CN113975401B - Medical hydrogen storage material and preparation method thereof - Google Patents
Medical hydrogen storage material and preparation method thereof Download PDFInfo
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- CN113975401B CN113975401B CN202111152132.2A CN202111152132A CN113975401B CN 113975401 B CN113975401 B CN 113975401B CN 202111152132 A CN202111152132 A CN 202111152132A CN 113975401 B CN113975401 B CN 113975401B
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/50—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates
- A61K47/51—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent
- A61K47/56—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent the modifying agent being an organic macromolecular compound, e.g. an oligomeric, polymeric or dendrimeric molecule
- A61K47/58—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent the modifying agent being an organic macromolecular compound, e.g. an oligomeric, polymeric or dendrimeric molecule obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. poly[meth]acrylate, polyacrylamide, polystyrene, polyvinylpyrrolidone, polyvinylalcohol or polystyrene sulfonic acid resin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K33/00—Medicinal preparations containing inorganic active ingredients
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P19/00—Drugs for skeletal disorders
- A61P19/08—Drugs for skeletal disorders for bone diseases, e.g. rachitism, Paget's disease
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P29/00—Non-central analgesic, antipyretic or antiinflammatory agents, e.g. antirheumatic agents; Non-steroidal antiinflammatory drugs [NSAID]
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P39/00—General protective or antinoxious agents
- A61P39/06—Free radical scavengers or antioxidants
Abstract
The invention is applicable to the biomedical field, and provides a medical hydrogen storage material and a preparation method thereof. The medical hydrogen storage material comprises a high molecular polymer containing alcoholic hydroxyl groups and ammonia borane and/or derivatives thereof. In the medical hydrogen storage material provided by the invention, amino in ammonia borane and/or derivatives thereof reacts with high molecular polymer containing alcoholic hydroxyl groups, and the amino and the high molecular polymer form stable chemical bonds, so that ammonia borane and/or derivatives thereof can store hydrogen stably, and the medical hydrogen storage material is suitable for situations requiring stable hydrogen release in biological medicine.
Description
Technical Field
The invention belongs to the field of biomedical use, and relates to a medical hydrogen storage material and a preparation method thereof.
Background
In the biomedical field, hydrogen (H 2 ) Is an effective antioxidant, which, due to its ability to diffuse rapidly on the membrane, can reach cells and react with cytotoxic ROS, preventing oxidative damage [ Ohsawa I, ishikawa M, takahashi K, et al, hydrogen acts as a therapeutic antioxidant by selectively reducing cytotoxic oxygen radicals [ J ]].Nature medicine,2007,13(6):688.]. Furthermore, H 2 Has obvious inhibiting effect on the proliferation of M1 type macrophages, can prevent the differentiation of related osteoclasts induced by RANKL (Receptor activator of nuclear factor kappa-B ligand), and achieves the effects of resisting inflammation and promoting bones. However, H 2 Problems exist in the current application process, such as difficult storage and the like, so that the problems are limited in the field of biological medicine.
Therefore, there is a need for a medical hydrogen storage material that can stably store hydrogen.
Disclosure of Invention
The embodiment of the invention aims to provide a medical hydrogen storage material and a preparation method thereof, aiming at solving the problem of unstable hydrogen storage.
The embodiment of the invention is realized in such a way that a medical hydrogen storage material is provided, and the medical hydrogen storage material comprises a high molecular polymer containing alcoholic hydroxyl groups and ammonia borane and/or derivatives thereof.
Preferably, the mass of the alcoholic hydroxyl groups accounts for 30-40% of the total mass of the high molecular polymer.
Preferably, the ammonia borane and/or derivative thereof comprises amino groups, the mass of which accounts for 50% -70% of the total mass of the ammonia borane and/or derivative thereof.
Preferably, the high molecular polymer containing the alcoholic hydroxyl group is polyvinyl alcohol and/or a derivative thereof.
Further, the polymerization degree of the polyvinyl alcohol is 1700-1900, and the alcoholysis degree is more than 99%.
Further, the medical hydrogen storage material also comprises magnesium salt.
The magnesium salt is selected from MgCl 2 、MgCO 3 CH (CH) 3 One or more of COOMg.
Further, the medical hydrogen storage material is prepared on the surface of a supporting framework to form a film, and the supporting framework is preferably polytetrafluoroethylene.
Another object of the embodiment of the present invention is to provide a method for preparing a medical hydrogen storage material, which includes the following steps:
s1: preparing a high molecular polymer solution containing alcoholic hydroxyl groups;
s2: preparing ammonia borane and/or derivative solution thereof;
s3: and (2) adding the ammonia borane and/or the derivative solution thereof prepared in the step (S2) into the high polymer solution containing the alcoholic hydroxyl groups prepared in the step (S1), and mixing and reacting.
Further, step S3 further comprises adding MgCl 2 。
Further, after step S3, step S4 is further included: washing with absolute ethanol.
Preferably, the mass of the alcoholic hydroxyl groups accounts for 33.3% of the total mass of the high molecular polymer; the mass of amino groups represents 51.6% of the total mass of aminoborane and/or derivatives thereof.
In the medical hydrogen storage material provided by the invention, amino in ammonia borane and/or derivatives thereof reacts with high molecular polymer containing alcoholic hydroxyl groups, and the amino and the high molecular polymer form stable chemical bonds, so that ammonia borane and/or derivatives thereof can store hydrogen stably, and the medical hydrogen storage material is suitable for situations requiring stable hydrogen release in biological medicine.
Drawings
FIG. 1 is a flow chart of a method for preparing a medical hydrogen storage material according to an embodiment of the present invention;
FIG. 2 shows the state of the polyvinyl alcohol and ammonia borane provided in the embodiment of the invention before and after reaction;
FIG. 3 is a graph showing the hydrogen release capacity of medical hydrogen storage materials with different amounts of ammonia borane added according to embodiments of the present invention;
FIG. 4 is a graph showing the degree of crosslinking of films formed on polytetrafluoroethylene of medical hydrogen storage materials with different amounts of ammonia borane added according to an embodiment of the present invention;
FIG. 5 is a graph showing the results of cell proliferation experiments provided in the examples of the present invention;
fig. 6 is a graph of the results of the ammonia and hydrogen release test of the medical hydrogen storage material provided by the embodiment of the invention.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Ammonia borane (NH) 3 BH 3 Represented by AB) molecular mass and hydrogen storage density of up to 19.6wt% and 153g/L, respectively, are a very excellent hydrogen storage material, and are widely used for energy hydrogen storage, such as in fuel cells. NH (NH) 3 BH 3 The hydrogen storage and release are unstable, and the application of the hydrogen storage and release in the biomedical field is restricted.
The invention provides a medical hydrogen storage material, which enables ammonia borane to have excellent hydrogen storage performance.
One embodiment provides a medical hydrogen storage material comprising a high molecular polymer containing alcoholic hydroxyl groups and ammonia borane and/or derivatives thereof.
Specifically, the mass of the alcoholic hydroxyl groups in the alcoholic hydroxyl group-containing high molecular polymer accounts for 30-40% of the total mass of the alcoholic hydroxyl group-containing high molecular polymer.
In particular, the mass of amino groups in the ammonia borane and/or derivatives thereof is 50-70% of the total mass of ammonia borane and/or derivatives thereof.
In the medical hydrogen storage material provided by the invention, amino in ammonia borane and/or derivatives thereof reacts with high molecular polymer containing alcoholic hydroxyl groups, and the amino and the high molecular polymer form stable chemical bonds, so that ammonia borane and/or derivatives thereof can store hydrogen stably, and the medical hydrogen storage material is suitable for situations requiring stable hydrogen release in biological medicine.
Further, the high molecular polymer containing an alcoholic hydroxyl group is polyvinyl alcohol (represented by PVA) and/or a homolog thereof.
Preferably, the polyvinyl alcohol has a polymerization degree of 1700-1900 and an alcoholysis degree of 99% or more.
In one embodiment, the high molecular polymer containing alcoholic hydroxyl groups is polyethylene and the aminoborane and/or derivative thereof is aminoborane.
In another embodiment, the medical hydrogen storage material further comprises a magnesium salt. The magnesium salt is selected from MgCl 2 、MgCO 3 CH (CH) 3 One or more of COOMg.
Referring to fig. 1, the invention also provides a preparation method of the medical hydrogen storage material, which comprises the following steps:
s1: preparing a high molecular polymer solution containing alcoholic hydroxyl groups;
s2: a solution of ammonia borane and/or derivatives thereof;
s3: and (3) taking the ammonia borane and/or the derivative solution thereof prepared in the step (S2), adding the high polymer solution containing the alcoholic hydroxyl groups prepared in the step (S1), and uniformly mixing.
The preparation method of the medical hydrogen storage material provided by the invention is simple in configuration method, is suitable for large-scale production, ensures the hydrogen storage performance of ammonia borane and/or derivatives thereof, and is suitable for biological medicine.
Further, the preparation method of the medical hydrogen storage material comprises the following steps:
s1: configuration 6.68 x 10 -4 mol/L of high molecular polymer solution containing alcoholic hydroxyl groups;
s2: preparing 1mol/L ammonia borane and/or derivative solution thereof;
s3: adding 1ml of 1mol/L ammonia borane and/or its derivative solution prepared in S1 into 6.68 x 10 prepared in S1, wherein the concentration of ammonia borane is 50-200 mu L S2 -4 The mol/L high molecular polymer solution containing the alcoholic hydroxyl groups is uniformly mixed.
In one embodiment, S3 further comprises adding 100-1000. Mu.L of MgCl at a concentration of 1mol/L to a 1mol/L ammonia borane and/or derivative solution thereof configured in 50-200. Mu. L S2 2 。
Adding MgCl 2 After that, the ammonia gas release amount of the medical hydrogen storage material is reduced, so that the biotoxicity of the medical hydrogen storage material can be reduced, the medical hydrogen storage material is more suitable for clinical medicine, the action mechanism is that Mg ions and N atoms form stable complexes, and the NH formed by combining N atoms with H atoms can be effectively reduced 3 Is a combination of the amounts of (a) and (b).
In one embodiment, the medical hydrogen storage material further comprises:
step 4: the mixture obtained in S3 was washed with absolute ethanol.
The purpose of this step is to wash the unreacted alcoholic hydroxyl group-containing polymer compound or aminoborane and/or derivatives thereof.
In one embodiment, 6.68×10 is configured in S1 -4 The method for preparing the mol/L high molecular polymer solution containing the alcoholic hydroxyl group is as follows:
0.023mol of polyvinyl alcohol is added into 20mL of solvent, and the mixture is stirred by adding a magnetic stirrer, heated to 90 ℃, and continuously stirred until the polyvinyl alcohol is completely dissolved, wherein the polymerization degree of the polyvinyl alcohol is 1700, and the alcoholysis degree is 99%.
The solvent may be any one of deionized water, ethanol, and methanol.
The medical hydrogen storage material prepared by the invention is a flexible jelly, and the higher the polymerization degree of the polyvinyl alcohol is, the higher the crosslinking degree of the medical hydrogen storage material is, and the higher the hardness is.
In one embodiment, the method of preparing 1mol/L ammonia borane and/or derivative solution thereof in S2 is as follows:
to 10mL of the solvent was added 0.01mol of ammonia borane, and the mixture was dissolved with stirring.
The solvent may be any one of deionized water, ethanol, and methanol.
The invention will be further illustrated by the following specific experimental examples of specific medical hydrogen storage materials.
EXAMPLE 1 preparation of medical Hydrogen storage Material
The polyvinyl alcohol used in the above examples had a polymerization degree of 1700 and an alcoholysis degree of 99%.
The mass of the ammonia borane in the ammonia borane aqueous solution added in the preparation process of the medical hydrogen storage material 1, the medical hydrogen storage material 2 and the medical hydrogen storage material 3 is 1.5mg, 3mg and 6mg respectively. The medical material 1, the medical material 2 and the medical material 3 are all washed three times by absolute ethyl alcohol in the preparation process.
Referring to fig. 2, fig. 2 a shows a state in which the aqueous polyvinyl alcohol solution and the aqueous ammonia borane solution are not crosslinked, and fig. B shows a state in which the aqueous polyvinyl alcohol solution and the aqueous ammonia borane solution are crosslinked. As can be seen from fig. a and B, the aqueous polyvinyl alcohol solution and the aqueous ammonia borane solution can crosslink to form a gel-like substance from a liquid state.
Example 2 Hydrogen release test of medical Hydrogen storage Material
2.1 materials
Medical hydrogen storage material 1, medical hydrogen storage material 2 and medical hydrogen storage material 3
2.2 laboratory apparatus
Hydrogen-rich water test pen
2.3 Experimental procedure
The medical hydrogen storage material 1, the medical hydrogen storage material 2 and the medical hydrogen storage material 3 are placed in ultrapure water, and the hydrogen release amount of the medical hydrogen storage material is tested by a hydrogen-rich water test pen.
2.4 results
As shown in fig. 3, the hydrogen gas release amount of the medical hydrogen storage material 3 > the hydrogen gas release amount of the medical hydrogen storage material 2 > the hydrogen gas release amount of the medical hydrogen storage material 3.
2.5 conclusion
With the increase of the mass of ammonia borane added in the preparation process of the medical hydrogen storage material, the hydrogen release amount of the medical hydrogen storage material is increased.
Example 3 observation of morphology of medical Hydrogen storage Material film
3.1 materials
Polytetrafluoroethylene film with film thickness of 0.22 mu m, polyvinyl alcohol aqueous solution and ammonia borane aqueous solution in the process of preparing medical hydrogen storage material 1, medical hydrogen storage material 2 and medical hydrogen storage material 3
3.2 laboratory apparatus
Field emission scanning electron microscope
3.3 Experimental procedure
The first step: the medical hydrogen storage material 1, the medical hydrogen storage material 2 and the medical hydrogen storage material 3 are prepared into a film shape in polytetrafluoroethylene.
And a second step of: and observing the surface of the medical hydrogen storage material subjected to metal spraying by using a field emission scanning electron microscope.
3.4 results
As shown in fig. 4, fig. a is the degree of crosslinking of the medical hydrogen storage material 1, fig. B is the degree of crosslinking of the medical hydrogen storage material 2, and fig. C is the degree of crosslinking of the medical hydrogen storage material 3.
3.5 conclusion
As the mass of ammonia borane added during the preparation of the medical hydrogen storage material increases, the degree of crosslinking of the medical hydrogen storage material increases.
EXAMPLE 4 cell proliferation assay of Membrane medical Material
4.1 materials
Polyvinyl alcohol film, preparation of medical hydrogen storage material 2, polyvinyl alcohol aqueous solution, ammonia borane aqueous solution and MgCl in medical hydrogen storage material 5 2
4.2 laboratory apparatus
0.22 mu m polytetrafluoroethylene film, 24-hole cell culture plate, MC3T3-E1 cell, multi-hole pipette, enzyme-labeled instrument with 450nm filter, carbon dioxide incubator and Cell counting Kit-8 (CCK-8 for short) reagent
4.3 Experimental procedures
The first step: the polyvinyl alcohol aqueous solution and the ammonia borane aqueous solution in the medical hydrogen storage material 2 and the medical hydrogen storage material 5 are respectively filtered and sterilized by a filter membrane, and are formed into films on the surfaces of polytetrafluoroethylene films with the thickness of 0.22 mu m.
And a second step of: the membranes of the medical hydrogen storage material 2 and the medical hydrogen storage material 5 are dried at 60 ℃ and then placed on a 24-hole cell culture plate, and 3 experimental groups of parallel samples are arranged for each medical hydrogen storage material. Meanwhile, a blank group and a control group were set, the control group was added with a polyvinyl alcohol film or a 0.22 μm polytetrafluoroethylene film, and each was set with one sample, and the blank group was a 24-well culture plate.
And a third step of: inoculation of experimental group, control group and blank group with 2×10 4 The MC3T3-E1 cells were inoculated with the MC3T3-E1 cells and cultured in a carbon dioxide incubator for 4 hours.
Fourth step: and (3) transferring one tenth of the volume of the CCK-8 reagent in the culture medium by using a multi-channel pipette, adding the CCK-8 reagent into the experimental group, the control group and the blank group, and culturing for 0.5-4 hours.
Fifth step: the absorbance at 450nm was measured for each of the set experiment, control and blank groups using an enzyme-labeled instrument.
4.4 results
As shown in FIG. 5, FIG. 5 shows the absorbance at 450nm of the experimental group, the control group and the blank group with the lapse of time, and the greater the absorbance, the greater the number of MC3T3-E1 cells. In the figure, the experimental group marked as a pore plate is a blank group, the control group marked as a filter membrane is added with a polytetrafluoroethylene membrane of 0.22 mu m, the experimental group marked as a PVA filter membrane is added with a polyvinyl alcohol membrane, the experimental group marked as a PVA+AB filter membrane is added with a membrane prepared by a medical hydrogen storage material 2, and the experimental group marked as PVA+AB+MgCl 2 The experimental group of the filter membrane is added with the membrane prepared by the medical hydrogen storage material 5.
4.5 conclusion
The control group with the addition of the 0.22 μm polytetrafluoroethylene membrane showed that the addition of the 0.22 μm polytetrafluoroethylene membrane favors the proliferation of MC3T3-E1 cells compared to the blank group well plate.
The control group to which the polyvinyl alcohol film and the 0.22 μm tetrafluoroethylene film were added had a larger number of MC3T3-E1 cells on the first and fifth days and a slightly smaller number on the third day than the control group to which the 0.22 μm polytetrafluoroethylene film was added. In general, the addition of polyvinyl alcohol film favors the proliferation of MC3T3-E1 cells.
Compared with a control group added with a polyvinyl alcohol film and a polytetrafluoroethylene film with the thickness of 0.22 mu m, the number of MC3T3-E1 cells in an experimental group added with the polyvinyl alcohol film, ammonia borane and the polytetrafluoroethylene film with the thickness of 0.22 mu m is obviously reduced, and the ammonia released by the ammonia borane in the process of generating hydrogen is proved to have cytotoxicity and is not beneficial to the propagation of MC3T3-E1 cells.
Compared with the experimental group added with the polyvinyl alcohol film, the ammonia borane and the 0.22 mu m tetrafluoroethylene film, the method adds the polyvinyl alcohol film, the ammonia borane and the MgCl 2 And the number of MC3T3-E1 cells in the experimental group with 0.22 μm polytetrafluoroethylene film increased significantly, indicating the addition of MgCl 2 Can obviously inhibit the release amount of ammonia in the medical hydrogen storage material 2 and reduce the biotoxicity.
And blank well plate, control group with 0.22 μm polytetrafluoroethylene membrane added and additionThe polyvinyl alcohol film, ammonia borane and MgCl are added compared with the control group of 0.22 mu m polytetrafluoroethylene film 2 And 0.22 μm polytetrafluoroethylene film, the number of MC3T3-E1 cells decreased on the first and third days, but not so much, and the number of MC3T3-E1 cells was greater on the fifth day than in the other blank and control groups.
Example 5 Ammonia gas release and Hydrogen gas test of medical Hydrogen storage Material
5.1 materials
0.22 mu m tetrafluoroethylene film, medical hydrogen storage material 2, medical hydrogen storage material 4, medical hydrogen storage material 5, polyvinyl alcohol aqueous solution, ammonia borane aqueous solution and MgCl in the process of preparing medical hydrogen storage material 6 2
5.2 laboratory apparatus
Nashi reagent and hydrogen-rich water test pen
5.3 Experimental procedures
The first step: the medical hydrogen storage material 2, the medical hydrogen storage material 4, the medical hydrogen storage material 5 and the medical hydrogen storage material 6 are prepared on polytetrafluoroethylene with the thickness of 0.22 mu m to form a film.
And a second step of: the release amount of the membrane ammonia gas of each medical hydrogen storage material is tested by adopting the national environmental protection standard of the people's republic of China HJ535-2009 and Nashi reagent.
And a third step of: the films of the above respective medical hydrogen storage materials were tested for the amount of hydrogen released in ultrapure water using a hydrogen-rich water test pen.
5.4 results
As shown in fig. 6, fig. a is the content of released hydrogen gas over time of the membranes of the medical hydrogen storage material 2, the medical hydrogen storage material 4, the medical hydrogen storage material 5, and the medical hydrogen storage material 6; fig. B shows refractive indexes of films of the medical hydrogen storage material 2, the medical hydrogen storage material 4, the medical hydrogen storage material 5 and the medical hydrogen storage material 6 over time, and the larger the refractive index is, the larger the ammonia gas content is. In FIG. 5, AB is a medical hydrogen storage material 2, AB+100. Mu.L of 1M MgCl 2 Is medical hydrogen storage material 4, AB+500 mu L1M MgCl 2 Is medical hydrogen storage material 5, AB+1000 mu L1M MgCl 2 Is medical hydrogen storage material 6
5.5 conclusion
Medical hydrogen storage material 4 and no MgCl 2 The amount of hydrogen released in the first 24 hours was decreased to a smaller extent than the medical hydrogen storage material 2 of (a), the amount of hydrogen released in the 36 th hour was leveled, and the amount of hydrogen released in the 48 th hour was decreased to a smaller extent.
Medical hydrogen storage material 4 and no MgCl 2 Can suppress the generation amount of ammonia gas in the first 24 hours, and has substantially no effect of suppressing the generation of ammonia gas after 36 hours, as compared with the medical hydrogen storage material 2 of (a).
Medical hydrogen storage material 5 and no MgCl added 2 The amount of hydrogen released in the first 36 hours is about half the amount of hydrogen released in the medical hydrogen storage material 2, and the amount of hydrogen released in the 48 th hour is increased but still lower than the amount of hydrogen released in the medical hydrogen storage material 2, as compared with the medical hydrogen storage material 2. The medical hydrogen storage material 5 is lower in hydrogen release amount than the medical hydrogen storage material 4 in each period of time as compared with the medical hydrogen storage material 4.
Medical hydrogen storage material 6 and no MgCl added 2 Compared with the medical hydrogen storage materials 2, 4 and 5, the hydrogen release amount in each time period is minimum.
Medical hydrogen storage materials 5 and 6 and no MgCl 2 Can obviously inhibit the generation of ammonia gas in the first 24 hours and has no obvious inhibition effect on the generation of ammonia gas after 36 hours compared with the medical hydrogen storage material 2. The medical hydrogen storage materials 5, 6 have a stronger ability to inhibit ammonia gas generation in the first 24 hours than the medical hydrogen storage material 4. The medical hydrogen storage material 5 has a uniform ability to suppress ammonia gas generation compared with the medical hydrogen storage material 6.
Therefore, small amount of MgCl is added into the medical hydrogen storage material 2 Has smaller inhibition effect on the generation of ammonia gas, and has smaller influence on the release amount of hydrogen gas, especially the release amount of hydrogen gas within 24 hours. Along with MgCl 2 The increase in the amount of addition significantly enhances the inhibition of ammonia gas generation, but the generation of hydrogen gas also has a slight effect. When MgCl 2 After the addition amount is increased to a certain extent, the inhibition effect on the generation of ammonia is not enhanced, and the release of hydrogen is further reducedAnd (5) measuring the amount.
The medical hydrogen storage material provided by the invention has stable hydrogen storage capacity, and simultaneously, as ammonia borane and polyvinyl alcohol undergo a crosslinking reaction, the release amount of ammonia gas can be reduced, and the biotoxicity of ammonia borane can be reduced. In the case where the amount of the polyvinyl alcohol substance is determined, the greater the amount of the aminoborane reacted therewith, the better the hydrogen storage capacity of the medical hydrogen storage material. On the basis, the invention also provides a medical hydrogen storage material containing magnesium chloride, and the hydrogen storage capacity of the medical hydrogen storage material is not obviously reduced under the condition of adding a proper amount of magnesium chloride, but the release amount of ammonia gas is further reduced, so that the medical hydrogen storage material has better biological safety and is suitable for the field of medicines.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (9)
1. A medical hydrogen storage material is characterized by comprising magnesium salt, high molecular polymer containing alcoholic hydroxyl group and ammonia borane;
the volume of the magnesium salt is 100-1000 mu L, and the concentration of the magnesium salt is 1mol/L;
the mass of the alcoholic hydroxyl groups in the high molecular polymer containing the alcoholic hydroxyl groups accounts for 30-40% of the total mass of the high molecular polymer;
the volume of the ammonia borane is 50-200 mu L, and the concentration of the ammonia borane is 1mol/L.
2. The medical hydrogen storage material according to claim 1, wherein the mass of the amino group is 50 to 70% of the total mass of the ammonia borane.
3. The medical hydrogen storage material according to claim 1, wherein the high molecular polymer containing an alcoholic hydroxyl group is polyvinyl alcohol.
4. The hydrogen storage material for medical use according to claim 3, wherein the polyvinyl alcohol has a polymerization degree of 1700 to 1900 and an alcoholysis degree of 99% or more.
5. The medical hydrogen storage material according to claim 1, wherein the medical hydrogen storage material is prepared on the surface of a supporting framework to form a film.
6. The preparation method of the medical hydrogen storage material is characterized by comprising the following steps of:
s1: preparing a high molecular polymer solution containing alcoholic hydroxyl groups, wherein the mass of the alcoholic hydroxyl groups in the high molecular polymer solution containing alcoholic hydroxyl groups accounts for 30-40% of the total mass of the high molecular polymer;
s2: a prepared ammonia borane solution;
s3: and (2) adding magnesium salt into the ammonia borane solution prepared in the step (S2) and the high polymer solution containing the alcoholic hydroxyl groups prepared in the step (S1), and mixing and reacting, wherein the volume of the ammonia borane solution is 50-200 mu L, the concentration of the ammonia borane solution is 1mol/L, the volume of the magnesium salt is 100-1000 mu L, and the concentration of the magnesium salt is 1mol/L.
7. The method of claim 6, wherein adding magnesium salt in step S3 comprises adding MgCl 2 。
8. The method for preparing a medical hydrogen storage material according to claim 6, further comprising S4: washing with absolute ethanol.
9. The method for producing a medical hydrogen storage material according to claim 6 or 7, wherein the mass of the alcoholic hydroxyl group is 33.3% of the total mass of the high molecular polymer;
the mass of amino groups accounts for 51.6% of the total mass of the ammonia borane.
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| CN104591088A (en) * | 2013-10-30 | 2015-05-06 | 扬光绿能股份有限公司 | Fuel treatment device and hydrogen purification device thereof |
-
2021
- 2021-09-29 CN CN202111152132.2A patent/CN113975401B/en active Active
- 2021-12-14 WO PCT/CN2021/138059 patent/WO2023050585A1/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030313A (en) * | 2010-11-26 | 2011-04-27 | 南开大学 | Organic matter and ammonia borane compounded hydrogen storage material and preparation method thereof |
| CN111153382A (en) * | 2020-01-07 | 2020-05-15 | 北京化工大学 | Hydrogen sustained release agent containing ammonia borane and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Krishna Kharel等."Thermal, Kinetic and Vibrational Property Investigation of Hydrogen Storage Composites of Ammonia Borane with Polyacrylamide in Bulk and Nanofiber Forms".《https://www.researchgate.net/publication/312120676_Thermal_Kinetic_and_Vibrational_Property_Investigation_of_Hydrogen_Storage_Composites_of_Ammonia_Borane_with_Polyacrylamide_in_Bulk_and_Nanofiber_Forms》.2016, * |
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| CN113975401A (en) | 2022-01-28 |
| WO2023050585A1 (en) | 2023-04-06 |
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