CN103977776A - Sugar-sensitive intelligent hydrogel based on gold surface and synthesis method thereof - Google Patents

Sugar-sensitive intelligent hydrogel based on gold surface and synthesis method thereof Download PDF

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CN103977776A
CN103977776A CN201410159698.1A CN201410159698A CN103977776A CN 103977776 A CN103977776 A CN 103977776A CN 201410159698 A CN201410159698 A CN 201410159698A CN 103977776 A CN103977776 A CN 103977776A
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gold
glucose
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gold plaque
aqueous gel
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CN103977776B (en
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戴庆
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In the cacom magnetic medical technology (Suzhou) Co., Ltd.
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SUZHOU QUANTZ MEDICAL TECHNOLOGY Co Ltd
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Abstract

The invention relates to sugar-sensitive intelligent hydrogel based on a gold surface and a synthesis method thereof. The synthesis method of the gold surface-based sugar-sensitive intelligent hydrogel comprises the following three steps of pre-treating a gold sheet so that the surface of the gold sheet is provided with -OH, efficiently introducing double bonds on the surface of the gold sheet orderly by a silane coupling agent and an acid anhydride, synthesizing the hydrogel on the surface of the gold sheet from acryamidophenylboronic acid as a monomer, a glucose molecule as a template and N, N'-methylene bisacrylamide as a cross-linking agent by an ultraviolet light-initiated polymerization reaction, and after the reaction, removing the glucose molecule by washing so that a large amount of glucose molecular imprinting cavities are formed on a hydrogel membrane on the surface of the gold sheet. The sugar-sensitive intelligent hydrogel based on a gold surface will be used in the field of biological signal detection and realizes dynamic identification and detection of glucose and other physiological indexes under the human physiological conditions.

Description

The quick intelligent aqueous gel capable of a kind of sugar based on gold surface and synthetic method thereof
Technical field
The present invention relates to the quick intelligent aqueous gel capable of a kind of sugar based on gold surface and synthetic method thereof, more precisely, relate to and a kind ofly can under Human Physiology condition, carry out the preparation of the sensitive aquagel film of Dynamic Recognition and detection to glucose, belong to biological technical field.
Background technology
As one of progressive accessory substance of epoch, the illness rate of diabetes increases year by year, the existing pandemic that has become a kind of serious threat human health.But medically also cannot effect a radical cure at present diabetes, can only postpone the appearance of complication by the blood sugar level of controlling patient.Therefore, for control and the treatment of diabetes, development can perception body in the intellectual material that changes of blood sugar concentration be very significant.Such material can real-time assessment detects patient's blood sugar concentration, feeds back in time the state of an illness and even automatically adjusts release medicine according to blood sugar level.
Intelligent aqueous gel capable (Intelligent Hydrogels) is that a class can respond the variation of environmental stimuli signal (as temperature, pH, solvent, ionic strength, electric field, magnetic field, light, pressure and special molecular etc.) and produce the macromolecular material of reversible volume phase transition.Because it has possessed induction and response function simultaneously, have pliability and the permeability of hydrogel concurrently, thereby receive much concern.Glucose-sensitive type hydrogel is as the one in intelligent aqueous gel capable, and its swellbility changes with the change of concentration of glucose, the variation of concentration of glucose under the identification that capable of dynamic is real-time human body physiological condition.Existing glucose-sensitive shaped material is mainly realized response by three kinds of modes: contain glucose oxidase (GOD), contain concanavalin A (ConA) agglutinin or contain phenylboric acid structure.Wherein, containing the hydrogel of phenyl boric acid group, its phenyl boric acid group can form compound with polyol glucose in the aqueous solution, if there is the polyol that can form stronger compound in system, can replace with glucose group.There is ionization equilibrium in phenyl boric acid, the compound that uncharged phenyl boric acid and glucose form is unstable in solution, and electronegative phenyl boric acid can form stable compound with glucose.The combination of glucose is moved the ionization equilibrium of phenyl boric acid, and electronegative phenyl boric acid is increased, and uncharged phenyl boric acid reduces, the water-soluble change of initiated polymerization thing thus, thus realize the real-time detection of glucose.Utilize phenyl boric acid structure to carry out the identification of glucose glycan molecule, have its uniqueness a little compared with other molecular recognition bodies.Boric acid base group and sugared recognition reaction are reversible reactions, and sensor, after finishing using, can, by changing the boric acid-saccharidic complexes of pH value hydrolysis generation of solution, be realized the regeneration of sensor and reuse.
But the method is prepared also its shortcoming of glucose-sensitive hydrogels: 1) because phenyl boric acid group can have a cis 1 with all, and 2-, 1, the hydroxy polymer reaction of 3-structure, selectively low to glucose; 2) phenyl boric acid based aquagel swelling rate is slow, and the responsive response time of sugar reaches 15h, does not meet diabetes patient's 2h-plasma glucose and reach the physiological requirement of peak value.
Molecular imprinting is preparation has the polymer of specificity selection process to a certain specific molecular.Utilize molecular engram skill to prepare progress in Intelligent Hydrogel, not only can improve the combination of hydrogel molecule to a certain specific molecular, and can control its switch to specific molecular memory function according to the variation of external environment, realize automatic identification, combination and release to specific molecular; Meanwhile, thus can the perception extraneous specific molecular of the intelligent aqueous gel capable based on molecular imprinting changes and occur swelling or shrink, and realizes the Dynamic Recognition to specific molecular.The large biological molecules such as the main protein of these specific moleculars, poly-peptide, nucleic acid, glucose, this technology has huge application prospect in fields such as medicine controlled releasing system, biology sensor and immunoassays.
The present invention combines molecular engram with boronate hydrogel compound, invented a kind of can be used for glucose in real time, the gel film of fast detecting glucose.This film has concurrently glucose molecule specific adsorption and reversible adsorption characteristic, can be used as glucose recognition unit, and glucose is carried out to Dynamic Recognition and detection.
Summary of the invention
The object of this invention is to provide a kind of in real time, the materials and methods of fast detecting glucose, to solve, conventional method cost is high, step is complicated, need to invade the problems such as human body.
Object of the present invention is achieved through the following technical solutions: the present invention is in order to solve the existing above-mentioned technical problem of prior art, boric acid base group sensitive hydrogel and surface molecule print technology are combined, provide a kind of high selectivity that has based on gold plaque surface, intelligent molecule imprinting hydrogel of boric acid class glucose molecule sensitivity and preparation method thereof.First the method carries out pretreatment by gold plaque, makes its surface with-OH; Then successively utilize silane coupler and acid anhydrides in gold surface, to introduce efficiently two keys; Finally taking acrylamido phenyl boric acid as monomer, glucose molecule is template, N, N '-methylene-bisacrylamide is crosslinking agent, by uv-light polymerization at gold surface synthetic water gel, after having reacted, wash away glucose molecule, on the aquagel membrane on gold plaque surface, leave a large amount of glucose molecule trace holes.
Technical scheme of the present invention is: synthesizing of a kind of quick intelligent aqueous gel capable of sugar based on gold surface, comprises the steps:
(1) gold plaque surface preparation: gold plaque is placed in to the Pierre's reagent (Piranha) configuring, ultrasonic 10 ~ 60 min, then use respectively acetone, ethanol, redistilled water ultrasonic cleaning, and Compressed Gas dries up, wherein, Pierre's reagent be configured to dense H2SO4:H2O2=5 ~ 10: 3(V: V), (2) amination: a certain amount of silane coupler is dissolved in solvent, the gold plaque of processing is placed in to above-mentioned solution, and inert atmosphere, after 50 ~ 110 DEG C of reaction 5 ~ 12 h, with absolute ethyl alcohol and redistilled water, gold plaque is washed down successively, Compressed Gas dries up, wherein, concentration=2 ~ 5 mmol/L of silane coupler, (3) two keys: a certain amount of acid anhydrides is dissolved in solvent, the gold plaque described in step (2) is placed in to above-mentioned solution, after 25 ~ 50 DEG C of reaction 5 ~ 20 h, with absolute ethyl alcohol and redistilled water, gold plaque is washed down successively, Compressed Gas dries up, wherein, concentration=0.5 ~ 2 mol/L of acid anhydrides, (4) polymerization: Pu Tao Tang ﹑ acrylamido phenyl boric acid is joined in dimethyl sulfoxide (DMSO), stirring at room temperature 5 ~ 24 h, then add N, N'-methylene-bisacrylamide and initator, after mixing, the mixed liquor of getting 0.1 ~ 1 uL is coated on the gold plaque described in step (3) equably, inert atmosphere under room temperature, be placed in light initiation polymerization 5 ~ 10 min under uviol lamp, react the rear dimethyl sulfoxide (DMSO) cyclic washing of using, wash away unreacted reactant, use again the mixed solution cyclic washing of acetic acid and methyl alcohol, until can't detect glucose in filtrate, use again ultra-pure water cyclic washing.By gained gel film drying at room temperature 3 days, then vacuum drying 1 day; Wherein, glucose, acrylamido phenyl boric acid, N, the concentration of N'-methylene-bisacrylamide, initator is respectively 10 ~ 50,50 ~ 100,100 ~ 200,0.2 ~ 0.5 mmol/L, and the volume ratio of acetic acid and methyl alcohol is 1 ~ 5: 10.
In described step (1), Compressed Gas is one or more in N2, Ar, He.
In described step (1), inert atmosphere is the one in N2, Ar, He atmosphere.
In described step (1), the diameter of gold plaque is 6 ~ 20 mm, and gold plaque is that on golden sheet metal or carrier, coating or chemical preparation have the one in the material of golden membranous layer.
In described step (2), silane coupler is one or more in 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, γ-aminopropyl methyldiethoxysilane and N-2-aminoethyl-3-aminopropyl methyl dimethoxysilane.
In described step (2), solvent is (ethanol, toluene and ethanol): distilled water=1:1(V: V=1: the one 1).
In described step (3), acid anhydrides is the one in succinic acid Gan ﹑ Shun butene dioic acid Gan ﹑ phthalic anhydride and trimellitic anhydride.
In described step (3), solvent is Er Jia base Ya Feng ﹑ N, one or more in N '-bis-methyl Jia Xian An ﹑ carrene and benzene.
Described step (4) medium ultraviolet light wavelength scope is 250 ~ 400 nm, and the exposure intensity of ultraviolet light is 1 ~ 100 W/cm2, and the ultraviolet source that uv photopolymerization irradiates use is ZF-1 type ultraviolet analyzer.
In described step (4), initator is diphenyl second two ketone ﹑ 2,2-diethoxy benzoylformaldoxime ﹑ a, a-dimethoxy-a-benzene benzoylformaldoxime ﹑ 2,4, one or more in 6-tri-methyl benzophenone and 2,4-diethyl thioxanthone.
Compared with prior art, advantage of the present invention is: (1) selected monomer acrylamido phenyl boric acid can generate the higher borate of stability with the reaction of glucose sugar 7.4 times at Human Physiology condition pH.(2) adopt molecular imprinting can effectively improve the specificity to glucose molecule.(3) the surface molecule print technology adopting, owing to being polymerization reaction take place on the surface of solid-phase matrix, can overcome the shortcoming that conventional method has, and also has the selective Gao ﹑ exchange of object ion resistance Di ﹑ adsorption capacity advantages of higher.(4) on gold plaque, the introducing of two keys adopts " two-step method " herein, has successfully avoided direct use γ-(methacryloxypropyl) propyl trimethoxy silicane to introduce polymerisable pair of key at microsphere surface, has improved the introducing efficiency of two keys.(5) this product is through follow-up study, synthetic biology sensor that can single-minded detection glucose molecule, and be expected to implant into body, realize the continuous monitoring to glucose.
Brief description of the drawings
Fig. 1 is the preparation flow figure of the embodiment of the present invention 1.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but the present invention is not limited thereto.
Embodiment 1:(1) gold plaque surface preparation: golden sheet metal is placed in to the Pierre's reagent (Piranha) configuring, ultrasonic 15 min, then use respectively acetone, ethanol, redistilled water ultrasonic cleaning 10 min, and N2 dries up, wherein, Pierre's reagent be configured to dense H2SO4:H2O2=5: 3(V:V), (2) amination: 3-aminopropyl trimethoxysilane is dissolved in toluene, the gold plaque of processing is placed in to above-mentioned solution, N2 atmosphere, after 110 DEG C of reaction 12 h, washes down gold plaque with absolute ethyl alcohol and redistilled water successively, and N2 dries up, wherein, the concentration of silane coupler is 3 mmol/L, (3) two keys: a certain amount of maleic anhydride is dissolved in dimethyl sulfoxide (DMSO), the gold plaque described in step (2) is placed in to above-mentioned solution, after 25 DEG C of reaction 10 h, with absolute ethyl alcohol and redistilled water, gold plaque is washed down successively, N2 dries up, wherein, concentration=1 mol/L of maleic anhydride, (4) polymerization: by Pu Tao Tang ﹑ acrylamido phenyl boric acid, join in dimethyl sulfoxide (DMSO), stirring at room temperature 5 h, then add N, N'-methylene-bisacrylamide and diphenylthanedione, after mixing, the mixed liquor that pipettes 0.5 μ L with micro syringe is coated on the gold plaque described in step (3) equably, N2 atmosphere under room temperature, be placed in light initiation polymerization 10 min under uviol lamp, react the rear dimethyl sulfoxide (DMSO) cyclic washing of using, wash away unreacted reactant, use again the mixed solution cyclic washing of acetic acid and methyl alcohol, until can't detect glucose in filtrate, use again ultra-pure water cyclic washing.By gained gel film drying at room temperature 3 days, then vacuum drying 1 day; Wherein, glucose, acrylamido phenyl boric acid, N, the concentration of N'-methylene-bisacrylamide, initator is respectively 30,50,150,0.2 mmol/L, and the volume ratio of acetic acid and methyl alcohol is 3:10.
In addition, synthetic for the non-trace hydrogel of gold surface boric acid class glucose-sensitive type that contrasts, step (4) is except not adding glucose, and all the other operations are identical with the preparation of the non-trace hydrogel of gold surface boric acid class glucose-sensitive type.
In addition, synthetic for the non-trace hydrogel of gold surface boric acid class glucose-sensitive type that contrasts, step (4) is except not adding glucose, and all the other operations are identical with the preparation of the non-trace hydrogel of gold surface boric acid class glucose-sensitive type.
Embodiment 2:(1) gold plaque surface preparation: gold-plated silicon chip is placed in to the Pierre's reagent (Piranha) configuring, ultrasonic 30 min, then use respectively acetone, ethanol, redistilled water ultrasonic cleaning 10 min, and N2 dries up, wherein, Pierre's reagent be configured to dense H2SO4:H2O2=7: 3(V:V), (2) amination: a certain amount of 3-ammonia third class triethoxysilane is dissolved in ethanol, the gold plaque of processing is placed in to above-mentioned solution, N2 atmosphere, after 78 DEG C of reaction 5 h, washes down gold plaque with absolute ethyl alcohol and redistilled water successively, and N2 dries up, wherein, the concentration of silane coupler is 5 mmol/L, (3) two keys: a certain amount of succinic anhydride is dissolved in to N, in N'-dimethyl formamide, the gold plaque described in step (2) is placed in to above-mentioned solution, after 25 DEG C of reaction 12 h, with absolute ethyl alcohol and redistilled water, gold plaque is washed down successively, N2 dries up, wherein, concentration=0.5 mol/L of succinic anhydride, (4) polymerization: by Pu Tao Tang ﹑ acrylamido phenyl boric acid, join in dimethyl sulfoxide (DMSO), stirring at room temperature 5 h, then add N, N'-methylene-bisacrylamide and 2, 4-diethyl thioxanthone, after mixing, the mixed liquor that pipettes 0.25 uL with micro syringe is coated on the gold plaque described in step (3) equably, N2 atmosphere under room temperature, be placed in light initiation polymerization 50 min under uviol lamp, react the rear dimethyl sulfoxide (DMSO) cyclic washing of using, wash away unreacted reactant, use again the mixed solution cyclic washing of acetic acid and methyl alcohol, until can't detect glucose in filtrate, use again ultra-pure water cyclic washing.By gained gel film drying at room temperature 3 days, then vacuum drying 1 day; Wherein, glucose, acrylamido phenyl boric acid, N, the concentration of N'-methylene-bisacrylamide, initator is respectively 20,50,150,0.3 mmol/L, and the volume ratio of acetic acid and methyl alcohol is 1:10.
Embodiment 3:(1) gold plaque surface preparation: gold-plated silicon chip is placed in to the Pierre's reagent (Piranha) configuring, ultrasonic 60 min, then use respectively acetone, ethanol, redistilled water ultrasonic cleaning 10 min, and N2 dries up, wherein, Pierre's reagent be configured to dense H2SO4:H2O2=4: 3(V:V), (2) amination: a certain amount of γ-aminopropyl methyldiethoxysilane is dissolved in the ethanol and distilled water that volume ratio is 1:1, the gold plaque of processing is placed in to above-mentioned solution, N2 atmosphere, after 50 DEG C of reaction 12 h, with absolute ethyl alcohol and redistilled water, gold plaque is washed down successively, N2 dries up, wherein, concentration=4 mmol/L of γ-aminopropyl methyldiethoxysilane, (3) two keys: a certain amount of phthalic anhydride is dissolved in carrene, the gold plaque described in step (2) is placed in to above-mentioned solution, after 35 DEG C of reaction 12 h, with absolute ethyl alcohol and redistilled water, gold plaque is washed down successively, N2 dries up, wherein, concentration=0.5 ~ 2 mol/L of phthalic anhydride, (4) polymerization: by Pu Tao Tang ﹑ acrylamido phenyl boric acid, join in dimethyl sulfoxide (DMSO), stirring at room temperature 10 h, then add N, N'-methylene-bisacrylamide and a, a-dimethoxy-a-phenyl acetophenone, after mixing, the mixed liquor that pipettes 0.25 uL with micro syringe is coated on the gold plaque described in step (3) equably, N2 atmosphere under room temperature, be placed in light initiation polymerization 5 min under uviol lamp, react the rear dimethyl sulfoxide (DMSO) cyclic washing of using, wash away unreacted reactant, use again the mixed solution cyclic washing of acetic acid and methyl alcohol, until can't detect glucose in filtrate, use again ultra-pure water cyclic washing.By gained gel film drying at room temperature 3 days, then vacuum drying 1 day; Wherein, glucose, acrylamido phenyl boric acid, N, the concentration of N'-methylene-bisacrylamide, initator is respectively 20,50,100,0.3 mmol/L, and the volume ratio of acetic acid and methyl alcohol is 1:10.
Embodiment 4:(1) gold plaque surface preparation: golden sheet metal is placed in to the Pierre's reagent (Piranha) configuring, ultrasonic 20 min, then use respectively acetone, ethanol, redistilled water ultrasonic cleaning 10 min, and N2 dries up, wherein, Pierre's reagent be configured to dense H2SO4:H2O2=7: 3(V:V), (2) amination: a certain amount of N-2-aminoethyl-3-aminopropyl methyl dimethoxysilane is dissolved in toluene, the gold plaque of processing is placed in to above-mentioned solution, and N2 atmosphere, after 110 DEG C of reaction 12 h, with absolute ethyl alcohol and redistilled water, gold plaque is washed down successively, N2 dries up, wherein, concentration=2.5 mmol/L of silane coupler, (3) two keys: a certain amount of trimellitic anhydride is dissolved in benzene, the gold plaque described in step (2) is placed in to above-mentioned solution, after 50 DEG C of reaction 10 h, with absolute ethyl alcohol and redistilled water, gold plaque is washed down successively, N2 dries up, wherein, concentration=2 mol/L of trimellitic anhydride, (4) polymerization: by Pu Tao Tang ﹑ acrylamido phenyl boric acid, join in dimethyl sulfoxide (DMSO), stirring at room temperature 24 h, then add N, N'-methylene-bisacrylamide and 2, 4, 6-tri-methyl benzophenone, after mixing, the mixed liquor that pipettes 1 uL with micro syringe is coated on the gold plaque described in step (3) equably, N2 atmosphere under room temperature, be placed in light initiation polymerization 5 min under uviol lamp, react the rear dimethyl sulfoxide (DMSO) cyclic washing of using, wash away unreacted reactant, use again the mixed solution cyclic washing of acetic acid and methyl alcohol, until can't detect glucose in filtrate, use again ultra-pure water cyclic washing.By gained gel film drying at room temperature 3 days, then vacuum drying 1 day; Wherein, glucose, acrylamido phenyl boric acid, N, the concentration of N'-methylene-bisacrylamide, initator is respectively 50,80,100,0.2 mmol/L, and the volume ratio of acetic acid and methyl alcohol is 2:10.
Embodiment 5:(1) gold plaque surface preparation: golden sheet metal is placed in to the Pierre's reagent (Piranha) configuring, ultrasonic 10 min, then use respectively acetone, ethanol, redistilled water ultrasonic cleaning 10 min, and N2 dries up, wherein, Pierre's reagent be configured to dense H2SO4:H2O2=5: 3(V:V), (2) amination: a certain amount of 3-aminopropyl triethoxysilane is dissolved in ethanol, the gold plaque of processing is placed in to above-mentioned solution, N2 atmosphere, after 78 DEG C of reaction 12 h, washes down gold plaque with absolute ethyl alcohol and redistilled water successively, and N2 dries up, wherein, the concentration of 3-aminopropyl triethoxysilane is 5 mmol/L, (3) two keys: a certain amount of maleic anhydride is dissolved in to N, in N'--dimethyl formamide, the gold plaque described in step (2) is placed in to above-mentioned solution, after 25 DEG C of reaction 20 h, with absolute ethyl alcohol and redistilled water, gold plaque is washed down successively, N2 dries up, wherein, concentration=1 mol/L of maleic anhydride, (4) polymerization: by Pu Tao Tang ﹑ acrylamido phenyl boric acid, join in dimethyl sulfoxide (DMSO), stirring at room temperature 24 h, then add N, N'-methylene-bisacrylamide and 2, 2-diethoxy acetophenone, after mixing, the mixed liquor that pipettes 1 uL with micro syringe is coated on the gold plaque described in step (3) equably, N2 atmosphere under room temperature, be placed in light initiation polymerization 10 min under uviol lamp, react the rear dimethyl sulfoxide (DMSO) cyclic washing of using, wash away unreacted reactant, use again the mixed solution cyclic washing of acetic acid and methyl alcohol, until can't detect glucose in filtrate, use again ultra-pure water cyclic washing.By gained gel film drying at room temperature 3 days, then vacuum drying 1 day; Wherein, glucose, acrylamido phenyl boric acid, N, the concentration of N-methylene-bisacrylamide, initator is respectively 40,80,150,0.5 mmol/L, and the volume ratio of acetic acid and methyl alcohol is 4: 10.
Above-described embodiment is used for the present invention that explains, instead of limits the invention, and in the protection domain of spirit of the present invention and claim, any amendment and change that the present invention is made, all fall into protection scope of the present invention.

Claims (10)

1. the quick intelligent aqueous gel capable of the sugar based on gold surface and a synthetic method thereof, is characterized by and comprise the steps:
(1) gold plaque surface preparation: gold plaque is placed in to the Pierre's reagent (Piranha) configuring, ultrasonic 10 ~ 60 min, then use respectively acetone, ethanol, redistilled water ultrasonic cleaning, and Compressed Gas dries up, wherein, Pierre's reagent be configured to dense H2SO4:H2O2=5 ~ 10: 3(V:V), (2) amination: a certain amount of silane coupler is dissolved in solvent, the gold plaque of processing is placed in to above-mentioned solution, and inert atmosphere, after 50 ~ 110 DEG C of reaction 5 ~ 12 h, with absolute ethyl alcohol and redistilled water, gold plaque is washed down successively, Compressed Gas dries up, wherein, concentration=2 ~ 5 mmol/L of silane coupler, (3) two keys: a certain amount of acid anhydrides is dissolved in solvent, the gold plaque described in step (2) is placed in to above-mentioned solution, after 25 ~ 50 DEG C of reaction 5 ~ 20 h, with absolute ethyl alcohol and redistilled water, gold plaque is washed down successively, Compressed Gas dries up, wherein, concentration=0.5 ~ 2 mol/L of acid anhydrides, (4) polymerization: by Pu Tao Tang ﹑ acrylamido phenyl boric acid, join in dimethyl sulfoxide (DMSO), stirring at room temperature 5 ~ 24 h, then add N, N'-methylene-bisacrylamide and initator, after mixing, the mixed liquor of getting 0.1 ~ 1 uL is coated on the gold plaque described in step (3) equably, inert atmosphere under room temperature, be placed in light initiation polymerization 5 ~ 10 min under uviol lamp, react the rear dimethyl sulfoxide (DMSO) cyclic washing of using, wash away unreacted reactant, use again the mixed solution cyclic washing of acetic acid and methyl alcohol, until can't detect glucose in filtrate, use again ultra-pure water cyclic washing, by gained gel film drying at room temperature 3 days, then vacuum drying 1 day, wherein, glucose, acrylamido phenyl boric acid, N, the concentration of N '-methylene-bisacrylamide, initator is respectively 10 ~ 50,50 ~ 100,100 ~ 200,0.2 ~ 0.5 mmol/L, and the volume ratio of acetic acid and methyl alcohol is 1 ~ 5:10.
2. the quick intelligent aqueous gel capable of sugar based on gold surface as claimed in claim 1 is synthetic, and it is characterized by Compressed Gas in described step (1) is one or more in N2, Ar, He.
3. the quick intelligent aqueous gel capable of sugar based on gold surface as claimed in claim 1 is synthetic, and it is characterized by inert atmosphere in described step (1) is the one in N2, Ar, He atmosphere.
4. the quick intelligent aqueous gel capable of sugar based on gold surface as claimed in claim 1 is synthetic, the diameter that it is characterized by gold plaque in described step (1) is 6 ~ 20 mm, and gold plaque is that on golden sheet metal or carrier, coating or chemical preparation have the one in the material of golden membranous layer.
5. the quick intelligent aqueous gel capable of sugar based on gold surface as claimed in claim 1 is synthetic, and it is characterized by silane coupler in described step (2) is one or more in 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, γ-aminopropyl methyldiethoxysilane and N-2-aminoethyl-3-aminopropyl methyl dimethoxysilane.
6. the quick intelligent aqueous gel capable of sugar based on gold surface as claimed in claim 1 is synthetic, and it is characterized by solvent in described step (2) is (ethanol, toluene and ethanol): distilled water=1:1(V: V=1: the one 1).
7. the quick intelligent aqueous gel capable of sugar based on gold surface as claimed in claim 1 is synthetic, and it is characterized by acid anhydrides in described step (3) is the one in succinic acid Gan ﹑ Shun butene dioic acid Gan ﹑ phthalic anhydride and trimellitic anhydride.
8. the quick intelligent aqueous gel capable of sugar based on gold surface as claimed in claim 1 is synthetic, and it is characterized by solvent in described step (3) is Er Jia base Ya Feng ﹑ N, one or more in N '-bis-methyl Jia Xian An ﹑ carrene and benzene.
9. the quick intelligent aqueous gel capable of sugar based on gold surface as claimed in claim 1 is synthetic, it is characterized by described step (4) medium ultraviolet light wavelength scope is 250 ~ 400 nm, the exposure intensity of ultraviolet light is 1 ~ 100 W/cm2, and the ultraviolet source that uv photopolymerization irradiates use is ZF-1 type ultraviolet analyzer.
10. the quick intelligent aqueous gel capable of sugar based on gold surface as claimed in claim 1 is synthetic, it is characterized by initator in described step (4) is diphenyl second Er Tong ﹑ 2,2-diethoxy benzoylformaldoxime ﹑ a, a-dimethoxy-a-benzene benzoylformaldoxime ﹑ 2,4, one or more in 6-tri-methyl benzophenone and 2,4-diethyl thioxanthone.
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CN111375355A (en) * 2019-12-17 2020-07-07 中科康磁医疗科技(苏州)有限公司 Boric acid hydrogel synthesis method for continuous monitoring of saliva glucose
CN115007147A (en) * 2022-03-22 2022-09-06 浙江理工大学 Photocatalytic composite material and preparation method thereof

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