CN114315956A - Method for preparing multiple response type gel by using oxidized glutathione derivative - Google Patents
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- YPZRWBKMTBYPTK-BJDJZHNGSA-N glutathione disulfide Chemical class OC(=O)[C@@H](N)CCC(=O)N[C@H](C(=O)NCC(O)=O)CSSC[C@@H](C(=O)NCC(O)=O)NC(=O)CC[C@H](N)C(O)=O YPZRWBKMTBYPTK-BJDJZHNGSA-N 0.000 title claims abstract description 48
- 230000004044 response Effects 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 claims description 8
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 claims description 8
- 229940043377 alpha-cyclodextrin Drugs 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 108010053070 Glutathione Disulfide Proteins 0.000 abstract description 11
- YPZRWBKMTBYPTK-UHFFFAOYSA-N oxidized gamma-L-glutamyl-L-cysteinylglycine Natural products OC(=O)C(N)CCC(=O)NC(C(=O)NCC(O)=O)CSSCC(C(=O)NCC(O)=O)NC(=O)CCC(N)C(O)=O YPZRWBKMTBYPTK-UHFFFAOYSA-N 0.000 abstract description 11
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical group C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 abstract description 7
- 238000005286 illumination Methods 0.000 abstract description 4
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 4
- 238000011160 research Methods 0.000 abstract description 4
- 238000007112 amidation reaction Methods 0.000 abstract description 3
- 230000004043 responsiveness Effects 0.000 abstract description 3
- 239000012046 mixed solvent Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 49
- 238000002360 preparation method Methods 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 108010038807 Oligopeptides Proteins 0.000 description 7
- 102000015636 Oligopeptides Human genes 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- YWGHUJQYGPDNKT-UHFFFAOYSA-N hexanoyl chloride Chemical compound CCCCCC(Cl)=O YWGHUJQYGPDNKT-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- -1 alkyl azobenzene Chemical compound 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- DXBULVYHTICWKT-UHFFFAOYSA-N ethyl 6-bromohexanoate Chemical compound CCOC(=O)CCCCCBr DXBULVYHTICWKT-UHFFFAOYSA-N 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BEYOBVMPDRKTNR-BUHFOSPRSA-N 4-Hydroxyazobenzene Chemical compound C1=CC(O)=CC=C1\N=N\C1=CC=CC=C1 BEYOBVMPDRKTNR-BUHFOSPRSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
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- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 239000001116 FEMA 4028 Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
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- 239000002537 cosmetic Substances 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
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- 238000001212 derivatisation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- VHJLVAABSRFDPM-QWWZWVQMSA-N dithiothreitol Chemical compound SC[C@@H](O)[C@H](O)CS VHJLVAABSRFDPM-QWWZWVQMSA-N 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- RGWOAXNKJWTDFA-UHFFFAOYSA-N ethyl 11-bromoundecanoate Chemical group CCOC(=O)CCCCCCCCCCBr RGWOAXNKJWTDFA-UHFFFAOYSA-N 0.000 description 1
- PQJJJMRNHATNKG-CQDYUVAPSA-N ethyl 2-bromoacetate Chemical group CCO[13C](=O)[13CH2]Br PQJJJMRNHATNKG-CQDYUVAPSA-N 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical class CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
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Abstract
The invention provides a method for preparing a multiple-response gel by using an oxidized glutathione derivative, belonging to the field of gel research. The invention takes oxidized glutathione as a raw material to carry out amidation reaction to obtain the oxidized glutathione derivative containing azobenzene group, and the derivative can carry out self-assembly in a mixed solvent of water and N, N-dimethylformamide and water and dimethyl sulfoxide to form gel. The gel prepared by the invention shows responsiveness to stimuli such as illumination, oxidation reduction, temperature and the like, is a multi-response type gel, and simultaneously provides a new method for preparing the multi-response type gel.
Description
Technical Field
The invention relates to the technical field of supermolecule chemical research, in particular to a method for preparing a multi-response gel by using an oxidized glutathione derivative.
Background
The gel is a typical soft material and plays an important role in the fields of cosmetics, foods, nano materials and the like. The micromolecule gel has the advantages of simple preparation, easy regulation and control and the like, and is widely concerned. The design and synthesis of the micromolecule gel with novel structure and unique property, and the research on the relationship between the molecular structure and the gel property are the key points of the research in the field of micromolecule gel.
Oligopeptide refers to peptide chain containing 2-10 amino acids, and the molecular weight is generally below 1000. The oligopeptide contains a plurality of amido bonds, so the oligopeptide derivative has stronger hydrogen bonding effect. Oligopeptide-based gels have been reported, and the common strategy is to link oligopeptides to some less polar groups, such as aromatic rings, alkyl chains, etc., via covalent bonds. The oligopeptide derivative molecules are aggregated to form gel under the drive of hydrogen bonds and other weak interactions such as pi-pi stacking action, van der waals force and the like. In addition, oligopeptides containing specific groups may exhibit more abundant properties, such as cysteine containing sulfhydryl groups, exhibiting redox response. Oxidized glutathione has a plurality of amido bonds, can form multiple hydrogen bonds, and disulfide bonds bring redox response. Gel systems based on oxidized glutathione derivatization have not been reported.
Azobenzene is a typical photoresponse group, the trans-structure is converted into the cis-structure under the irradiation of ultraviolet light, and the cis-structure can be converted into the trans-structure reversibly after the irradiation of visible light or heating. Azobenzene is the most commonly used group for building photoresponsive supramolecular systems, including photoresponsive gel systems. Meanwhile, in supramolecular chemistry, azobenzene is a typical guest of alpha-cyclodextrin and beta-cyclodextrin, and a host-guest complex also shows photoresponse formation and dissociation. The introduction of azobenzene group into target molecule can lay foundation for the application of target molecule in supermolecular host-guest chemistry.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for preparing a multiple response type gel by using an oxidized glutathione derivative. The molecular structure, preparation method and gel property of the substance are provided in the invention. The gel prepared by the invention shows responsiveness to stimuli such as illumination, oxidation reduction, temperature and the like, and is a multi-response gel. The invention provides a novel method for preparing the multi-response gel.
The first object of the present invention is to provide an oxidized glutathione derivative, the structural formula of which is shown in the following formula (I):
wherein:
n is any integer from 1 to 10;
r is-CH 3 or-CH 2CH 3.
The second object of the present invention is to provide a method for preparing a multiple response type gel using oxidized glutathione derivatives, comprising the steps of:
(1) dissolving the oxidized glutathione derivative of claim 1 in a solvent to obtain a clear solution; the solvent is a mixed solution of water and N, N-dimethylformamide or a mixed solution of water and dimethyl sulfoxide;
(2) and heating the clear solution, and then cooling to room temperature to prepare the multi-response gel.
The oxidized glutathione derivative molecule contains a plurality of amido bonds, and multiple hydrogen bonds exist among the molecules. In addition, there is a pi-pi stacking effect between adjacent azobenzene groups. Driven by the weak interaction between the two molecules, the oxidized glutathione derivative of the invention generates molecular self-assembly to form gel.
Preferably, the concentration of the oxidized glutathione derivative in the clear solution is 1-5 mmol/L.
Preferably, the volume percentage of water in the solvent is 30-80%.
Preferably, the temperature of the heating is 45-55 ℃.
Preferably, the heating time is 3 to 8 minutes, and more preferably, the heating time is 5 minutes.
Preferably, the temperature of the cooling is room temperature, and more preferably 25 ℃.
Preferably, the clear solution obtained in the step (1) is added with alpha-cyclodextrin, fully and uniformly stirred, then is subjected to heating treatment, and is cooled to room temperature to prepare the supramolecular gel.
Preferably, the amount of the α -cyclodextrin added (amount concentration of the substance) is 2 to 3 times, more preferably 2 times, that of the oxidized glutathione derivative.
It is a third object of the present invention to provide a multiple response gel prepared by any of the above methods.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides an oxidized glutathione derivative modified by alkyl azobenzene, which is synthesized by taking oxidized glutathione and azobenzene as raw materials. The substance self-assembles in a mixed solvent of water, N-dimethylformamide and dimethyl sulfoxide to form gel. The gel system based on the oxidized glutathione derivative has no literature report and belongs to pioneering work.
The gel prepared from the oxidized glutathione derivative provided by the invention shows triple reversible responses of illumination, oxidation reduction and temperature, and has potential application prospects in the fields of supramolecular chemistry, drug delivery, nano materials and the like.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of an oxidized glutathione derivative prepared in example 1 of the present invention, and the solvent is DMSO-d 6;
FIG. 2 is a graph showing the change in modulus of the formed gel in example 1 of the present invention (25 ℃ C.);
FIG. 3 is a graph of the change in modulus with temperature of the gel formed in example 1 of the present invention;
figure 4 is a graph of the change in modulus (25 c) of the supramolecular gel formed after addition of alpha-cyclodextrin in example 1 of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The test methods or test methods described in the following examples are conventional methods unless otherwise specified; the starting materials and auxiliaries are, unless otherwise specified, obtained from customary commercial sources or prepared in customary manner.
Example 1
1) Oxidized glutathione derivative (n ═ 5; r is-CH3) The synthetic route of the preparation method is composed of the following steps:
(1) preparation of oxidized glutathione methyl ester hydrochloride
(2) 4-hydroxyazobenzene reacts with 6-bromoethyl hexanoate, and (E) -6- (4-azophenoxy) hexanoyl chloride is obtained after further hydrolysis reaction and acyl chlorination reaction
(3) Carrying out amidation reaction on oxidized glutathione methyl ester hydrochloride and azobenzene modified caproyl chloride to obtain a final product
The oxidized glutathione derivative (n ═ 5; R ═ CH)3) The specific preparation steps are as follows:
the preparation method of the oxidized glutathione methyl ester hydrochloride in the step (1) comprises the following steps:
oxidized glutathione (10.00g, 16.32mmol) was added to a methanol (4mol/L, 800mL) solution containing hydrochloric acid, the reaction was stirred at 40 ℃ for 1 hour, and rotary evaporation was carried out under reduced pressure to give a crude oxidized glutathione methyl ester hydrochloride (14.00 g).
The preparation of (E) -6- (4-azophenoxy) hexanoyl chloride in step (2) comprises the following steps:
4-hydroxyazobenzene (30.00g, 151.35mmol), potassium carbonate (25.10g, 181.62mmol), potassium iodide (5.02g, 30.27mmol), ethyl 6-bromohexanoate (33.77g, 151.35mmol) were dissolved in acetone (800mL) and the reaction was stirred at 60 ℃ for 16 h. The solvent was distilled off under reduced pressure, extracted with water/ethyl acetate (2/3, v/v), and the organic phase was collected, dried over anhydrous sodium sulfate and rotary evaporated to give a crude product. Purification by column chromatography (petrol ether/ethyl acetate, 10/1, v/v) to give azobenzene-modified ethyl hexanoate (17.00g, 49.94 mmol);
② hydrolysis reaction is carried out, azobenzene modified ethyl caproate (17.00g, 49.94mmol) obtained in the step I is dissolved in ethanol (200mL), potassium hydroxide (5.60g, 99.88mmol) aqueous solution (10mL) is added, stirring and refluxing are carried out for 3h, rotary evaporation is carried out, solvent is removed, and crude product (20.00g) is obtained;
③ dissolving the product (17.00g, 52.09mmol) obtained in the step (c) in tetrahydrofuran (500mL), adding oxalyl chloride (9.92g, 78.14mmol) under the protection of nitrogen, and carrying out reflux reaction for 2h to obtain (E) -6- (4-azophenoxy) hexanoyl chloride (20.00 g).
The amidation reaction in the step (3) comprises the following steps: oxidized glutathione methyl ester hydrochloride (11.96g, 16.12mmol) was dissolved in N, N-dimethylformamide (300mL), cooled to 0 deg.C, triethylamine (8.16g, 80.61mmol) was added, a solution of (E) -6- (4-azophenoxy) hexanoyl chloride (16.00g, 48.37mmol) in tetrahydrofuran (300mL) was added, stirring was continued for 2h, allowed to return to room temperature, and stirring was continued for 16 h. Purification by preparative liquid phase gave the final product (3.30g, 2.41mmol) oxidized glutathione derivative (n ═ 5; R ═ CH3) in 14.96% yield.
The product was characterized by mass spectrum and nuclear magnetic hydrogen spectrum, LCMS: for C60H76N10O16S 2: m/z 1256.49; found: m/z 1257.0. The nuclear magnetic hydrogen spectrum is shown in FIG. 1.
2) Preparation of multiple response type gel
(1) Taking oxidized glutathione derivative (n ═ 5; R ═ CH)3) Dissolving 0.0754g of solid in 10mL of N, N-dimethylformamide to prepare a solution with the concentration of 6 mmol/L;
(2) placing 1mL of the solution in an empty bottle, and adding 2mL of water to obtain oxidized glutathione derivative (n ═ 5; R ═ CH)3) The water/N, N-dimethylformamide (2/1, v/v) mixed solution with the concentration of 2mmol/L is reserved;
(3) and (3) heating and cooling the mixed solution obtained in the step (2), namely, placing the mixed solution in a water bath at 50 ℃ for heating for 5 minutes, taking out the mixed solution, placing the mixed solution at room temperature for cooling, and forming gel when the temperature is reduced to 25 ℃, wherein the modulus change of the gel is shown in figure 2.
3) Study of the stimulus responsiveness of a Multi-responsive gel
Light response of the multiple response gel: placing the prepared gel under an ultraviolet lamp, irradiating with ultraviolet light with wavelength of 360nm, after 4-6 minutes, the gel begins to collapse and gradually turns into solution, placing the solution under visible light for irradiation, keeping the appearance unchanged, then heating-cooling the solution, namely placing the solution in a water bath at 50 ℃ for heating for 5 minutes, then taking out and placing at room temperature for cooling, and forming the gel when the temperature is reduced to 25 ℃.
(ii) redox response of the multiple response gel: adding dithiothreitol into the prepared gel to convert the gel into a solution, adding hydrogen peroxide into the solution, and performing heating-cooling treatment, namely placing the solution in a water bath at 50 ℃ for heating for 5 minutes, then taking out the solution, placing the solution at room temperature for cooling, and forming the gel when the temperature is reduced to 25 ℃.
③ temperature response of the multiple response type gel: the gel was gradually destroyed by increasing the temperature of the gel, the temperature was increased to 85 + -2 deg.C, the gel was completely converted into a solution, the change curve of modulus with temperature in this process is shown in FIG. 3, and after cooling to room temperature, the gel was formed.
4) Application of multiple response type gel in supermolecule chemistry field
To the oxidized glutathione derivative described in the 2 nd step of the preparation of the multiple responsive gel of the step 2) (n ═ 5; r is-CH3) 2 equivalents of alpha-cyclodextrin are added into the mixed solution of water/N, N-dimethylformamide (2/1, v/v), and the solution is heated and cooled, namely the solution is placed in a water bath at 50 ℃ for heating for 5 minutes and then is taken out and placed at room temperature for cooling, and the supramolecular gel is obtained when the temperature is reduced to 25 ℃.
The change in modulus of the gel is shown in figure 4. Similarly, the supramolecular gel with the participation of alpha-cyclodextrin shows triple responsivity of illumination, oxidation reduction and temperature.
Example 2
Oxidized glutathione derivative (n ═ 5; R ═ CH)2CH3) The preparation method comprises the following steps:
in example 1, oxidized glutathione derivative (n-5; R-CH) was obtained by changing methanol to ethanol in the production of oxidized glutathione methyl ester hydrochloride under otherwise unchanged conditions2CH3). The yield was 15.20%.
Example 3
Oxidized glutathione derivative (n ═ 1; R ═ CH)3) The preparation method comprises the following steps:
in example 1, ethyl 6-bromohexanoate was replaced with ethyl 2-bromoacetate under otherwise unchanged conditions to give an oxidized glutathione derivative (n ═ 1; R ═ CH)3). The yield was 17.65%.
Example 4
Oxidized glutathione derivative (n ═ 10; R ═ CH)3) The preparation method comprises the following steps:
in example 1, ethyl 6-bromohexanoate was replaced with ethyl 11-bromoundecanoate under otherwise unchanged conditions to give an oxidized glutathione derivative (n ═ 10; R ═ CH)3). The yield was 10.87%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. An oxidized glutathione derivative is characterized in that the structural formula of the derivative is shown as the formula (I):
wherein:
n is any integer from 1 to 10;
r is-CH3or-CH2CH3。
2. A method for preparing a multi-response gel by using an oxidized glutathione derivative is characterized by comprising the following steps:
(1) dissolving the oxidized glutathione derivative of claim 1 in a solvent to obtain a clear solution; the solvent is a mixed solution of water and N, N-dimethylformamide or a mixed solution of water and dimethyl sulfoxide;
(2) and heating the clear solution, and then cooling to room temperature to prepare the multi-response gel.
3. The method of claim 2, wherein the concentration of the oxidized glutathione derivative in the clarified solution is 1 to 5 mmol/L.
4. The method of claim 2, wherein the volume percentage of water in the solvent is 30-80%.
5. The method for preparing a multi-responsive gel using an oxidized glutathione derivative according to claim 2, wherein the heating temperature is 45 to 55 ℃.
6. The method of preparing a multi-responsive gel using oxidized glutathione derivative of claim 2, wherein the heating time is 3 to 8 minutes.
7. The method for preparing a multi-response gel from oxidized glutathione derivatives according to claim 2, wherein the clear solution obtained in step (1) is added with alpha-cyclodextrin and stirred uniformly, and then heated and cooled to room temperature to form the supramolecular gel.
8. The method of claim 7, wherein the α -cyclodextrin is added in an amount of 2 to 3 times the amount of the oxidized glutathione derivative in terms of the concentration of the substance.
9. A multiple response gel prepared by the method of any one of claims 2 to 8.
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