A metal trace element releasing material and its preparation method and application

Abstract

The present invention discloses a metal trace element releasing material and its preparation method and application. The metal trace element releasing material comprises a base material and a complex metal element releasing body, the complex metal releasing body comprises a metal salt and a metal ion releasing agent, a mutually penetrable network structure is formed between the complex metal element releasing body and the base material to control the release of the metal trace element, and the metal trace element releasing material is used to prepare a beverage container. The present invention provides a new method of forming a SOD mimetic enzyme with metal trace elements and polyphenols and replenishing metal trace elements. The beverage container is made of a material capable of releasing metal trace elements, and the metal ions are released according to the actual content of polyphenols or other organic substances that can bind to metal ions in the beverage, so as to obtain a human free radical killer-SOD mimetic enzyme and a metal-organic compound or metal binding protein that is easily absorbed by the human body.

Description

Technical Field

[0001] The invention relates to the technical field of beverage container materials, and in particular to a metal trace element releasing material and a preparation method and application thereof. Background Art

[0002] Metal trace elements are essential life elements for the human body. However, the content in the human body is not much, but metal trace elements play a very important role in disease resistance, cancer prevention, longevity and other aspects. It is difficult to ensure the adequate supplementation of metal trace elements in normal food, and the prior art generally uses metal trace element preparations to supplement. For example, patent CN102716150A discloses a zinc sulfate syrup oral liquid preparation, which is an oral zinc supplement liquid preparation with inorganic zinc sulfate as the main drug, sucrose as a sweetener, ethylparaben as a preservative, citric acid and sodium citrate as pH stabilizers. Although the zinc source preparation developed in the above patent has a certain zinc supplement effect, the metal trace element preparation usually contains a variety of auxiliary agents such as sweeteners, preservatives, solubilizing stabilizers, etc. that are completely unnecessary for the human body, which increases unnecessary preparation costs and causes potential harm to the body.

[0003] Recent studies have also found that metal elements can be complexed with polyphenol compounds to simulate the activity of superoxide dismutase (SOD). Superoxide dismutase is a metal enzyme necessary for the human body. With age, the amount of SOD, a substance that scavenges free radicals in the human body, becomes less and less, while free radicals in the human body are constantly produced, and the scavenging function loses balance, leading to the occurrence of various diseases. Therefore, the human body needs to supplement SOD in time to restore the normal SOD level in the body for the prevention and adjuvant treatment of various diseases. Although SOD is widely distributed in various organisms, such as animals, plants, and microorganisms, the cost of SOD extraction is high and it is sensitive to temperature and acidity and alkalinity. High cooking temperatures, seasonings, and gastric acid and proteases in the human body can destroy SOD. Compared with the natural SOD enzyme, the polyphenol-metal SOD mimetic enzyme not only has high enzyme activity, but also has low cost, stable structure, and is not affected by temperature and acidity and alkalinity.

[0004] Theoretically, polyphenol compounds are widely present in many foods such as coffee, tea, chocolate, etc. People can obtain polyphenol-metal SOD mimetic enzymes by adding metal trace element supplements to polyphenol-containing beverages such as tea, coffee, chocolate, etc. in their daily drinking, which can be used to prevent and treat diseases and delay aging. However, it is very difficult in actual operation. If people take metal trace element supplements while drinking polyphenol beverages, it is difficult to control the dosage of both, and it is impossible to grasp and determine the effectiveness of polyphenols and metal trace elements in the beverages to synthesize SOD mimetic enzymes in the human body, so it is difficult to ensure its antioxidant effect. If metal trace elements are added before drinking polyphenol beverages, the following problems will also be faced: First, due to the large difference in polyphenol content in different beverages, and the concentration and volume of polyphenol beverages are also different, it is impossible to determine the amount of metal trace elements added to the polyphenol beverages; second, metal trace element supplements usually contain other additives, such as sweeteners, preservatives, solubilizing stabilizers, etc. These additives are not only potentially harmful to the body, but also seriously affect the taste of the beverage. Summary of the invention

[0005] In view of the deficiencies of the prior art, the purpose of the present invention is to develop a technology that can conveniently and harmlessly supplement the metal trace elements of the human body and can effectively complex with polyphenols to form a SOD mimetic enzyme.

[0006] To achieve the above-mentioned objectives, the first aspect of the present invention provides a metal trace element releasing material, comprising a matrix material and a complex metal element releasing body, wherein the complex metal releasing body comprises a metal salt and a metal ion releasing agent, and a mutually penetrable network structure is formed between the complex metal element releasing body and the matrix material, and the metal trace element releasing material is used to prepare a beverage container.

[0007] The present invention provides a completely new way to supplement metal trace elements. The beverage container is made of a material capable of releasing metal trace elements. The metal ions are released according to the actual content of polyphenols or other organic substances in the beverage that can bind to metal ions, and the human free radical killer-SOD mimic enzyme (SOD mimics) and metal-organic compounds or metal binding proteins that are easily absorbed by the human body are obtained, thereby converting ordinary beverages into beverages with free radical scavenging, anti-oxidation functions and rich in metal trace elements. In addition to the release of metal trace elements, the new material does not release any other additives that may be harmful to human health, and can completely maintain the original flavor of various beverages.

[0008] Furthermore, the mass parts of the matrix material are 100 parts, the mass parts of the metal salt are 1 to 30 parts, and the mass parts of the metal ion releaser are 0.1 to 20 parts.

[0009] Furthermore, the metal salt is an inorganic metal salt or an organic metal salt, and the metal element thereof is selected from one or more of zinc, iron, copper, manganese, molybdenum and cobalt.

[0010] Furthermore, the metal ion releaser is a polymer compound that can form a complex with a metal salt, such as natural polymers such as starch, cellulose, chitosan and their derivatives, and synthetic polymers such as polyethylene glycol, polyvinyl alcohol, polyacrylic acid and the like.

[0011] The present invention combines metal salts with metal ion releasers to form relatively stable metal ion complexes. The metal ion releasers have both hydrophilic groups and hydrophobic groups, which are beneficial to achieving uniform distribution and slow release of metal ions in the matrix material.

[0012] Furthermore, the matrix material is a polymer material, such as PP, PE, PC, PET, PVC, etc.

[0013] Due to the intermolecular force, the matrix material and the complex metal element releaser have good affinity and compatibility, thus forming a mutually penetrable network structure between the complex metal element releaser and the matrix material to control the release of metal trace elements. This network structure not only makes the metal element complex have a better uniform distribution in the matrix material, but also embeds a large number of metal ions in the form of complexes in the matrix material, forming a "channel" that can continuously release metal ions.

[0014] When milk, coffee, tea and other beverages are put into the container made of the metal trace element releasing material, the metal ions in the complex can be slowly dissolved in the aqueous solution because the water molecules contact the complex metal element releasing body on the surface of the material to form hydrated metal ions, and after the metal ions on the surface of the material are released, the water molecules can continue to form hydrated metal ions through the "channel" of the material, so that the container made of the metal trace element releasing material of the present invention realizes the continuous release of metal trace elements. The small molecules such as proteins, polypeptides, polyphenols in the drinks such as milk, coffee, tea and other beverages have stronger complexing ability with metal ions, so they are more conducive to combining with metal ions, so that the metal ions are quickly released from the material, and the release rate and amount of metal trace elements are improved.

[0015] The second aspect of the present invention provides a method for preparing the above-mentioned metal trace element releasing material, comprising the following steps:

[0016] S1, weighing a metal salt and a metal ion releaser, mixing them, adding water and stirring into a paste, stirring and reacting at a set temperature, drying and grinding after the reaction, to obtain a complex metal element releaser;

[0017] S2. Mixing the complex metal element releasing body with the matrix material, melting them at high temperature, and molding them to obtain the metal trace element releasing material.

[0018] The present invention firstly mixes a metal salt and a metal ion releaser for reaction. Since the metal ion releaser has both hydrophilic groups such as carboxyl, hydroxyl or amino groups and hydrophobic groups with long carbon chains, the metal salt and the metal ion releaser can form a relatively stable complex metal element releaser, which lays a foundation for the uniform distribution and slow release of metal trace elements in the matrix material. Then, the complex metal element releaser and the matrix material are blended and refined. Due to the intermolecular force, the two have good affinity and compatibility, thereby forming a mutually penetrable network structure between the complex metal element releaser and the matrix material, so that the metal trace elements are uniformly distributed in the matrix material in the form of ion complexes, and a channel for continuously releasing the metal trace elements is formed.

[0019] Furthermore, in step S1, the reaction temperature is 0-60° C., and the reaction time is 6-48 hours. The reaction of the metal salt and the metal ion releasing agent is carried out at a relatively low temperature, the conditions are easily controlled, and the steps are simple.

[0020] Furthermore, in step S1, the drying process is heating and drying at a temperature of 40 to 100° C., or natural air drying.

[0021] Furthermore, in step S2, the obtained metal trace element releasing material is in the form of powder, plate, wire or granule. The appropriate material form can be selected according to the container requirements and processing technology.

[0022] The third aspect of the present invention provides an application of the above-mentioned metal trace element releasing material, wherein the metal trace element releasing material is made into a container for a drink containing polyphenols, proteins or small molecule peptides.

[0023] The metal trace element releasing material of the present invention can release metal ions in a quantitative and controllable manner, and complexes with polyphenol compounds such as chlorogenic acid and tea polyphenols contained in polyphenol beverages to form polyphenol-metal SOD mimetic enzymes, which have free radical scavenging and antioxidant properties. The complexation of polyphenol compounds with metal ions is a quantitative reaction, and the amount of metal ions released is related to the content (concentration and volume) of polyphenols in the container, while the release rate of metal ions is controlled by the polyphenol content in the beverage, the complexation ability, and the regulation of the metal ion release "channel" in the material. The higher the polyphenol content, the stronger the complexation ability, the higher the proportion of metal ion release agent in the material, and the faster the metal ion release rate, and vice versa. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 The test results of zinc ion concentration of coffee solution in three water cups in Example 7 of the present invention are as follows;

[0025] Figure 2 The zinc ion concentration test results of the milk solution in three water cups in Example 9 of the present invention;

[0026] Figure 3 These are the test results of zinc ion concentrations of green tea solution and black tea solution in three types of water cups in Example 10 of the present invention. DETAILED DESCRIPTION

[0027] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, specific embodiments of the present invention are described in detail below with reference to the accompanying drawings.

[0028] It should be understood that the terms described in the present invention are only for describing special embodiments and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0029] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present application description and examples are exemplary only.

[0030] Example 1

[0031] Take 1500 grams of PP plastic particles as the base material, 75 grams of food-grade zinc acetate, and 4.5 grams of potato starch.

[0032] The zinc salt (zinc acetate) and the zinc ion releaser (potato starch) are mixed and 200 ml of water are added to form a paste. The mixture is stirred and reacted at 40°C for 24 hours. The mixture is dried at 50°C and then ground to form a zinc ion complex with uniform distribution and relative stability, i.e., a complex zinc releaser.

[0033] The prepared complex zinc releaser and the matrix material PP are melted at 200-220° C. and fully mixed to form a zinc element release material in the form of particles.

[0034] Example 2

[0035] Take 1500 grams of PP plastic particles as the base material, 75 grams of food-grade zinc acetate, and 45 grams of potato starch.

[0036] The zinc salt (zinc acetate) and the zinc ion releaser (potato starch) are mixed and 200 ml of water are added to form a paste. The mixture is stirred and reacted at 40°C for 24 hours. The mixture is dried at 50°C and then ground to form a zinc ion complex with uniform distribution and relative stability, i.e., a complex zinc releaser.

[0037] The prepared complex zinc releaser and the matrix material PP are melted at 200-220° C. and fully mixed to form a zinc element release material in the form of particles.

[0038] Example 3

[0039] Take 1800 grams of HDPE plastic particles as the matrix material, 100 grams of food-grade ferrous sulfate, and 10 grams of chitosan.

[0040] The iron salt (ferrous sulfate) and the iron ion releaser (chitosan) were mixed and 250 ml of water were added to form a paste. The mixture was stirred at 45°C for 12 hours, dried at 55°C and ground to form an iron ion complex, i.e., a complex iron releaser.

[0041] The prepared complex iron releaser and the matrix material HDPE are melted at 250-260° C. and fully mixed to obtain an iron element release material in the form of powder.

[0042] Example 4

[0043] Take 1000 grams of PC plastic particles as the matrix material, 50 grams of food-grade copper gluconate, and 20 grams of polyethylene glycol.

[0044] The copper salt-copper gluconate and the copper ion releaser-polyethylene glycol were mixed and then 180 ml of water was added to form a paste, and the mixture was stirred and reacted at 35° C. for 20 hours, dried at 50° C. and ground to obtain a complex copper releaser.

[0045] The prepared complex copper releaser and the matrix material PC are melted at 230-240° C. and fully mixed to form a copper element release material in the form of particles.

[0046] Example 5

[0047] Take 2000 grams of PVC plastic particles as the base material, 150 grams of food-grade manganese lactate, and 50 grams of polyvinyl alcohol.

[0048] Manganese salt (manganese lactate) and manganese ion releaser (polyvinyl alcohol) were mixed and 250 ml of water was added to form a paste. The mixture was stirred at 40° C. for 24 hours, dried at 60° C. and ground to obtain a complex manganese releaser.

[0049] The prepared complex manganese releaser and the base material PVC are melted and fully mixed at 180-200° C., and molded to obtain a manganese element releasing material in the form of wire.

[0050] Example 6

[0051] Take 1600 grams of PET plastic particles as the matrix material, 90 grams of food-grade cobalt methionine, and 30 grams of cellulose.

[0052] The cobalt salt (cobalt methionine) and the cobalt ion releaser (cellulose) were mixed and 220 ml of water was added to form a paste. The mixture was stirred at 45° C. for 18 hours, dried at 50° C. and ground to obtain a complex cobalt releaser.

[0053] The prepared complex cobalt releaser and the matrix material PET are melted and fully mixed at 270-290° C. to form a cobalt element release material in the form of particles.

[0054] Example 7

[0055] The zinc-releasing materials of Example 1 and Example 2 were respectively made into two types of cups, and a cup was made of PP material as a control group.

[0056] Weigh 3 portions of instant coffee powder, 10 grams each, and add them to 3 cups respectively, dissolving them with boiling water. Samples of the dissolved coffee solution were taken after 10 minutes, 20 minutes, and 30 minutes respectively, and then the concentration of zinc ions in the coffee solution was measured according to GB5009.268-2016 "National Food Safety Standard - Determination of Multiple Elements in Food".

[0057] The measurement results are as follows Figure 1 As shown, the results show that: since the PP plastic cup does not release zinc ions and the coffee solution does not contain zinc ions, the zinc ion concentration in the coffee solution in the PP plastic cup is always zero; while the cups made of the materials of Example 1 and Example 2 release zinc ions, so the zinc ion concentration in the coffee solution increases; although the materials of Example 1 and Example 2 have the same PP matrix material, the same amount of zinc salt-zinc acetate and the same amount of instant coffee, due to the different content of zinc ion releaser, the zinc ion release rate of the cup made of the material of Example 2 is much faster than that of the cup made of Example 1.

[0058] Example 8

[0059] The freshly ground coffee was divided into two equal portions (250 ml each), one portion was poured into a PP cup, and the other portion was poured into a cup made of the zinc-releasing material of Example 2. After standing for 30 minutes, the antioxidant effect of the coffee in the cup on scavenging DPPH free radicals was tested in the following two ways.

[0060] Method 1: Pipette 0.2 ml of coffee solution from two cups respectively, add 0.8 ml of Tris-HCl buffer (pH 7.4), then add 1 ml of DPPH-ethanol solution, and then place the sample in a spectrophotometer to measure the absorbance value (A value) at a wavelength of 517 nm. Compare the free radical scavenging effects of the two different coffees based on the A value. The composition of the blank control sample solution is: 0.2 ml of distilled water + 0.8 ml of Tris-HCl buffer + 1 ml of DPPH-ethanol solution, and the reference solution is: 0.2 ml of distilled water + 0.8 ml of Tris-HCl buffer + 1 ml of ethanol solution.

[0061] Experimental results: The A value of the blank control sample (i.e., the control solution without coffee) is 1.160, the A value of the coffee solution in the PP cup is 0.698, and the A value of the coffee solution in the cup made of the material of Example 2 is 0.273. Since the absorbance value (A value) at a wavelength of 517nm is the characteristic absorption peak of the DPPH free radical, the larger the A value, the more DPPH free radicals there are, and vice versa. The A value (0.273) of the coffee solution in the cup made of the material of Example 2 is much lower than that of the ordinary PP cup (0.698), which proves that the amount of DPPH free radicals remaining in the coffee solution in the cup made of the material of Example 2 is much lower than that of the ordinary PP cup, indicating that the zinc ions released by the material of Example 2 are complexed with polyphenol compounds to form a polyphenol-metal SOD mimetic enzyme, which has a good free radical scavenging ability.

[0062] Method 2: Take 1 ml of coffee liquid diluted with Tris (1:4) and place it in a test tube. Add DPPH-ethanol solution drop by drop. At the beginning, the liquid in the test tube is brown-yellow. With the addition of DPPH, its color continues to deepen and gradually turns into dark brown-yellow. When the purple color dissipates very slowly after adding DPPH, stop adding and record the volume of DPPH consumed at this time.

[0063] Experimental results: When the 95th drop (19 ml) of coffee in the PP cup was added to 1 ml of coffee liquid diluted with Tris (1:4), it was found that the purple color dissipated very slowly; while the purple color dissipated slowly only when the 115th drop (23 ml) of coffee in the cup made of the material of Example 2 was added.

[0064] From the above two tests on the antioxidant effect of coffee solutions in different cups on scavenging DPPH free radicals, it can be seen that the coffee in the cup made of the metal trace element releasing material of the present invention can scavenge more DPPH free radicals, proving that the metal trace element releasing material has excellent free radical scavenging and antioxidant capabilities when used to hold polyphenol beverages. Since the zinc ion concentration in the coffee solution is proportional to the amount of polyphenol-zinc ion complexes, and the amount of polyphenol-zinc ion complexes is proportional to the free radical scavenging and antioxidant properties of the coffee solution, the higher the zinc ion concentration in the same coffee solution, the stronger its antioxidant properties.

[0065] Example 9

[0066] The zinc-releasing materials of Example 1 and Example 2 were respectively made into two types of cups, and a cup was made of PP material as a control group.

[0067] Weigh 3 portions of milk powder, 25 grams each, and add them to 3 cups respectively, dissolving them with boiling water. Take samples of the dissolved milk solution after 15 minutes and 10 hours, and then measure the concentration of zinc ions in the milk solution according to GB5009.268-2016 "National Food Safety Standard - Determination of Multiple Elements in Food".

[0068] The measurement results are as follows Figure 2 As shown, the results show that: commercial milk powder already contains a small amount of trace element zinc, but the PP plastic cup does not release zinc ions, so the zinc ion concentration in the milk solution in the PP plastic cup is very low; while the cups made of the materials of Example 1 and Example 2 can release zinc ions, and the zinc ion concentration in the milk solution in these two cups is significantly increased; the content of zinc ion releaser in the materials of Example 1 and Example 2 is different, and the zinc ion release rate of the cup made of the material of Example 2 is much faster than that of the cup made of Example 1.

[0069] Example 10

[0070] The zinc-releasing materials of Example 1 and Example 2 were respectively made into two types of cups, and a cup was made of PP material as a control group.

[0071] Weigh 3 portions of green tea extract powder, 10 grams each, add them to 3 cups respectively, dissolve them with boiling water, and take samples of the dissolved green tea solution after 15 minutes and 10 hours respectively. Weigh 3 portions of black tea extract powder, 10 grams each, dissolve them in the above 3 cups in the same way, and take samples of the dissolved black tea solution after 15 minutes and 10 hours respectively. Measure the concentration of zinc ions in green tea solution and black tea solution according to GB5009.268-2016 "National Food Safety Standard - Determination of Multiple Elements in Food".

[0072] The measurement results are as follows Figure 3As shown, the results show that: since the PP cup does not release zinc ions and the tea liquid does not contain zinc ions, the zinc ion concentrations in the green tea solution and the black tea solution in the PP cup are basically zero; since green tea contains more tea polyphenols than black tea, which can effectively complex zinc ions, the zinc ion concentration in the green tea solution is much higher than that in the black tea solution; the material in Example 2 has a higher content of zinc ion releaser, and the zinc ion concentration of the tea in the water cup made of the material in Example 1 is higher.

[0073] Although the present invention is disclosed as above, the protection scope of the present invention is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, and these changes and modifications will fall within the protection scope of the present invention.

Claims

1. A metal trace element releasing material, characterized in that: It comprises a base material and a complex metal element releaser, wherein the complex metal element releaser comprises a metal salt and a metal ion releaser, a mutually penetrable network structure is formed between the complex metal element releaser and the base material, the base material has 100 parts by mass, the metal salt has 1 to 30 parts by mass, the metal ion releaser has 0.1 to 20 parts by mass, the metal salt is an inorganic metal salt, and its metal element is selected from one or more of zinc, iron, copper, manganese, molybdenum and cobalt, the metal ion releaser is selected from starch, the base material is a polymer material, and the metal trace element release material is used to prepare a container containing polyphenols, proteins or small molecule peptide drinks.

2. A method for preparing the metal trace element releasing material according to claim 1, characterized in that: The following steps are involved: S1, weighing a metal salt and a metal ion releaser, mixing them, adding water and stirring into a paste, stirring and reacting at a set temperature, drying and grinding after the reaction, to obtain a complex metal element releaser; S2. Mixing the complex metal element releasing body with the matrix material, melting them at high temperature, and molding them to obtain the metal trace element releasing material.

3. The method for preparing the metal trace element releasing material according to claim 2, characterized in that: In the step S1, the reaction temperature is 0-60° C. and the reaction time is 6-48 hours.

4. The method for preparing the metal trace element releasing material according to claim 3, characterized in that: In step S1, the drying process is heating and drying at a temperature of 40-100° C., or natural air drying.

5. The method for preparing the metal trace element releasing material according to claim 2, characterized in that: In the step S2, the obtained metal trace element releasing material is in the form of powder, plate, wire or granule.

6. An application of the metal trace element releasing material as claimed in claim 1, characterized in that: The metal trace element releasing material is made into a container for a drink containing polyphenols, proteins or small molecule peptides.

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