CN102643375A - Preparation method of biocompatible photo-thermal response self-healing conductive hydrogel - Google Patents

Preparation method of biocompatible photo-thermal response self-healing conductive hydrogel Download PDF

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CN102643375A
CN102643375A CN201210124992XA CN201210124992A CN102643375A CN 102643375 A CN102643375 A CN 102643375A CN 201210124992X A CN201210124992X A CN 201210124992XA CN 201210124992 A CN201210124992 A CN 201210124992A CN 102643375 A CN102643375 A CN 102643375A
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hydrogel
preparation
graphene
healing
biocompatible
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李耀刚
侯成义
张青红
王宏志
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Donghua University
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Donghua University
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Abstract

The invention relates to a preparation method of biocompatible photo-thermal response self-healing conductive hydrogel, which includes: preparing solution from N,N-dimethyl acrylamide monomer, potassium persulfate serving as initiator and N,N,N',N'-tetramethylethylenediamine serving as accelerator; then soaking graphene hydrogel into the monomer solution for solution displacement and standing; and finally, initiating polymerization reaction at the room temperature, so that the biocompatible photo-thermal response self-healing conductive hydrogel is prepared. The preparation method is simple in process, mild in reaction condition, short in reaction time and suitable for industrial production. The hydrogel uses the graphene as a three-dimensional network framework, the graphene is high in reduction degree, chemical stability, electric conductivity and mechanical strength and good in photothermal conversion effect, and the hydrogel shows good self-healing performance within the body temperature range and under near-infrared irradiation.

Description

A kind of preparation method of biocompatible photothermal response self-healing conductive hydrogel
Technical field
The invention belongs to the preparation field of conductive hydrogel, particularly a kind of preparation method of biocompatible photothermal response self-healing conductive hydrogel.
Background technology
Self-healing is a kind of performance that system is repaired self-inflicted injury.At occurring in nature, the self-healing phenomenon can find expression in little reparation to the dna molecular chain, big healing to organic life entity wound.The material that the human development of trial already has the self-healing ability is used for multinomial sciemtifec and technical sphere, even the artificial bionic self-healing material is used for substituting organic life entity.Main artificial self-healing material comprises at present: polymkeric substance, pottery, cement, metal etc.Wherein, polyalcohol hydrogel is the material that is widely used in biomedical sector, and recent research person has reported multiple self-healing polyalcohol hydrogel material system.Yet the self-healing hydrogel of report scarcely has electrochemical activity at present, so it can't play the neural effect that connects; In addition, most of self-healing hydrogel need issue in long-time or hot conditions is conigenous the healing phenomenon, and material itself do not have biocompatibility, and these all are them as artificial tissue or huge challenge that the organ material faced.
Recently, grapheme material is proved to be has excellent biological compatibility, and existing report has been studied its application in vivo.In addition, Graphene has excellent chemical property and photo-thermal conversion performance, is expected to be applied to the self-healing aquogel system to break through its application bottleneck in biomedical sector.People such as Shi use solvent thermal method to prepare physical strength height, Graphene hydrogel that specific conductivity is high last report of ACS Nano 4 (2010) 4324-4330.On this basis, contriver Li Yao has just waited in the last use solvent thermal method of having reported of Carbon 50 (2012) 1959-1965 and has prepared Graphene-PNIPAM hydrogel and also propose the graphene-polymer hydrogel is applied to the human tissue engineering material.This shows that biocompatible graphene-polymer self-healing hydrogel has application prospect in the reparation of life entity with in substituting.
Do not see at present the report of the biocompatible graphene-polymer self-healing hydrogel of preparation.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of biocompatible photothermal response self-healing conductive hydrogel; This method technology is simple; Reaction conditions is gentle, and the hydrogel that obtains shows good self-healing performance in body temperature and under the near infrared light.
The preparation method of a kind of biocompatible photothermal response self-healing conductive hydrogel of the present invention comprises:
With N, N-DMAA monomer, initiator potassium persulfate and accelerator N, N; N '; N '-Tetramethyl Ethylene Diamine be mixed with monomer solution, the Graphene hydrogel is soaked in carries out the solution displacement in the above-mentioned monomer solution then, leave standstill; Initiated polymerization at room temperature promptly gets Graphene-polydimethylacrylamiin hydrogel at last.
Described Graphene hydrogel is made in 100~200 ℃ of following hydro-thermal reaction 8~12h by the graphite oxide aqueous solution of 1~2mg/ml.
The mass ratio of described Graphene hydrogel and monomer solution is 0.04~0.12: 1.
Described solution metathetical temperature is 2~5 ℃, and the time is 12~24h.
N in the described monomer solution, the mass ratio of N-DMAA and water are 0.08~0.12: 1, and the mass ratio of Potassium Persulphate and water is 0.0008~0.0012: 1, and the mass ratio of N,N,N and water is 0.002~0.003: 1.
The time of described polyreaction is 48~72h.
Beneficial effect
(1) method technology of the present invention is simple, and reaction conditions is gentle, and the reaction times is short, is suitable for suitability for industrialized production;
(2) as the three-dimensional network skeleton, the Graphene reducing degree is high with Graphene for graphene-polymer hydrogel of the present invention, and chemicalstability is good, and specific conductivity is high, and physical strength is high, and the photo-thermal conversion effect is good;
(3) graphene-polymer hydrogel of the present invention shows good self-healing performance in body temperature and under the near infrared light.
Description of drawings
Fig. 1 is Fourier's infared spectrum of the hydrogel of embodiment 1 preparation;
Fig. 2 is the electron scanning micrograph of the hydrogel of embodiment 1 preparation;
Fig. 3 is the temperature response self-healing demonstration photo of the hydrogel of embodiment 1 preparation;
Fig. 4 is the near infrared light response self-healing demonstration photo of the hydrogel of embodiment 1 preparation.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
With 3.2gN, N-DMAA monomer, 0.032g initiator potassium persulfate and 0.08g accelerator N,N,N dissolve in the 30g water, are mixed with monomer solution; The graphite oxide aqueous solution of 1mg/ml is made the Graphene hydrogel in 200 ℃ of following hydro-thermal reaction 8~12h; Under 2 ℃, the 3.6g Graphene hydrogel of Hydrothermal Preparation is soaked in that 24h carries out the solution displacement in the monomer solution; The Graphene hydrogel that will contain monomer solution leaves standstill, and at room temperature obtains Graphene-polydimethylacrylamiin hydrogel behind the initiated polymerization 48h.
Fig. 1 is Fourier's infared spectrum of product, and collection of illustrative plates shows the N in the Graphene hydrogel, and N-DMAA monomer success polymerization forms polydimethylacrylamiin.
Fig. 2 is the electron scanning micrograph of product, can find out Graphene-polydimethylacrylamiin hydrogel with the Graphene three-dimensional network as skeleton structure, polymkeric substance is filled in the Graphene three-dimensional network.The specific conductivity of product is 0.67 * 10 -4S/cm, ultimate compression strength is 2.62MPa, the impedance under biological neuroscience important frequencies 1kHz is low to moderate 1.3k Ω and has good neurocyte consistency.
Fig. 3 is the temperature response self-healing demonstration photo of product, and the Graphene of cutting open-polydimethylacrylamiin hydrogel places under 38 ℃, through 12h the self-healing phenomenon takes place.
Fig. 4 is the near infrared light response self-healing demonstration photo of product; The Graphene of cutting open-polydimethylacrylamiin hydrogel thin slice places (wavelength: 1064nm under the near infrared light; Power: 500mW; Spot diameter: 45mm), through 2h circulation irradiation hydrogel thin slice contact surface, hydrogel generation self-healing phenomenon.
Embodiment 2
With 5gN, N-DMAA monomer, 0.05g initiator potassium persulfate and 0.125g accelerator N,N,N dissolve in the 50g water, are mixed with monomer solution; The graphite oxide aqueous solution of 2mg/ml is made the Graphene hydrogel in 100 ℃ of following hydro-thermal reaction 8h; Under 4 ℃, the 4g Graphene hydrogel of Hydrothermal Preparation is soaked in that 18h carries out the solution displacement in the monomer solution; The Graphene hydrogel that will contain monomer solution leaves standstill, and at room temperature obtains Graphene-polydimethylacrylamiin hydrogel behind the initiated polymerization 60h.
N in the Graphene hydrogel, N-DMAA monomer success polymerization forms polydimethylacrylamiin.As skeleton structure, polymkeric substance is filled in the Graphene three-dimensional network Graphene-polydimethylacrylamiin hydrogel with the Graphene three-dimensional network.The specific conductivity of product, ultimate compression strength are high, and the impedance under biological neuroscience important frequencies 1kHz is low and have a good neurocyte consistency.Product shows good temperature and near infrared light response self-healing phenomenon.
Embodiment 3
With 7.2gN, N-DMAA monomer, 0.072g initiator potassium persulfate and 0.18g accelerator N,N,N dissolve in the 90g water, are mixed with monomer solution; The graphite oxide aqueous solution of 1.5mg/ml is made the Graphene hydrogel in 150 ℃ of following hydro-thermal reaction 10h; Under 5 ℃, the 3.6g Graphene hydrogel of Hydrothermal Preparation is soaked in that 12h carries out the solution displacement in the monomer solution; The Graphene hydrogel that will contain monomer solution leaves standstill, and at room temperature obtains Graphene-polydimethylacrylamiin hydrogel behind the initiated polymerization 72h.
N in the Graphene hydrogel, N-DMAA monomer success polymerization forms polydimethylacrylamiin.As skeleton structure, polymkeric substance is filled in the Graphene three-dimensional network Graphene-polydimethylacrylamiin hydrogel with the Graphene three-dimensional network.The specific conductivity of product, ultimate compression strength are high, and the impedance under biological neuroscience important frequencies 1kHz is low and have a good neurocyte consistency.Product shows good temperature and near infrared light response self-healing phenomenon.

Claims (6)

1. the preparation method of a biocompatible photothermal response self-healing conductive hydrogel comprises:
With N, N-DMAA monomer, initiator potassium persulfate and accelerator N, N; N ', N '-Tetramethyl Ethylene Diamine be mixed with monomer solution, the Graphene hydrogel is soaked in carries out the solution displacement in the above-mentioned monomer solution then; Leave standstill, initiated polymerization at room temperature promptly gets at last.
2. the preparation method of a kind of biocompatible photothermal response self-healing conductive hydrogel according to claim 1 is characterized in that: described Graphene hydrogel is made in 100~200 ℃ of following hydro-thermal reaction 8~12h by the graphite oxide aqueous solution of 1~2mg/mL.
3. the preparation method of a kind of biocompatible photothermal response self-healing conductive hydrogel according to claim 1 is characterized in that: the mass ratio of described Graphene hydrogel and monomer solution is 0.04~0.12: 1.
4. the preparation method of a kind of biocompatible photothermal response self-healing conductive hydrogel according to claim 1 is characterized in that: described solution metathetical temperature is 2~5 ℃, and the time is 12~24h.
5. the preparation method of a kind of biocompatible photothermal response self-healing conductive hydrogel according to claim 1; It is characterized in that: N in the described monomer solution, the mass ratio of N-DMAA and water are 0.08~0.12: 1, and the mass ratio of Potassium Persulphate and water is 0.0008~0.0012: 1; N; N, N ', the mass ratio of N '-Tetramethyl Ethylene Diamine and water are 0.002~0.003: 1.
6. the preparation method of a kind of biocompatible photothermal response self-healing conductive hydrogel according to claim 1 is characterized in that: the time of described polyreaction is 48~72h.
CN201210124992XA 2012-04-26 2012-04-26 Preparation method of biocompatible photo-thermal response self-healing conductive hydrogel Pending CN102643375A (en)

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CN104030278A (en) * 2014-06-13 2014-09-10 北京化工大学 Method for preparing crosslinking graphene sponge and application thereof in traumatic hemostasis
CN105107019A (en) * 2015-09-10 2015-12-02 西南交通大学 Preparing method for infrared response high-strength hydrogel for cartilago articularis repair
CN105153359A (en) * 2015-08-25 2015-12-16 东莞市万康医疗器械有限公司 Conductive hydrogel, conductive hydrogel coil and their preparation methods
CN105816881A (en) * 2015-12-29 2016-08-03 温州生物材料与工程研究所 Composite system based on near-infrared photothermal agent and temperature-sensitive polymer, drug carrier and preparation method
CN105949364A (en) * 2016-07-22 2016-09-21 合肥工业大学 Novel photo-irradiation induced self-repairing precious metal nano composite hydrogel and preparation method thereof
CN106008799A (en) * 2016-05-23 2016-10-12 西南交通大学 Preparation method of hydrogel electrode with high mechanical property and self-healing property
CN106674434A (en) * 2017-01-16 2017-05-17 合肥工业大学 Preparation method of anti-notch-sensitivity graphene-type nano composite aquagel
CN106773143A (en) * 2016-12-06 2017-05-31 东华大学 A kind of near infrared light mutagens shape Graphene/NIPAAm laminated films and its preparation and application
CN107440686A (en) * 2017-06-13 2017-12-08 菏泽学院 One kind is used for mouse femoral bone impairment model and its multi-functional fixed system
CN109870417A (en) * 2019-04-13 2019-06-11 中国科学院新疆理化技术研究所 A kind of comparator gel and preparation method thereof quickly detecting non-standard explosion raw material urea
CN111518309A (en) * 2020-06-04 2020-08-11 东北林业大学 Biomass nanocellulose/polypyrrole composite aerogel and preparation method and application thereof
CN114634593A (en) * 2022-03-18 2022-06-17 四川大学 pNIPAm gel device, method for regulating response temperature, light management and durability

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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104030278B (en) * 2014-06-13 2016-06-01 北京化工大学 A kind of preparation method of crosslinked graphene sponge and the application in trauma hemostasis thereof
CN104030278A (en) * 2014-06-13 2014-09-10 北京化工大学 Method for preparing crosslinking graphene sponge and application thereof in traumatic hemostasis
CN105153359A (en) * 2015-08-25 2015-12-16 东莞市万康医疗器械有限公司 Conductive hydrogel, conductive hydrogel coil and their preparation methods
CN105107019B (en) * 2015-09-10 2018-05-18 西南交通大学 A kind of preparation method of the high-strength hydrogel of infrared response for articular cartilage reparation
CN105107019A (en) * 2015-09-10 2015-12-02 西南交通大学 Preparing method for infrared response high-strength hydrogel for cartilago articularis repair
CN105816881A (en) * 2015-12-29 2016-08-03 温州生物材料与工程研究所 Composite system based on near-infrared photothermal agent and temperature-sensitive polymer, drug carrier and preparation method
CN105816881B (en) * 2015-12-29 2019-02-19 温州生物材料与工程研究所 Combined system, pharmaceutical carrier and preparation method based near infrared light thermit powder and temperature sensing polymer
CN106008799A (en) * 2016-05-23 2016-10-12 西南交通大学 Preparation method of hydrogel electrode with high mechanical property and self-healing property
CN105949364A (en) * 2016-07-22 2016-09-21 合肥工业大学 Novel photo-irradiation induced self-repairing precious metal nano composite hydrogel and preparation method thereof
CN106773143A (en) * 2016-12-06 2017-05-31 东华大学 A kind of near infrared light mutagens shape Graphene/NIPAAm laminated films and its preparation and application
CN106674434A (en) * 2017-01-16 2017-05-17 合肥工业大学 Preparation method of anti-notch-sensitivity graphene-type nano composite aquagel
CN106674434B (en) * 2017-01-16 2019-08-02 合肥工业大学 A kind of preparation method of the graphite ene-type Nanometer composite hydrogel of anti-notch sensitivity
CN107440686A (en) * 2017-06-13 2017-12-08 菏泽学院 One kind is used for mouse femoral bone impairment model and its multi-functional fixed system
CN107440686B (en) * 2017-06-13 2020-08-04 菏泽学院 Be used for damaged model of mouse thighbone and multi-functional fixing system thereof
CN109870417A (en) * 2019-04-13 2019-06-11 中国科学院新疆理化技术研究所 A kind of comparator gel and preparation method thereof quickly detecting non-standard explosion raw material urea
CN109870417B (en) * 2019-04-13 2021-07-02 中国科学院新疆理化技术研究所 Colorimetric gel for rapidly detecting non-standard explosive raw material urea and preparation method thereof
CN111518309A (en) * 2020-06-04 2020-08-11 东北林业大学 Biomass nanocellulose/polypyrrole composite aerogel and preparation method and application thereof
CN114634593A (en) * 2022-03-18 2022-06-17 四川大学 pNIPAm gel device, method for regulating response temperature, light management and durability
CN114634593B (en) * 2022-03-18 2023-11-17 四川大学 pNIPAm gel device, method for regulating response temperature, light management and durability

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Application publication date: 20120822