CN102706929A - Method for preparing photo-crosslinkable modified hyaluronic acid molecular imprinting sensor - Google Patents
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Abstract
The invention discloses a method for preparing a photo-crosslinkable modified hyaluronic acid molecular imprinting sensor and belongs to the technical field of a combination of high polymer material science and chemical sensors. The method includes that a natural macromolecule hyaluronic acid and a photosensitive monomer are subjected to a reaction to prepare a photo-crosslinkable modified hyaluronic acid, and the photo-crosslinkable modified hyaluronic acid and template molecules (imprinting molecules) are mutually dissolved to obtain an imprinting macromolecule colloidal solution. An electrode is inserted into the solution, by means of a constant potential electro-deposition method, a photo-crosslinkable macromolecular membrane is formed on an electrode surface, and after an ultraviolet irradiation crosslinking and a template molecule elution, an electrode which is modified by an imprinting polymer film is obtained. The modified electrode and sensing devices are connected with a computer to form a molecular recognition sensor which is capable of specifically recognizing the template molecules. The method has the advantages that the prepared sensor has a distinctive selectivity and can be widely applied to the fields of bio-medicine, food safety, environmental protection monitoring and the like.
Description
Technical field
The present invention relates to a kind of preparation method of Photocrosslinkable modification hyaluronan molecule trace sensor, through the synthetic macromolecule of MOLECULE DESIGN with specific functionality.Obtain having the molecular engram sensor of selecting response through molecular engram and electro-deposition.Belong to the technical field that polymer material science and chemical sensor combine.
Background technology
Hyaluronic acid (HA) is a kind of linear macromolecule acid mucopolysaccharide of uniqueness, by glucuronic acid and N
2The disaccharide unit of acetylglucosamine alternately is formed by connecting repeatedly, has excellent biological compatibility and degradability.
Molecular imprinting (MIT) is also claimed the template imprinting technology, is to adopt the manual method preparation that specific molecular (being microsphere or template molecule) is had the selectivity combination, and has the technology that specific sky is asked the molecularly imprinted polymer in structure hole (MIP).Because MIP has highly cross-linked structure, good stability can use in severe rugged environments such as high temperature, high pressure, organic solvent, acid, alkali, and cheap, thereby becomes the desirable sensitive material of sensor.MIPs is applied to sensor, can processes the MIPs sensor, its principle is that the high sensitivity with peculiar high selectivity of MIT and various sensing technologies combines, thereby realizes the selectivity rapidly and efficiently of target compound is detected.
In recent years; Molecular imprinting is from the bionics angle; Adopt the method for synthetic to obtain on space and binding site, to mate fully with a certain specific molecular (microsphere, template molecule); Can specificity combine the macromolecular material of this specific molecular, thereby realize molecular recognition, finally be applied to molecular recognition sensor.Resulting molecularly imprinted polymer is otherwise known as " plastics antibody ", promptly has recognition performance and the selectivity same with natural antibody, has high stability and the weatherability same with macromolecule again, thereby has more actual application value.
From the molecularly imprinted polymer to the molecular recognition sensor, the immobilization of imprinted polymer is a committed step, and electrodeposition process film forming thickness homogeneous is controlled, excellent, the good weatherability of base material adhesion.
Therefore; The identification stability that natural macromolecular excellent biological compatibility and degradability and molecular imprinting are provided; Mode with electro-deposition combines, and the sensor of preparing will be widely used in fields such as biological medicine, food security and environment monitorings.
Yet in scope that the applicant reads up the literature, also not seeing has the document that hyaluronic acid is used for molecular engram sensor preparation to disclose with patent.Southern Yangtze University is (application number: 201010109960) proposed a kind of electro-deposition preparation method of molecular recognition sensor in its application for a patent for invention is open.The applicant obtains the trace micella of coated die plate molecule with the synthetic photosensitive multipolymer self assembly of ion-type; Through the constant potential electro-deposition; Ultraviolet irradiation is crosslinked; And the template molecule wash-out, obtain the film modified electrode of trace micella, itself and sensing equipment and computing machine are connected and composed molecular recognition sensor that can single-minded recognition template molecule and be used for the analyzing and testing of template molecule.But the described photosensitive multipolymer of this patent only is confined to some synthetic macromolecule.The present invention breaks through this limitation this natural macromolecular of hyaluronic acid is introduced the molecular engram sensor; Realize the combining of identification stability of natural macromolecular good biocompatibility and degradability and molecular engram with the mode of electro-deposition, thereby further widened the application of natural macromolecular.
Summary of the invention
(1) hyaluronic acid (HA) modification: with the hyaluronic acid massfraction that is made into soluble in water is 1～10% hyaluronic acid aqueous solution; Add triethylamine, tetra-n-butyl ammonium bromide and photosensitive monomer successively; Rising temperature to 50 ℃ after evenly stirring 12～24h under the room temperature～70 ℃; After reacting 5～10h with this understanding, be cooled to room temperature.Unreacted monomer, freeze drying are removed in dialysis, or supercritical drying had both obtained the modification hyaluronic acid of Photocrosslinkable.
(2) preparation of photosensitive molecular trace electrodeposited film modified electrode: the modification hyaluronic acid and the light trigger ring azo amidine class VA-044 of the Photocrosslinkable that makes is soluble in water altogether; Subsequently template molecule is added in this solution; The template molecule addition is 2%～30% of a photosensitive polymerization amount; Stirred overnight makes trace macromolecular colloid solution.Electrode applies a constant potential to it after inserting colloidal solution, makes charged trace colloidal particle to electrode surface swimming and electro-deposition film forming.After ultraviolet light irradiation obtains molecularly imprinted polymer (MIP) electrode film.At last, wash-out is removed template molecule, obtains the molecularly imprinted polymer modified electrode.
(3) preparation of molecular engram sensor: will by the molecularly imprinted polymer electrode of (2) step gained with get final product after sensing equipment is connected molecular recognition sensor.
Use the natural macromolecular hyaluronic acid to be used for the preparation of electrochemical sensor, hyaluronic structure is as shown in Figure 1:
The hyaluronic structure of Photocrosslinkable modification is as shown in Figure 2:
Wherein R is:
The photosensitive monomer of described hyaluronic acid modified use is selected for use and is methyl propenoic acid glycidyl ether, allyl glycidyl ether, 7-glycidoxy-4-methylcoumarin.
The preparation method of described Photocrosslinkable modification hyaluronan molecule trace sensor is characterized in that having given modification hyaluronic acid photaesthesia response, pH susceptibility and electro-deposition film forming through initial MOLECULE DESIGN.
Described template molecule is selected for use: acamol, glucose, trimerization piperazine amine.
Described electrode is the electrode of sensing equipment, and the electrode surface material is the material with electric conductivity, can be gold, glass carbon.
Described electrodeposition technology condition is: the constant potential value is 0.1V～60V, electrodeposition time 5s～10min.
The ultraviolet of described photosensitive molecular imprinted polymer film is that (uviol lamp is a high-pressure sodium lamp to 5min～15min, power: 1000～2000W, irradiation distance: 1～5cm) according to the spoke time
The molecular engram application of sensor: this sensor can selectivity detect masterplate molecule (microsphere), has single-minded selectivity.During use, with this molecular recognition sensor and computer link, whether its electrode engaged test liquid is according to having signal to detect and the power of signal judges whether to contain the size of template molecule and concentration.
Beneficial effect of the present invention: select for use this natural macromolecular of hyaluronic acid to carry out modification,, prepared molecular engram sensor with specific selectivity through the fusion of itself characteristic and molecular imprinting and electro-deposition techniques.The present invention has opened up a feasible really road for natural macromolecular in the application in electrochemical sensor field.This method can also be through choosing different template molecules simultaneously; And starting monomer carried out corresponding Molecular Structure Design; The molecule that the final decision sensor can be discerned, so the present invention can be widely used in association areas such as chemical industry, biological medicine, food, environmental protection tests.
Description of drawings:
Fig. 1 is embodiment 1 resulting K
3[Fe (CN)
6] at bare electrode, deposited the cyclic voltammetric spectrogram of MIP membrane electrode.Fig. 2 is to be the DPVs curve of the prepared MIP sensor that obtains of template molecule in 0.2mM acamol solution with paracetamol (acamol).
Embodiment
Technical scheme of the present invention is not limited to the following embodiment of lifting, and also comprises the combination in any between each embodiment.
Embodiment 1
(1) the hyaluronic modification of Photocrosslinkable modification is synthetic:
(molecular weight is 2 * 10 to weighing 1.02g hyaluronic acid
5Da) be dissolved in the 100mL deionized water, after the dissolving fully, add 5.62g methyl propenoic acid glycidyl ether respectively; 2.2mL triethylamine, the 2.2g TBAB evenly stirs 24h under room temperature; Rising temperature to 60 ℃, react 5h with this understanding after, be cooled to room temperature.Unreacted monomer is removed in dialysis, and freeze drying had both got Photocrosslinkable modification hyaluronic acid.
(2) preparation of trace colloidal solution:
Photocrosslinkable modification hyaluronic acid and light trigger ring azo amidine class VA-044 that step (1) makes is water-soluble altogether, and massfraction is respectively 5% and 3 ‰, subsequently the template molecule acamol is added in this solution stirred overnight.Acamol and Photocrosslinkable modification hyaluronic acid mass ratio are 1: 3.
(3) preparation of galvanochemistry molecular recognition sensor:
Glass-carbon electrode is used the Al of 1.0 μ m and 0.3 μ m successively
2O
3Slurry is polished to minute surface on chamois leather, move into ultrasonic cleaning 2～3min in the ultrapure water again, uses 1: 1 ethanol, 1: 1HNO then successively
3, ultrapure water and absolute ethyl alcohol ultrasonic cleaning, dry.The glass-carbon electrode that pre-service is good inserts trace colloidal solution; Apply the voltage of one+2V; The trace colloidal particle that makes bear electricity is to the electrode surface swimming and deposit film forming; Electrode surface places irradiation 5min under the uviol lamp after washing with a large amount of ultrapure waters, makes electrode surface colloidal particle generation photo-crosslinking.Again electrode being soaked in volume ratio is in 2: 8 the acetic acid, methanol solution, stirs 10h, and the wash-out acamol obtains the blotting membrane modified electrode.This electrode is connected with electrochemical workstation and is molecular recognition sensor, and it has single-minded selectivity to acamol.
Embodiment 2
(1) the Photocrosslinkable modification is hyaluronic synthetic:
(molecular weight is 2 * 10 to weighing 1.02g hyaluronic acid
5Da) be dissolved in the 100mL deionized water, after the dissolving fully, add 7.49g methyl propenoic acid glycidyl ether respectively; 3.3mL triethylamine, 3.3g TBAB, rising temperature to 60 ℃ after evenly stirring 24h under the room temperature; After reacting 5h with this understanding, be cooled to room temperature.Unreacted monomer is removed in dialysis, and freeze drying had both got Photocrosslinkable modification hyaluronic acid.
(2) preparation of trace colloidal solution is identical with example 1.
(3) preparation of galvanochemistry molecular recognition sensor is identical with example 1.
Embodiment 3
(1) the Photocrosslinkable modification is hyaluronic synthetic:
(molecular weight is 3 * 10 to weighing 1.02g hyaluronic acid
5Da) be dissolved in the 100mL deionized water, after the dissolving fully, add 7.49g methyl propenoic acid glycidyl ether respectively; 3.3mL triethylamine, 3.3g TBAB, rising temperature to 60 ℃ after evenly stirring 24h under the room temperature; After reacting 5h with this understanding, be cooled to room temperature.Unreacted monomer is removed in dialysis, and freeze drying had both got Photocrosslinkable modification hyaluronic acid.
(2) preparation of molecular engram electrochemical sensor is identical with example 1.
(3) preparation of galvanochemistry molecular recognition sensor is identical with example 1
Embodiment 4
(1) the hyaluronic modification of Photocrosslinkable modification is synthetic identical with example 1.
(2) preparation of trace colloidal solution:
Photocrosslinkable modification hyaluronic acid and light trigger ring azo amidine class VA-044 that step (1) makes is water-soluble altogether, and massfraction is respectively 5% and 3 ‰, subsequently template molecule glucose is added in this solution stirred overnight.Glucose and Photocrosslinkable modification hyaluronic acid mass ratio are 1: 3.
(3) preparation of galvanochemistry molecular recognition sensor:
Glass-carbon electrode is used the Al of 1.0 μ m and 0.3 μ m successively
2O
3Slurry is polished to minute surface on chamois leather, move into ultrasonic cleaning 2～3min in the ultrapure water again, uses 1: 1 ethanol, 1: 1HNO then successively
3, ultrapure water and absolute ethyl alcohol ultrasonic cleaning; Dry the glass-carbon electrode that pre-service is good and insert trace colloidal solution; Apply the voltage of one+2V, the trace colloidal particle that makes bear electricity is to the electrode surface swimming and deposit film forming, after electrode surface washes with a large amount of ultrapure waters; Place irradiation 5min under the uviol lamp, make electrode surface colloidal particle generation photo-crosslinking.Electrode is soaked in the ethyl acetate solution again, stirs 10h, wash-out glucose obtains the blotting membrane modified electrode.This electrode is connected with electrochemical workstation and is molecular recognition sensor, and it has single-minded selectivity to glucose.
Embodiment 5
(1) the Photocrosslinkable modification is hyaluronic synthetic identical with example 3
(2) preparation of molecular engram electrochemical sensor: Photocrosslinkable modification hyaluronic acid and light trigger ring azo amidine class VA-044 that step (1) makes is water-soluble altogether; Massfraction is respectively 5% and 3 ‰; Subsequently template molecule trimerization piperazine amine is added in this solution stirred overnight.Trimerization piperazine amine and Photocrosslinkable modification hyaluronic acid mass ratio are 1: 3.
(3) preparation of galvanochemistry molecular recognition sensor:
Glass-carbon electrode is used the Al of 1.0 μ m and 0.3 μ m successively
2O
3Slurry is polished to minute surface on chamois leather, move into ultrasonic cleaning 2～3min in the ultrapure water again, uses 1: 1 ethanol, 1: 1HNO then successively
3, ultrapure water and absolute ethyl alcohol be ultrasonic, dry.The glass-carbon electrode that pre-service is good inserts trace colloidal solution; Apply one+2V voltage, the trace colloidal particle that makes bear electricity is to the electrode surface swimming and deposit film forming, after electrode surface washes with a large amount of ultrapure waters; Place irradiation 5min under the uviol lamp, make electrode surface colloidal particle generation photo-crosslinking.Again electrode being soaked in volume ratio is in 2: 8 the acetic acid, methanol solution, stirs 8h, and wash-out trimerization piperazine amine obtains the blotting membrane modified electrode.This electrode is connected with electrochemical workstation and is molecular recognition sensor, and it has single-minded selectivity to trimerization piperazine amine.
Claims (8)
1. the preparation method of a Photocrosslinkable modification hyaluronan molecule trace sensor is characterized in that, comprises the steps:
(1) hyaluronic acid (HA) modification: with the hyaluronic acid massfraction that is made into soluble in water is 1～10% hyaluronic acid aqueous solution; Add triethylamine, tetra-n-butyl ammonium bromide and photosensitive monomer successively; Rising temperature to 50 ℃ after evenly stirring 12～24h under the room temperature～70 ℃; After reacting 5～10h with this understanding, be cooled to room temperature.Unreacted monomer, freeze drying are removed in dialysis, or supercritical drying had both obtained the modification hyaluronic acid of Photocrosslinkable.
(2) preparation of photosensitive molecular trace electrodeposited film modified electrode: the modification hyaluronic acid and the light trigger ring azo amidine class VA-044 of the Photocrosslinkable that makes is soluble in water altogether; Subsequently template molecule is added in this solution; The template molecule addition is 2%～30% of a photosensitive polymerization amount; Stirred overnight makes trace macromolecular colloid solution.Electrode applies a constant potential to it after inserting colloidal solution, makes charged trace colloidal particle to electrode surface swimming and electro-deposition film forming.After ultraviolet light irradiation obtains molecularly imprinted polymer (MIP) electrode film.At last, wash-out is removed template molecule, obtains the molecularly imprinted polymer modified electrode.
(3) preparation of molecular engram sensor: will by the molecularly imprinted polymer electrode of (2) step gained with get final product after sensing equipment is connected molecular recognition sensor.
2. according to right 1 described preparation method, it is characterized in that used hyaluronic molecular weight is 2 * 10
4～3 * 10
5
3. according to right 1 described preparation method, it is characterized in that photosensitive monomer that modification is used can select following one or more for use: methyl propenoic acid glycidyl ether, allyl glycidyl ether, 7-glycidoxy-4-methylcoumarin.And the mol ratio of hyaluronic acid and photosensitive monomer is 1: 5～1: 30.
4. according to right 1 described preparation method, it is characterized in that having given modification hyaluronic acid photaesthesia response, pH susceptibility and electro-deposition film forming through initial MOLECULE DESIGN.
5. according to right 1 described preparation method, it is characterized in that the template molecule that uses selects for use: acamol, glucose, trimerization piperazine amine.
6. according to right 1 described preparation method, it is characterized by the electrode surface material is the material with electric conductivity, can be gold, glass carbon.
7. according to right 1 described preparation method, it is characterized in that the process conditions of electro-deposition are: the constant potential value is 0.1V～60V, electrodeposition time 5s～10min.
8. according to right 1 described preparation method, it is characterized in that the ultraviolet of photosensitive molecular imprinted polymer film is that (uviol lamp is a high-pressure sodium lamp to 5min～15min, power: 1000～2000W, irradiation distance: 1～5cm) according to the spoke time.
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Cited By (8)
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|---|---|---|---|---|
| CN103757683A (en) * | 2014-01-07 | 2014-04-30 | 江南大学 | Electrodeposition preparation method of light-crosslinking bio-based coating |
| CN105113054A (en) * | 2015-09-05 | 2015-12-02 | 常州大学 | Method for preparing hyaluronic acid derivative crosslinking fiber |
| CN105353010A (en) * | 2015-10-28 | 2016-02-24 | 江南大学 | Making method of molecularly imprinted electrochemical sensing electrode for detecting propylene chorohydrin |
| CN105353022A (en) * | 2015-10-28 | 2016-02-24 | 江南大学 | Flexible electrode-based molecularly imprinted electrochemical sensor making method |
| CN106908495A (en) * | 2017-01-05 | 2017-06-30 | 江南大学 | A kind of method that flexible molecule trace sensor is prepared based on carbon nanotube loaded polymer micelle |
| CN107976472A (en) * | 2017-11-22 | 2018-05-01 | 江南大学 | A kind of preparation method of sensor electrode surface stable against biological contamination coating |
| CN108562629A (en) * | 2018-04-24 | 2018-09-21 | 中南民族大学 | A kind of ion-selective electrode and detection method for detecting melamine |
| CN109481729A (en) * | 2018-11-23 | 2019-03-19 | 南京华开生物科技有限公司 | A kind of low molecular weight sodium hyaluronate isotonic liquid dressing and preparation method thereof |
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| CN103757683A (en) * | 2014-01-07 | 2014-04-30 | 江南大学 | Electrodeposition preparation method of light-crosslinking bio-based coating |
| CN103757683B (en) * | 2014-01-07 | 2016-05-25 | 江南大学 | A kind of electro-deposition preparation method of photo-crosslinking type bio-based coating |
| CN105113054A (en) * | 2015-09-05 | 2015-12-02 | 常州大学 | Method for preparing hyaluronic acid derivative crosslinking fiber |
| CN105353010A (en) * | 2015-10-28 | 2016-02-24 | 江南大学 | Making method of molecularly imprinted electrochemical sensing electrode for detecting propylene chorohydrin |
| CN105353022A (en) * | 2015-10-28 | 2016-02-24 | 江南大学 | Flexible electrode-based molecularly imprinted electrochemical sensor making method |
| CN106908495A (en) * | 2017-01-05 | 2017-06-30 | 江南大学 | A kind of method that flexible molecule trace sensor is prepared based on carbon nanotube loaded polymer micelle |
| CN107976472A (en) * | 2017-11-22 | 2018-05-01 | 江南大学 | A kind of preparation method of sensor electrode surface stable against biological contamination coating |
| CN107976472B (en) * | 2017-11-22 | 2020-01-10 | 江南大学 | Preparation method of biological pollution-resistant coating on surface of sensor electrode |
| CN108562629A (en) * | 2018-04-24 | 2018-09-21 | 中南民族大学 | A kind of ion-selective electrode and detection method for detecting melamine |
| CN108562629B (en) * | 2018-04-24 | 2020-02-18 | 中南民族大学 | Ion selective electrode for detecting melamine and detection method |
| CN109481729A (en) * | 2018-11-23 | 2019-03-19 | 南京华开生物科技有限公司 | A kind of low molecular weight sodium hyaluronate isotonic liquid dressing and preparation method thereof |
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