatment methods, the nano-sized magnesium malate calcium magnesium product prepared using seaweed powder (Example 2) as the magnesium source has a smaller particle size than that prepared using magnesium hydroxide (Comparative Example 6), indicating that this treatment method has a better effect on controlling the particle size of seaweed. Particle size results and... Figure 2 The results obtained from the aggregation coefficient are consistent.

[0091] Figure 3 , Figure 4 The results showed that, compared with the traditional water bath heating reaction, high-voltage pulsed electric field treatment not only significantly shortened the reaction time but also improved the calcium / magnesium chelation rate and increased the reaction efficiency. Since pulsed and ultrasonic treatments have a stronger effect on preventing agglomeration and controlling particle size of seaweed powder than magnesium hydroxide, calcium-magnesium composite products using seaweed powder as the magnesium source have a higher calcium / magnesium chelation rate.

[0092] Figure 5 , Figure 6 The results showed that the composite calcium malate magnesium product with seaweed powder as the magnesium source had a higher digestibility and absorption rate, and could supplement calcium and magnesium at the same time, promoting the balanced absorption of trace elements. Moreover, the nano-scale calcium malate magnesium composite product prepared by treating seaweed powder with high voltage pulse electric field and ultrasound in this study had a significantly improved digestibility and absorption rate compared with other comparative studies.

Claims

1. A method for preparing a nanoscale calcium-magnesium-malate complex product, characterized by, It comprises the following steps: (1) seaweed pretreatment: after washing and drying the seaweed, it is crushed and sieved to obtain seaweed powder; the seaweed is selected from any one of Undaria pinnatifida, Porphyra, Laminaria; the crushing in step (1) is to crush the seaweed into powder that can pass through an 80-150 mesh sieve; (2) preparation of calcium-magnesium malate: stirring is performed on the seaweed powder with deionized water to obtain solution a; excess calcium hydroxide is added to the solution a, and the mixture is put into a high-pressure pulse treatment chamber for reaction to obtain solution b; ethanol solution is added to the solution b for alcohol precipitation treatment, the precipitate is obtained by centrifugation, and freeze-drying is performed to obtain precipitate a as a magnesium hydroxide / calcium hydroxide composite; high-pressure pulse treatment is performed on the precipitate a after adding malic acid to obtain a solution containing calcium-magnesium malate; the pulse electric field strength of the high-pressure pulse treatment is 10.0-25.0 kV / cm, the pulse number is 10-25, the pulse width is 100-200 μs, and the pulse electric field treatment time is 10-40 s; (3) preparation of nano calcium-magnesium malate: the solution containing calcium-magnesium malate prepared in step (2) is adjusted in pH, ice-bath is performed, a surfactant is added and mixed, and then the mixture is put into an ultrasonic instrument for oscillation to promote the precipitation of nanocrystals; the pH in step (3) is adjusted to 6-7.5, the mass percentage content of the surfactant is 0.05-0.2%, the surfactant is a mixture of sodium alginate and soybean phospholipid in a mass ratio of 1-2:0.05-2, the ultrasonic power is 100-300 W, and the ultrasonic time is 5-15 min; (4) separation of nano calcium-magnesium malate: the crystals prepared in step (3) are filtered and dried to obtain nano calcium-magnesium malate composite product.

2. A method of preparing a nanoscale calcium-magnesium malate product according to claim 1, characterized in that, In step (2), the mass ratio of the calcium content of the added calcium hydroxide to the magnesium content of the solution a is 2:1-4:1; the solid-liquid ratio of the mixture of seaweed powder and calcium hydroxide to water is 1:0.5-1:2 g / mL, and the mass ratio of malic acid to calcium hydroxide is 3.42:

1.

3. A nanoscale calcium-magnesium-malate complex product, characterized in that, The method is prepared by any one of claims 1-2.

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