CN105860107A - Preparation method of hydrogen-peroxide-responsive chitosan hydrogel with electrochemical activity - Google Patents

Preparation method of hydrogen-peroxide-responsive chitosan hydrogel with electrochemical activity Download PDF

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Publication number
CN105860107A
CN105860107A CN201610266748.5A CN201610266748A CN105860107A CN 105860107 A CN105860107 A CN 105860107A CN 201610266748 A CN201610266748 A CN 201610266748A CN 105860107 A CN105860107 A CN 105860107A
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chitosan
electro
hydrogen peroxide
response
aquagel
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CN105860107B (en
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刘又年
李烁
王立强
刘颖
邓留
李娟�
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Central South University
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
    • G01N27/3277—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction being a redox reaction, e.g. detection by cyclic voltammetry
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof

Abstract

The invention discloses a preparation method of a hydrogen-peroxide-responsive chitosan hydrogel with electrochemical activity. The method comprises the following step: carrying out reaction on chitosan and 1,1'-ferrocene dicarboxylic acid in a solution system at the temperature of not lower than 50 DEG C under the pH value of 4-8. The 1,1'-ferrocene dicarboxylic acid is used for carrying out coordination hydrogen bond crosslinking on the chitosan to obtain the three-dimensional-network-structure hydrogen-peroxide-responsive chitosan hydrogel with electrochemical activity. The method has the advantage of cheap and accessible raw materials, is simple to operate, and satisfies the requirements for industrial production.

Description

A kind of hydrogen peroxide response and there is the preparation of aquagel of electro-chemical activity Method
Technical field
The present invention relates to the response of a kind of hydrogen peroxide and there is the preparation method of aquagel of electro-chemical activity, belonging to In functional high molecule material synthesis technical field.
Background technology
Hydrogel (Hydrogel) refer on a kind of main chain or side chain containing a large amount of hydrophilic radicals, can adsorb a certain amount of Moisture, the new function macromolecule of the composition tridimensional network that is cross-linked with each other by effects such as covalent bond, hydrogen bond or Van der Waals forces Material.When hydrogel is by outside environmental elements, and when stimulating such as temperature, solution ph, light etc., some hydrogel will ring therewith Should, shrinking, expand, bend the change of equal-volume or shape, this environmental change to external world has the water of stimulating responsive Gel is referred to as progress in Intelligent Hydrogel, and since progress in Intelligent Hydrogel is come out, the hydrogel applied research in this field is the most deep.
Chitosan, i.e. (Isosorbide-5-Nitrae)-2 amino-2-deoxidation-β-D glucosan, is the natural biological polysaccharide of a kind of abundance.It Have nontoxic, tasteless, cheap, relative to synthetic material, there is excellent hydrophilic, biocompatibility and biodegradable Property, there are bioadhesive and multiple biological activity, non-immunogenicity, can be by internal multiple enzyme biodegradation, catabolite is nontoxic And can be fully absorbed by organism, become functional high molecule material and one hot subject of field of biomedical materials.
1,1 '-ferrocenedicarboxylic acid is the ferrocene derivatives modifying carboxyl at cyclopentadienyl ring.At present, the compound containing ferrocene Electrochemistry, asymmetry catalysis, Electrochemical Modification, molecule sensor and nonlinear optics it are widely used in.
Prior art has by using the cross-linked chitosan such as chemical cross-linking agent glutaraldehyde or metal ion, prepares some gels Compounds, but to there is biocompatibility relatively poor for these gels, the shortcomings such as self-repairing capability is poor, and toxicity is big so that it is Application is limited to.But up to the present, also do not have have hydrogen peroxide sound any preparation about ferrocenecarboxylic acid and chitosan Should and the report of aquagel of electro-chemical activity.
Summary of the invention
The defect existed for prior art, it is an object of the invention to provide a kind of with 1,1 '-ferrocenedicarboxylic acid pair Chitosan carries out coordination cross-linked, obtains kind and has three-dimensional net structure, and has hydrogen peroxide response and the shell of electro-chemical activity The method of polysaccharide hydrogel；The method cheaper starting materials is easy to get, simple to operate, meets industrialization production requirements.
For achieving the above object, the invention provides the response of a kind of hydrogen peroxide and there is the chitosan water of electro-chemical activity The preparation method of gel, this preparation method is in solution system, chitosan and 1,1 '-ferrocenedicarboxylic acid, is 4～8 at pH, Temperature is reacted under conditions of being not less than 50 DEG C, to obtain final product.
The 1 of present invention employing, 1 '-ferrocenedicarboxylic acid has the physico-chemical property similar in appearance to ferrocene, such as chemical property Deng, particularity is that 1,1 '-ferrocenedicarboxylic acid adds two polarity carboxyls, carboxyl and the ammonia on chitosan relative to ferrocene Base and hydroxyl etc. are formed and are coordinated hydrogen bond, and 1,1 '-ferrocenedicarboxylic acid plays the effect being equivalent to cross-linking agent, makes chitosan pass through to join Position hydrogen bond crosslinks chain formation three-dimensional net structure.1,1 '-ferrocenedicarboxylic acid and chitosan are by coordination hydrogen bond crosslinks, and it is biological The compatibility is good, and bio-toxicity is low.1,1 '-ferrocenedicarboxylic acid and chitosan are coordination cross-linked by hydrogen bond, and self-repairing capability is relatively By force, it is easy to restore, it has the function of response hydrogen peroxide, and can restore.By introducing ferrocene group so that it is have certain Electro-chemical activity.
Preferably scheme, reaction temperature is 50 DEG C～70 DEG C.Great many of experiments shows, 1, and 1 '-ferrocenedicarboxylic acid and shell gather Sugar is not easily formed gel when ambient temperature is relatively low, initially forms gel at 50 DEG C, and the gel of the too high formation of temperature shows color Slightly deepen, it may be possible to there occurs small amounts, but still can form the gel of steady statue.
More preferably scheme, the response time is 0.5～6h.Lot of experiment validation, when ambient temperature is not less than 50 DEG C, Time is not the most easily formed gel, and the time can form gel more than 0.5h, and overlong time occurs in that gel darkens equally Phenomenon, but do not affect the formation of gel.
Preferably scheme, chitosan and 1 in solution system, the mass ratio of 1 '-ferrocenedicarboxylic acid is (2～15): 1.
Preferably scheme, solution system by the organic acid/aqueous solution of chitosan-containing with containing 1, the alkali of 1 '-ferrocenedicarboxylic acid Solution composition.
More preferably scheme, in the organic acid/aqueous solution of chitosan-containing the mass percent concentration of chitosan be 1%～ 3%.
More preferably scheme, in the aqueous slkali containing 1,1 '-ferrocenedicarboxylic acid 1, the concentration of 1 '-ferrocenedicarboxylic acid is 20 ～100g/L.
Further preferred scheme, in organic acid/aqueous solution, the volume ratio of organic acid and water is (1～5%): (95～ 99%).Organic acid is most preferably glacial acetic acid.
Further preferred scheme, in aqueous slkali, the molar concentration of alkali is 2～4M；Alkali be most preferably sodium hydroxide and/or Potassium hydroxide.
In technical scheme, permissible when 1, the solution system pH=4 of 1 '-ferrocenedicarboxylic acid and chitosan reaction Form gel, still can form gel along with pH increases, but start during pH=8 to occur being polymerized to thing.
Hinge structure, the remarkable result that technical scheme is brought is:
1) chitosan that technical scheme uses is that the chitin being widely present by nature is obtained by deacetylated Arriving, raw material sources are extensive, cheap.
2) technical scheme utilizes chitosan and 1,1 '-ferrocenedicarboxylic acid to form coordination compound by coordination hydrogen bond Build three-dimensional net structure, by the non-covalent bond effect of hydrogen bond, make gel have good self-repairing capability, pass through machine After tool power destroys gel state, standing a period of time can recover.
3) technical scheme utilizes 1,1 '-ferrocenedicarboxylic acid to be cross-linked to form with the coordination hydrogen bond of chitosan Gel, the gel phase ratio obtained as chemical cross-linking agent with existing glutaraldehyde etc., its biocompatibility is more preferable, and toxicity is lower.
4) gel prepared by technical scheme has response hydrogen peroxide character, owing to hydrogen peroxide is not only perhaps The intermediate of many industrial process, or the by-product of many biochemical reactions, relevant with many bioprocesss, the gel therefore prepared It is expected to apply further in industrial pollutants process and biomedical aspect.
5) gel prepared by technical scheme has certain redox electro-chemical activity, and contains in gel Some chitosans tool is a bit sticky, can be as set electron mediator and adhesive agent function electrode modification material Material, can be applicable to build electrochemical sensor.
6) method preparing gel of the present invention, technique is simple, is not required to expensive instrument, it is easy to operation, mild condition, process Safety.
Accompanying drawing explanation
[Fig. 1] is chitosan/1,1 '-ferrocene dicarboxylic acid hydrogel pictorial diagram.
[Fig. 2] is chitosan/1,1 '-ferrocene dicarboxylic acid hydrogel scanning electron microscope (SEM) figure.
[Fig. 3] is the schematic diagram of hydrogel response hydrogen peroxide.
[Fig. 4] is cyclic voltammetric (CV) curve chart of hydrogel modified electrode.
[Fig. 5] is the inversion figure detecting plastic situation under conditions of different bath temperature, water bath time, different pH value； All solution chitosan mass percent concentrations are 2%, 1, and the concentration of 1 '-ferrocene dicarboxylic acid is 2mg/mL；(a) water bath time 1h, system pH is 5, and bath temperature is followed successively by 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C from left to right； (b) bath temperature 50 DEG C, system pH is 5, water bath time be followed successively by from left to right 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h；C () bath temperature 50 DEG C, water bath time 1h, system pH is followed successively by 3,4,5,6,7,8 from left to right.
Detailed description of the invention
Following example are intended to further illustrate present invention rather than limit the protection model of the claims in the present invention Enclose.
Embodiment 1
1) weigh 200mg chitosan to be dissolved in the glacial acetic acid aqueous solution that 9.8mL mass fraction is 2%；
2) weighing 100mg1,1 '-ferrocene dicarboxylic acid is dissolved in the sodium hydrate aqueous solution that 5mL concentration is 2M, shakes molten Solve；
3) the 1 of 900 μ L is pipetted) solution and the 2 of 100 μ L) mixing；
4) it is placed in the water-bath of 50 DEG C reaction 1h, cooling, obtains chitosan/1,1 '-ferrocene dicarboxylic acid hydrogel.
Chitosan/1,1 '-ferrocene dicarboxylic acid hydrogel pictorial diagram is as shown in Figure 1.
Chitosan/1,1 '-ferrocene dicarboxylic acid hydrogel scanning electron microscope (SEM) figure is as shown in Figure 2.
Embodiment 2
1) weigh 200mg chitosan to be dissolved in the glacial acetic acid aqueous solution that 9.8mL mass fraction is 2%；
2) weighing 500mg1,1 '-ferrocene dicarboxylic acid is dissolved in the sodium hydrate aqueous solution that 5mL concentration is 2M, shakes molten Solve；
3) the 1 of 900 μ L is pipetted) solution and the 2 of 100 μ L) mixing；
4) it is placed in the water-bath of 50 DEG C reaction 1h, cooling, obtains chitosan/1 that form is similar to Example 1,1 '-two Cyclopentadienyl ferrum dioctyl phthalate hydrogel.
Embodiment 3
1) weigh 200mg chitosan to be dissolved in the glacial acetic acid aqueous solution that 9.8mL mass fraction is 2%, 30～40 DEG C of heating Dissolve；
2) weighing 100mg1,1 '-ferrocene dicarboxylic acid is dissolved in the sodium hydrate aqueous solution that 5mL concentration is 2M, shakes molten Solve；
3) the 1 of 900 μ L is pipetted) solution and the 2 of 100 μ L) mixing；
4) reaction 1h, cooling it are placed in the water-bath of 50 DEG C；
5) hydrogenperoxide steam generator pipetting 30uL concentration 0.2M adds in gel.
6) after 45min, gel is liquid by solid state transformation, and phenomenon is as shown in Figure 3.
Embodiment 4
1) weigh 200mg chitosan to be dissolved in the glacial acetic acid aqueous solution that 9.8mL mass fraction is 2%；
2) weighing 100mg1,1 '-ferrocene dicarboxylic acid is dissolved in the sodium hydrate aqueous solution that 5mL concentration is 2M, shakes molten Solve；
3) the 1 of 900 μ L is pipetted) solution and the 2 of 100 μ L) mixing；
4) reaction 1h, cooling it are placed in the water-bath of 50 DEG C；
5) gel obtained is shaken at distilled water scattered, dilute 10 times, pipette 10 μ L and drip on the glass-carbon electrode of milled, room temperature Lower dry；
6) preparation acetic acid/sodium acetate buffer (100mmol/L, pH=5.2)；
7) the hydrogel modified electrode prepared is in HAc/NaAc (10mmol/L, pH=5.2), and sweep speed is 0.1V S-1Carry out CV test, phenomenon such as Fig. 3.
Embodiment 5
1) weigh 200mg chitosan to be dissolved in the glacial acetic acid aqueous solution that 9.8mL mass fraction is 2%, 30～40 DEG C of heating Dissolve；
2) weighing 100mg1,1 '-ferrocene dicarboxylic acid is dissolved in the sodium hydrate aqueous solution that 5mL concentration is 2M, shakes molten Solve；
3) the 1 of 900 μ L is pipetted) solution and the 2 of 100 μ L) mixing；
4) repeat step 3) 8 times, and solution is respectively placed in 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C water-bath in react 1h, cool down to obtain gel, Fig. 5 (a) is shown in by photo in kind.
Embodiment 6
1) weigh 200mg chitosan to be dissolved in the glacial acetic acid aqueous solution that 9.8mL mass fraction is 2%, 30～40 DEG C of heating Dissolve；
2) weighing 100mg1,1 '-ferrocene dicarboxylic acid is dissolved in the sodium hydrate aqueous solution that 5mL concentration is 2M, shakes molten Solve；
3) the 1 of 900 μ L is pipetted) solution and the 2 of 100 μ L) mixing；
4) repeat step 3) 9 times, and solution is placed in the water-bath of 50 DEG C, react respectively 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, cool down to obtain gel, and Fig. 5 (b) is shown in by photo in kind.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, all according to the present patent application patent model Enclose done impartial change and modify, all should belong to the covering scope of the present invention.All made within the spirit and principles in the present invention Any amendment, equivalent and improvement etc., should be included within the scope of the present invention.

Claims (10)

1. hydrogen peroxide response and there is the preparation method of aquagel of electro-chemical activity, it is characterised in that: In solution system, chitosan and 1,1 '-ferrocenedicarboxylic acid, is 4～8 at pH, and temperature is reacted, i.e. under conditions of being not less than 50 DEG C ?.
Hydrogen peroxide the most according to claim 1 response and there is the preparation side of aquagel of electro-chemical activity Method, it is characterised in that: reaction temperature is 50 DEG C～70 DEG C.
Hydrogen peroxide the most according to claim 2 response and there is the preparation side of aquagel of electro-chemical activity Method, it is characterised in that: the response time is 0.5～6h.
4. respond and have the aquagel of electro-chemical activity according to the hydrogen peroxide described in any one of claims 1 to 3 Preparation method, it is characterised in that: chitosan and 1 in described solution system, the mass ratio of 1 '-ferrocenedicarboxylic acid be (2～ 15):1。
Hydrogen peroxide the most according to claim 4 response and there is the preparation side of aquagel of electro-chemical activity Method, it is characterised in that: described solution system by the organic acid/aqueous solution of chitosan-containing with containing 1,1 '-ferrocenedicarboxylic acid Aqueous slkali forms.
Hydrogen peroxide the most according to claim 5 response and there is the preparation side of aquagel of electro-chemical activity Method, it is characterised in that: in the organic acid/aqueous solution of described chitosan-containing the mass percent concentration of chitosan be 1%～ 3%；In the described aqueous slkali containing 1,1 '-ferrocenedicarboxylic acid, 1,1 '-ferrocenedicarboxylic acid concentration is 20～100g/L.
Hydrogen peroxide the most according to claim 6 response and there is the preparation side of aquagel of electro-chemical activity Method, it is characterised in that: in described organic acid/aqueous solution, organic acid is (1～5%) with the volume ratio of water: (95～99%).
Hydrogen peroxide the most according to claim 7 response and there is the preparation side of aquagel of electro-chemical activity Method, it is characterised in that: described organic acid is glacial acetic acid.
Hydrogen peroxide the most according to claim 6 response and there is the preparation side of aquagel of electro-chemical activity Method, it is characterised in that: in described aqueous slkali, the molar concentration of alkali is 2～4M.
Hydrogen peroxide the most according to claim 9 response and there is the preparation side of aquagel of electro-chemical activity Method, it is characterised in that: described alkali is sodium hydroxide and/or potassium hydroxide.
CN201610266748.5A 2016-04-26 2016-04-26 A kind of hydrogen peroxide response and the preparation method of the aquagel with electro-chemical activity Expired - Fee Related CN105860107B (en)

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