CN110511320B - Oxidized konjac glucomannan composite hydrogel based on Schiff base reaction and preparation method and application thereof - Google Patents
Oxidized konjac glucomannan composite hydrogel based on Schiff base reaction and preparation method and application thereof Download PDFInfo
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Abstract
本发明涉及了一种基于席夫碱反应的氧化魔芋葡甘聚糖复合水凝胶及其制备方法，其制备方法包括以下步骤：在冰水浴条件下向氧化魔芋葡甘聚糖水溶液中加入丙烯酰胺和引发剂，并通惰性气体或氮气排除溶液中的氧气，混合均匀，得凝胶前驱体，将凝胶前驱体静置反应，即得所述复合水凝胶。本发明提供的一种基于席夫碱反应的氧化魔芋葡甘聚糖复合水凝胶的制备方法，简单易行，环境友好；采用本发明提供的制备方法制备得到的一种氧化魔芋葡甘聚糖复合水凝胶的黏弹性好，粘附性强，其粘附强度可高达49.02 kPa，且具有自愈合性能。The invention relates to an oxidized konjac glucomannan composite hydrogel based on Schiff base reaction and a preparation method thereof. The preparation method comprises the following steps: adding propylene to an oxidized konjac glucomannan aqueous solution under ice-water bath conditions The amide and the initiator are mixed with inert gas or nitrogen to remove the oxygen in the solution, and the gel precursor is obtained. The composite hydrogel is obtained by standing and reacting the gel precursor. The preparation method of the oxidized konjac glucomannan composite hydrogel based on the Schiff base reaction provided by the invention is simple, easy to implement, and environmentally friendly; an oxidized konjac glucomannan prepared by the preparation method provided by the invention The sugar composite hydrogel has good viscoelasticity and strong adhesion, its adhesion strength can be as high as 49.02 kPa, and it has self-healing properties.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to an oxidized konjac glucomannan composite hydrogel with self-healing performance and adhesion performance based on Schiff base reaction, and a preparation method and application thereof.
Background
The hydrogel is a multi-element system formed by a three-dimensional cross-linking network and a medium, has good water absorption, water retention, biocompatibility and other intelligent characteristics, and has important application prospects in the fields of bionic intelligent devices, tissue engineering scaffolds, disease diagnosis and treatment and wound dressing materials, stretchable electronic equipment, medical equipment coatings, soft robots, mechanical equipment and the like. In the above fields, the adhesive hydrosol is widely used, for example, the conductive gel with adhesion can perform a bonding function at an interface between an electronic device and a human body, thereby achieving a therapeutic effect.
However, most of the existing hydrogel crosslinking methods with strong adhesion property adopt the method of oxidative coupling of catechol structure in dopamine or catechol, for example, Chinese patent CN106589409A discloses a polyglutamic acid/sodium alginate adhesive hydrogel and a preparation method thereof, wherein dopamine-modified oxidized sodium alginate and hydrazide-modified polyglutamic acid are added into Fe3+Curing to form the glue. The patent utilizes catechol and Fe in dopamine catechol3+Complex crosslinking, although hydrogel with certain adhesiveness can be obtained in the way, Fe is added in the preparation process3+Has toxic and side effects, and the formed hydrogel chain segment is lack of hydrogen bonds and ionic bonds based on self-healing and has no self-healing performance. Under the influence of an adhesion mechanism of natural mussels, the xylol and the like use dopamine and acrylamide as raw materials to synthesize hydrogel with excellent adhesion performance under a cross-linking agent MBA (N, N-dimethyl bisacrylamide), but the dopamine is easily oxidized excessively in the oxidation process, once the gel prepared by excessive oxidation loses viscosity and is not easy to control, the content of the acrylamide used in experiments is generally more than 20%, the acrylamide belongs to a synthetic substance and is not easy to degrade, and the acrylamide is harmful to human bodies and the environment when the amount is large, so that the preparation of the hydrogel with higher adhesion and self-healing performance by a simple, easy and environment-friendly method has important significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of oxidized konjac glucomannan composite hydrogel based on Schiff base reaction, which is simple and easy to implement and environment-friendly; the oxidized konjac glucomannan composite hydrogel prepared by the method has good self-healing property, adhesiveness and biocompatibility, and has important application in preparation of biomedical materials and adhesives.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of oxidized konjac glucomannan composite hydrogel based on Schiff base reaction comprises the following steps:
adding acrylamide and an initiator into the oxidized konjac glucomannan aqueous solution under the ice-water bath condition, introducing inert gas or nitrogen to remove oxygen in the solution, uniformly mixing to obtain a gel precursor, and standing the gel precursor for reaction to obtain the composite hydrogel.
The preparation method of the oxidized konjac glucomannan composite hydrogel based on the Schiff base reaction comprises the step of preparing the oxidized konjac glucomannan aqueous solution by using a solvent, wherein the mass fraction of the oxidized konjac glucomannan aqueous solution is 2% -12%.
The preparation method of the oxidized konjac glucomannan composite hydrogel based on the Schiff base reaction comprises the following step of mixing acrylamide and water, wherein the amount of the acrylamide is 9-11% of the mass of a gel precursor.
The preparation method of the oxidized konjac glucomannan composite hydrogel based on the Schiff base reaction comprises the step of preparing a composite hydrogel by using a Schiff base reaction method, wherein the initiator is potassium persulfate or ammonium persulfate.
The preparation method of the oxidized konjac glucomannan composite hydrogel based on the Schiff base reaction comprises the step of preparing a composite hydrogel by using a reaction solution, wherein the amount of the initiator is 3 per mill-1% of the mass of acrylamide.
The preparation method of the oxidized konjac glucomannan composite hydrogel based on the Schiff base reaction comprises the step of standing reaction at the temperature of 50-75 ℃ for 8-12 hours.
The oxidized konjac glucomannan composite hydrogel is prepared by any one of the methods.
The oxidized konjac glucomannan composite hydrogel has self-healing property, adhesiveness and biocompatibility.
The oxidized konjac glucomannan composite hydrogel is applied to preparation of biomedical materials and adhesives.
The preparation method of the oxidized konjac glucomannan composite hydrogel provided by the invention is simple and feasible, is environment-friendly and nontoxic, takes the oxidized konjac glucomannan aqueous solution and acrylamide as base materials, in the reaction process, aldehyde groups of the oxidized konjac glucomannan and amino groups on part of the acrylamide are subjected to Schiff base reaction to form a graft structure, carbon-carbon double bonds of the acrylamide are subjected to free radical polymerization initiated by an initiator to form long-chain polyacrylamide (PAAm), and the carbon-carbon double bonds of the acrylamide grafted on the oxidized konjac glucomannan chain become crosslinking points of the konjac glucomannan and the polyacrylamide. Due to the fact that-N = C-structure of Schiff base exists in the molecular structure of the cross-linking point position in the cross-linking network of the gel, the formed composite hydrogel has good adhesion. Meanwhile, hydrogen bond interaction also exists between hydroxyl of the oxidized konjac glucomannan and amino on the polyacrylamide, so that the network structure of the gel can be further enhanced and stabilized, and the adhesion of the composite hydrogel is further enhanced. And hydrogen bonds between polyacrylamide chain segments and hydrogen bonds between hydroxyl groups of the konjac glucomannan oxide and amino groups on the polyacrylamide enable the formed hydrogel chain segments to have hydrogen bonds based on self-healing, so that the formed composite hydrogel has self-healing performance.
According to the preparation method of the oxidized konjac glucomannan composite hydrogel based on the Schiff base reaction, the oxidized konjac glucomannan aqueous solution and acrylamide are used as matrix materials, under the action of an initiator, the oxidized konjac glucomannan can be subjected to the Schiff base reaction with the acrylamide and can also be used as a cross-linking agent to be combined with the polyacrylamide, no additional cross-linking agent is required to be added, and the preparation method is simple and easy and is environment-friendly; the oxidized konjac glucomannan composite hydrogel prepared by the preparation method provided by the invention has good viscoelasticity and strong adhesion, the adhesion strength can reach 49.02 kPa, and the oxidized konjac glucomannan composite hydrogel has self-healing performance and biocompatibility and has important application in preparation of biomedical materials and adhesives.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an infrared spectrum of konjac glucomannan and oxidized konjac glucomannan of example 1;
FIG. 2 is a scanning electron micrograph of the composite hydrogel prepared in example 4 at different magnifications;
FIG. 3 is a graph showing the results of the rheological measurements on the composite hydrogels prepared in examples 1 to 6, wherein 3 (a) is the change curve of the storage modulus G ' of the composite hydrogel with the scanning strain, 3 (b) is the change curve of the loss modulus G ' of the composite hydrogel with the scanning strain, 3 (c) is the change curve of the loss factor tan delta of the composite hydrogel with the scanning strain, and 3 (d) is the change curve of G ', tan delta with the OKGM content at 1% strain;
FIG. 4 is a graph of the change in storage modulus G' and loss modulus G ″ from composite hydrogel prepared in example 4 scanned three times alternately at 1% (less than critical strain) of small strain and 200% (above critical strain) of large strain for 200 s;
FIG. 5 is a graph showing the results of testing the healing properties of the composite hydrogels prepared in examples 2 to 5, and FIGS. 5 (a), 5 (b), 5 (c), and 5 (d) are graphs showing the results of testing the healing properties of the composite hydrogels prepared in examples 2, 3, 4, and 5, respectively;
FIG. 6 is a graph showing the experimental phenomenon that the composite hydrogel prepared in example 3 adheres to different materials, which are nitrile gloves, plastic centrifuge tubes, wood, metal, glass, coins, rubber and pork in sequence;
FIG. 7 is a graph showing the experimental appearance that the composite hydrogel obtained in example 3 was adhered to the skin;
FIG. 8 is a graph showing the results of adhesion strength tests of the composite hydrogel obtained in example 3 to aluminum (Al), Rubber (Rubber) and Glass (Glass);
FIG. 9 is a graph showing the results of toxicity tests on L929 cells using the composite hydrogels obtained in examples 2 to 5.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The reagents used in the invention are purchased and obtained, and the specifications are AR grade, wherein, Konjac Glucomannan (KGM) is purchased from Hubei Qiangsen konjac science and technology Co., Ltd, acrylamide (AAm) is purchased from Alantin reagent Shanghai Co., Ltd, potassium persulfate and ammonium persulfate are purchased from national drug group chemical reagent Co., Ltd, rhodamine is purchased from Nanjing chemical reagent Co., Ltd, sodium periodate is purchased from national drug group chemical reagent Co., Ltd, and ethylene glycol is purchased from Tianjin Feng boat chemical reagent science and technology Co., Ltd.
The technical scheme of the invention is as follows:
a preparation method of oxidized konjac glucomannan composite hydrogel based on Schiff base reaction comprises the following steps:
(1) preparing an Oxidized Konjac Glucomannan (OKGM) aqueous solution with the mass fraction of 2-12%;
(2) adding acrylamide (AAm) and an initiator into the oxidized konjac glucomannan aqueous solution prepared in the step (1) under the condition of ice-water bath, introducing inert gas or nitrogen to remove oxygen in the solution, and uniformly mixing to obtain a gel precursor, wherein the dosage of the acrylamide is 9-11% of the mass of the gel precursor, the initiator is potassium persulfate or ammonium persulfate, and the dosage of the initiator is 3-1% of the mass of the acrylamide;
(3) and (3) standing and reacting the gel precursor prepared in the step (2) for 8-12 h at the temperature of 50-75 ℃ to obtain the composite hydrogel.
The oxidized konjac glucomannan composite hydrogel prepared by the preparation method provided by the embodiment has good viscoelasticity and strong adhesion, the adhesion strength can reach 49.02 kPa, and the oxidized konjac glucomannan composite hydrogel has self-healing performance and biocompatibility and has important application in preparation of biomedical materials and adhesives.
The present invention will be described in detail with reference to specific examples.
Example 1 preparation of PAAm-OKGM-2 hydrogel
A preparation method of oxidized konjac glucomannan composite hydrogel based on Schiff base reaction comprises the following steps:
(1) preparation of Oxidized Konjac Glucomannan (OKGM)
Dispersing 6 g KGM in 600 mL deionized water, heating and stirring at 50 ℃ for 2 h to prepare a uniform solution with the concentration of 1%, then adding 1.58 g of sodium periodate, controlling the reaction temperature at 30 ℃, stirring in the dark for 12 h, then adding 10 mL of ethylene glycol into the reaction mixed solution, and continuing stirring for 2 h to remove the unreacted sodium periodate. After the reaction is finished, dialyzing the reaction solution in deionized water for 3 days until the dialyzate is free of iodate (silver nitrate can be used for detecting whether the dialyzate also contains iodate), centrifuging the dialyzate at the rotating speed of 3000 rpm for 20 min, collecting supernatant, freezing and drying to obtain OKGM for later use, and carrying out infrared test on KGM and the prepared OKGM, wherein the specific test result is shown in figure 1;
(2) weighing 0.0602 g of OKGM prepared in the step (1), dissolving in 2.9399 g of deionized water, heating at 40 ℃ and magnetically stirring until the OKGM is completely dissolved to prepare an OKGM aqueous solution with the mass fraction of 2%, adding 0.3336 g of AAm and 0.0032 g of potassium persulfate into the OKGM aqueous solution under the ice-water bath condition, introducing nitrogen for 10min to remove oxygen in the solution, uniformly mixing, and standing at 55 ℃ for reaction for 10 h to obtain the composite hydrogel with the number of PAAm-OKGM-2, wherein 2 represents that the mass fraction of the OKGM aqueous solution is 2%.
FIG. 1 is an infrared spectrum of KGM and OKGM in this example, from which it can be seen that 3311 cm is shown in the infrared spectrum of KGM-1The wide peak appears as O-H stretching vibration, 1734 cm-1A stretching vibration of C = O in the acetyl group was observed, which after oxidation of KGM to OKGM resulted in OKGM around 1730 cm-1And 895 cm-1Two characteristic peaks occur, the former due to the symmetric oscillation of the aldehyde group (carbonyl group) and the latter due to the hemiacetal structure between the aldehyde group and the adjacent hydroxyl group, demonstrating that KGM is successfully oxidized to OKGM.
Example 2 preparation of PAAm-OKGM-4 hydrogel
A preparation method of oxidized konjac glucomannan composite hydrogel based on Schiff base reaction comprises the following steps:
(1) oxidized Konjac Glucomannan (OKGM) was prepared as in example 1;
(2) weighing 0.1201 g of OKGM prepared in the step (1), dissolving in 2.8801 g of deionized water, heating at 40 ℃ and magnetically stirring until the OKGM is completely dissolved to prepare an OKGM aqueous solution with the mass fraction of 4%, adding 0.3335 g of AAm and 0.0033 g of potassium persulfate into the OKGM aqueous solution under the ice-water bath condition, introducing nitrogen for 10min to remove oxygen in the solution, uniformly mixing, and standing at 55 ℃ for reaction for 10 h to obtain the composite hydrogel with the number of PAAm-OKGM-4.
Example 3 preparation of PAAm-OKGM-6 hydrogel
A preparation method of oxidized konjac glucomannan composite hydrogel based on Schiff base reaction comprises the following steps:
(1) oxidized Konjac Glucomannan (OKGM) was prepared as in example 1;
(2) weighing 0.1800 g of OKGM prepared in the step (1), dissolving in 2.8199 g of deionized water, heating at 40 ℃ and magnetically stirring until the OKGM is completely dissolved to prepare an OKGM aqueous solution with the mass fraction of 6%, adding 0.3336 g of AAm and 0.0034 g of potassium persulfate into the OKGM aqueous solution under the ice-water bath condition, introducing nitrogen for 10min to remove oxygen in the solution, uniformly mixing, and standing at 55 ℃ for reaction for 10 h to obtain the composite hydrogel with the number of PAAm-OKGM-6.
Example 4 preparation of PAAm-OKGM-8 hydrogel
A preparation method of oxidized konjac glucomannan composite hydrogel based on Schiff base reaction comprises the following steps:
(1) oxidized Konjac Glucomannan (OKGM) was prepared as in example 1;
(2) weighing 0.2403 g of OKGM prepared in the step (1), dissolving in 2.7601 g of deionized water, heating at 40 ℃ and magnetically stirring until the OKGM is completely dissolved, preparing an OKGM aqueous solution with the mass fraction of 8%, adding 0.3335 g of AAm and 0.0033 g of potassium persulfate into the OKGM aqueous solution under the ice-water bath condition, introducing nitrogen for 10min to remove oxygen in the solution, uniformly mixing, and standing at 55 ℃ for reaction for 10 h to obtain the composite hydrogel with the number of PAAm-OKGM-8;
(3) SEM test is carried out on the composite hydrogel with the number of PAAm-OKGM-8, and the specific test result is shown in figure 2. Fig. 2 is SEM pictures of the composite hydrogel prepared in this example at different magnifications, from which it can be seen that a stable three-dimensional network porous structure is formed inside the gel, the pore walls are smooth and thick, and present a similar skeleton structure, which is due to schiff base reaction between aldehyde group of OKGM and amino group on AAm to form an interpenetrating network structure, hydroxyl group of OKGM and-OCNH of PAAm2The hydrogen bonding interaction between them further strengthens and stabilizes the network structure of the gel.
Example 5 preparation of PAAm-OKGM-10 hydrogel
A preparation method of oxidized konjac glucomannan composite hydrogel based on Schiff base reaction comprises the following steps:
(1) oxidized Konjac Glucomannan (OKGM) was prepared as in example 1;
(2) weighing 0.3001 g of OKGM prepared in the step (1), dissolving in 2.6998 g of deionized water, heating at 40 ℃ and magnetically stirring until the OKGM is completely dissolved to prepare an OKGM aqueous solution with the mass fraction of 10%, adding 0.3335 g of AAm and 0.0033 g of potassium persulfate into the OKGM aqueous solution under the ice-water bath condition, introducing nitrogen for 10min to remove oxygen in the solution, uniformly mixing, and standing at 55 ℃ for reaction for 10 h to obtain the composite hydrogel with the number of PAAm-OKGM-10.
Example 6 preparation of PAAm-OKGM-12 hydrogel
A preparation method of oxidized konjac glucomannan composite hydrogel based on Schiff base reaction comprises the following steps:
(1) oxidized Konjac Glucomannan (OKGM) was prepared as in example 1;
(2) weighing 0.3603 g of OKGM prepared in the step (1), dissolving in 2.6401 g of deionized water, heating at 40 ℃ and magnetically stirring until the OKGM is completely dissolved to prepare an OKGM aqueous solution with the mass fraction of 12%, adding 0.3335 g of AAm and 0.0033 g of potassium persulfate into the OKGM aqueous solution under the ice-water bath condition, introducing nitrogen for 10min to remove oxygen in the solution, uniformly mixing, and standing at 55 ℃ for reaction for 10 h to obtain the composite hydrogel with the number of PAAm-OKGM-12.
Example 7-testing of rheological Properties of composite hydrogels prepared in examples 1-6
The rheological properties of the composite hydrogels prepared in examples 1 to 6 were tested, and the specific test results are shown in fig. 3, and the rheological property test is mainly to discuss the influence of different amounts of OKGM on the rheological properties of the composite hydrogels. Fig. 3 (a) is a curve of the change of the storage modulus G 'of the composite hydrogel with the scanning strain, and it can be seen from the graph that the storage modulus G' is basically constant in a small strain range, the G 'begins to decrease with the increase of the scanning strain, and the strain value corresponding to the decrease of the storage modulus G' is critical strain, which represents the range of the linear viscoelastic region, and the internal structure of the gel is stable in the region. It can be seen from fig. 3 (a) that with the increase of the content of OKGM, the critical strain value of the gel increases first and then decreases, and the linear viscoelastic region of the gel is the longest when the content of OKGM is 10%, which indicates that the gel numbered PAAm-OKGM-10 has a strong ability to withstand strain damage, and the gel structure is not easily damaged under large strain;
fig. 3 (b) is a graph of the loss modulus G "of the composite hydrogel as a function of scanning strain, and it can be seen from the graph that when the content of OKGM is increased from 2% to 10%, G" is gradually increased, and when the content of OKGM is 10%, G "reaches the maximum value, and when the content of OKGM is greater than 10%, G" is decreased. The storage modulus value (G') of the hydrogel was higher than the loss modulus value (G ") at all frequencies tested, indicating that the elastic properties in the hydrogel predominate.
FIG. 3 (c) is a graph of the change of the loss factor tan delta of the composite hydrogel with the scanning strain, and it can be seen from the graph that when the OKGM content is increased from 2% to 10%, the tan delta value is decreased from 0.57 to 0.26, which indicates that the crosslinking density inside the gel is increased, and a more and more compact three-dimensional pore structure is formed;
FIG. 3 (d) is a graph showing the change in G', tan. delta. with OKGM content at a strain of 1%. The rheological parameters of the gel directly reflect the viscoelasticity behavior of the gel, the storage modulus (G ') represents the elastic property of the material, the loss modulus (G' ') represents the viscous property of the material, and the loss factor (tan delta) is the ratio of the loss modulus (G' ') to the storage modulus (G'). From the combination of fig. 3 (a) -3 (d), it can be seen that when the fixed AAm content is 10% and the OKGM content varies between 2% and 10%, the storage modulus G' or loss modulus G ″ of the gel increases and then decreases, the loss factor tan δ decreases and then increases as the OKGM content increases, and the storage modulus reaches 6390 Pa at maximum and the tan δ value decreases to 0.26 at 10% of the OKGM. This is mainly because as the OKGM content increases, the aldehyde content gradually increases, the number of aldehyde groups undergoing schiff base reaction with the amide groups in AAm gradually increases, the number of cross-linking points forming a gel network structure increases, and the elastic properties of the gel become stronger, so that the storage modulus G' increases, the loss modulus G ″ of the gel also has the same trend of change, but the tan δ gradually decreases. However, when the OKGM exceeds 10%, the aldehyde group and the amino group participating in the Schiff base reaction reach saturation, the content of the OKGM is increased, the density of cross-linking points among molecular chains is reduced, and the phenomena of reduction of the storage modulus G ' and the loss modulus G ' ' of the gel and increase of the loss factor tan delta occur.
Example 8 testing of storage modulus G ' and loss modulus G ' ' for the composite hydrogel prepared in example 4
Fig. 4 is a graph of the change of storage modulus G' and loss modulus G ″ from the composite hydrogel prepared in example 4 (code PAAm-OKGM-8) scanned alternately three times for 200 s at a small strain of 1% (less than the critical strain) and a large strain of 200% (above the critical strain) to study the elastic responsiveness and self-healing performance of the gel. The gel structure is stable under 1% strain, hydrogen bonds and Schiff base bonds are easy to break under 200% large strain, the network structure becomes loose, G 'is reduced rapidly, when 1% strain is applied, G' of the gel is recovered to an initial value rapidly, the internal network structure is damaged under the large strain of the hydrogel, but the internal structure can be rapidly recombined, a new hydrogen bond and Schiff base bond recovery network structure is formed, and the OKGM/PAAm gel has rapid and efficient self-repairing capability.
Example 9 testing of healing Performance of composite hydrogels
The healing properties of the composite hydrogels prepared in examples 2-5 were tested, the specific test method was as follows:
the method comprises the steps of cutting different freshly prepared composite hydrogels into two halves by a blade, dyeing the half gels by rhodamine for obviously observing the self-healing phenomenon of the gels, contacting the two halves of the gels along the positions of the sections, placing the two halves of the gels in a sealed bag for 12 hours under the condition of 25 ℃, and taking a digital photo to observe the healing capacity of the gels.
Fig. 5 is a result graph of the healing performance of the composite hydrogels prepared in examples 2-5, which is an intuitive method for further evaluating the self-healing ability of the composite hydrogels following the step-change rheological test. Wherein, fig. 5 (a), 5 (b), 5 (c), 5 (d) are the test results of the healing performance of the composite hydrogels prepared in examples 2, 3, 4, 5, respectively, and it can be seen from the figure that half of the freshly prepared gel is dyed red with rhodamine, the boundary between the two gels can be clearly observed when the hydrogels are contacted for the first time, and after healing for 12 h without the influence of external conditions, the boundary between the two gels disappears, indicating that the two gels have healed. After the healing gel was stretched, it was observed that the self-healing capacity of the gel gradually increased with increasing amounts of OKGM in the system (to 4% later). However, when the OKGM content is too large (more than or equal to 10%), self-healing is not facilitated, because the aldehyde group is supersaturated and the system is viscous when the OKGM content is too high, which is not conducive to Schiff base reaction between the aldehyde group and the amino group, resulting in reduced healing capacity. Therefore, when the OKGM content is 4% -8%, the self-healing performance of the prepared composite hydrogel is better.
Example 10 testing of adhesion to composite hydrogels
Fig. 6 is an experimental image of adhesion of the composite hydrogel (numbered PAAm-OKGM-6) prepared in example 3 to different materials, which are butyronitrile gloves, plastic centrifuge tubes, wood, metal, glass, coins, rubber, and pork in sequence, and it can be seen from the figure that the composite hydrogel numbered PAAm-OKGM-6 shows good adhesion to butyronitrile gloves, plastic, wood, metal, glass, coins, rubber, and pork.
FIG. 7 is a graph showing the skin adhesion test of the composite hydrogel (PAAm-OKGM-6) prepared in example 3, and it can be seen that the composite hydrogel (PAAm-OKGM-6) can be adhered to fingers without falling off, has no irritation and inflammatory reaction to skin, can be firmly adhered to fingers when stretched, and can be stretched nearly 4 times as much as before with the movement of fingers, indicating that it has excellent adhesion to skin. The gel material has considerable application prospect in the fields of tissue engineering, wound dressing, adhesives and the like.
FIG. 8 is a graph showing the results of the adhesion strength test of the composite hydrogel (PAAm-OKGM-6) prepared in example 3 on aluminum, rubber and glass, wherein the adhesion performance of the composite hydrogel is tested at room temperature by a universal tester, and it can be seen from the graph that the PAAm-OKGM-6 composite hydrogel has strong adhesion capability on aluminum, rubber and glass, and the adhesion strength varies from 40.52 + -1.52 kPa to 46.69 + -2.33 kPa, indicating that the gel has potential application value as an adhesive. The adhesive property of the gel to different materials can be related to chemical bond crosslinking formed by Schiff base reaction, and in addition, due to the existence of hydroxyl and amino, electrostatic interaction and hydrogen bond interaction can occur between the gel and different substrate materials, which is beneficial to enhancing the adhesive capacity of the gel.
It should be emphasized that the composite hydrogel with the number of PAAm-OKGM-6 in the adhesion performance test of the composite hydrogel has no specificity, but the adhesion performance is described by using the composite hydrogel adhesion performance picture with the number of PAAm-OKGM-6, and the examples 1 to 6 are all searched for the adhesion investigation, and it is found that the nitrile gloves, plastic centrifuge tubes, wood, metal, glass, coins, rubber, pork, skin, aluminum, rubber and glass have good adhesion performance when the mass fraction of the aqueous solution of OKGM is between 2% and 12%, and especially the adhesion performance is better when the mass fraction of the aqueous solution of OKGM is between 4% and 8%.
Example 11 testing of cytotoxicity
The composite hydrogels prepared in examples 2-5 were tested for cytotoxicity as follows:
cytotoxicity test methods:
(1) taking 0.5 g of composite hydrogel sample, carrying out ultraviolet disinfection and sterilization for 12 h, taking a DMEM (DMEM) culture medium as a leaching solution, adding 5 mL of DMEM (dulbecco's modified eagle medium) culture solution into each 0.5 g of material, and soaking for 24 h under the aseptic condition to prepare the leaching solution;
(2) cell plating: digesting cells (L929 cells) in logarithmic phase with trypsin to prepare cell suspension, inoculating 3000-5000 cells into a 96-well plate, adding 100 mu L of culture solution into each well, and placing the culture solution into CO2(5%) the cells were incubated overnight at 37 ℃ in an incubator and the marginal wells were filled with sterile PBS. Pouring out the culture solution, adding 100 mu L of leaching liquor of different samples, and performing a 6-hole parallel experiment on each group of samples for 24 h;
(3) MTT reaction: 20 mu L of MTT solution (5 mg/mL, namely 0.5% MTT) is added into all the wells respectively, and the mixture is incubated for 4 hours in an incubator at 37 ℃;
(4) dissolving formazan in DMSO: carefully absorbing and removing the supernatant, adding 150 mu L of DMSO (dimethyl sulfoxide) into each hole, and oscillating at a low speed (120-140 rpm/min) of a shaking table for 10min to fully dissolve crystals;
(5) and (3) measuring an absorbance value: measuring the 490 nm light absorption value by using an enzyme-labeling instrument, and calculating the inhibition rate of the drug to cells according to a formula;
experimental groups: absorbance values of DMSO-solubilized experimental group cells;
negative control: absorbance values of control cell DMSO lysis;
blank control: absorbance values of DMSO solutions (no cells added);
proliferation rate ═ 100% (experimental group-blank)/(negative control-blank);
inhibition rate is 100- (experimental group-blank)/(negative control-blank) × 100%;
the specific test results are shown in fig. 9, and it can be seen from the figure that after different samples are cultured for 24 h, the proliferation rate of the cells is over 90%, which indicates that all the composite hydrogel samples have no obvious cytotoxicity to mouse L929 cells. With increasing OKGM content, there was a decreasing trend in cell proliferation rates between groups. When the dosage of OKGM is less than 10%, the cell proliferation rate is over 100%, and the OKGM/PAAm composite hydrogel has the function of promoting cell growth. The results can prove that the composite hydrogel has no cytotoxicity and excellent cell compatibility, and the OKGM/PAAm composite hydrogel can promote the proliferation of mouse L929 cells at low OKGM concentration.
Example 12
A preparation method of oxidized konjac glucomannan composite hydrogel based on Schiff base reaction comprises the following steps:
(1) oxidized Konjac Glucomannan (OKGM) was prepared as in example 1;
(2) weighing 0.1802 g of OKGM prepared in the step (1), dissolving in 2.8201 g of deionized water, heating at 44 ℃ and magnetically stirring until the OKGM is completely dissolved, preparing an OKGM aqueous solution with the mass fraction of 6%, adding 0.2968 g of AAm and 0.0010 g of ammonium persulfate into the OKGM aqueous solution under the ice-water bath condition, introducing helium for 10min to remove oxygen in the solution, uniformly mixing, and standing at 50 ℃ for reaction for 12 h to obtain the composite hydrogel.
The composite hydrogel prepared by the embodiment has good viscoelasticity and strong adhesiveness, the adhesive strength of the composite hydrogel can reach 45.2 kPa, and the composite hydrogel has good self-healing performance.
Example 13
A preparation method of oxidized konjac glucomannan composite hydrogel based on Schiff base reaction comprises the following steps:
(1) oxidized Konjac Glucomannan (OKGM) was prepared as in example 1;
(2) weighing 0.2401 g of OKGM prepared in the step (1), dissolving in 2.7598 g of deionized water, heating at 42 ℃ and magnetically stirring until the OKGM is completely dissolved to prepare an OKGM aqueous solution with the mass fraction of 8%, adding 0.3708 g of AAm and 0.0019 g of potassium persulfate into the OKGM aqueous solution under the ice-water bath condition, introducing nitrogen for 10min to remove oxygen in the solution, uniformly mixing, and standing at 60 ℃ for reaction for 8 h to obtain the composite hydrogel.
The composite hydrogel prepared by the embodiment has good viscoelasticity and strong adhesiveness, the adhesive strength of the composite hydrogel can reach 45.9 kPa, and the composite hydrogel has good self-healing performance.
Example 14
A preparation method of oxidized konjac glucomannan composite hydrogel based on Schiff base reaction comprises the following steps:
(1) oxidized Konjac Glucomannan (OKGM) was prepared as in example 1;
(2) weighing 0.1203 g of OKGM prepared in the step (1), dissolving in 2.8801 g of deionized water, heating at 44 ℃ and magnetically stirring until the OKGM is completely dissolved to prepare an OKGM aqueous solution with the mass fraction of 4%, adding 0.31495 g of AAm and 0.0031 g of potassium persulfate into the OKGM aqueous solution under the ice-water bath condition, introducing nitrogen for 10min to remove oxygen in the solution, uniformly mixing, and standing at 58 ℃ for reaction for 10 h to obtain the composite hydrogel.
The composite hydrogel prepared by the embodiment has good viscoelasticity and strong adhesiveness, the adhesive strength of the composite hydrogel can reach 44.9 kPa, and the composite hydrogel has good self-healing performance.
Comparative example 1
A preparation method of oxidized konjac glucomannan composite hydrogel based on Schiff base reaction comprises the following steps:
(1) oxidized Konjac Glucomannan (OKGM) was prepared as in example 1;
(2) weighing 0.1801 g of OKGM prepared in the step (1), dissolving in 2.8199 g of deionized water, heating at 40 ℃ and magnetically stirring until the OKGM is completely dissolved to prepare an OKGM aqueous solution with the mass fraction of 6%, adding 0.2601g of AAm and 0.0026 g of potassium persulfate into the OKGM aqueous solution under the ice-water bath condition, introducing nitrogen for 10min to remove oxygen in the solution, uniformly mixing, and standing at 55 ℃ for reaction for 10 h to obtain the composite hydrogel with the number of PAAm-OKGM-6-1.
This comparative example is different from example 3 in the amount of added AAm compared with example 3, the amount of added AAm in example 3 being 10% of the mass of the gel precursor, while the amount of added AAm in this comparative example being 8% of the mass of the gel precursor, resulting in the unshaped PAAm-OKGM-6-1 hydrogel. This is mainly because when the aldehyde group of the OKGM reacts with the amino group of the AAm with a schiff base, the OKGM mainly acts to crosslink the polyacrylamide chain formed by radical polymerization of the AAm, and when the AAm content is small, the polymerized macromolecular chain is short and a gel having a stable structure is not easily formed.
Comparative example 2
A preparation method of oxidized konjac glucomannan composite hydrogel based on Schiff base reaction comprises the following steps:
(1) oxidized Konjac Glucomannan (OKGM) was prepared as in example 1;
(2) weighing 0.1801 g of OKGM prepared in the step (1), dissolving in 2.8199 g of deionized water, heating at 40 ℃ and magnetically stirring until the OKGM is completely dissolved to prepare an OKGM aqueous solution with the mass fraction of 6%, adding 0.5294 g of AAm and 0.0053 g of potassium persulfate into the OKGM aqueous solution under the ice-water bath condition, introducing nitrogen for 10min to remove oxygen in the solution, uniformly mixing, and standing at 55 ℃ for reaction for 10 h to obtain the composite hydrogel with the number of PAAm-OKGM-6-2.
This comparative example was compared with example 3 in which the amount of added AAm was different from that of example 3, the amount of added AAm was 10% by mass of the gel precursor in example 3, whereas the amount of added AAm was 15% by mass of the gel precursor in this comparative example, and the resultant PAAm-OKGM-6-2 hydrogel was free from adhesiveness and self-healing properties.
Comparative example 3
A preparation method of konjac glucomannan composite hydrogel comprises the following steps:
weighing 0.0451 g of Konjac Glucomannan (KGM) prepared in the step (1), dissolving in 2.9550 g of deionized water, heating at 40 ℃ and magnetically stirring until the Konjac Glucomannan (KGM) is completely dissolved, preparing KGM aqueous solution with the mass fraction of 1.5%, adding 0.3336 g of AAm, 0.0034 g of potassium persulfate and 0.0002 g of MBA (cross-linking agent, N, N-dimethyl bisacrylamide) into the KGM aqueous solution under the condition of ice-water bath, introducing nitrogen for 10min to remove oxygen in the solution, uniformly mixing, and standing at 55 ℃ for 10 h to obtain the composite hydrogel with the number of PAAm-KGM-1.5.
The comparative example adopts the composite hydrogel prepared by konjac glucomannan, and experiments show that when KGM is used for preparing the hydrogel by reacting with AAm, the hydrogel can be formed only after a cross-linking agent is added, and the prepared composite hydrogel with the number of PAAm-KGM-1.5 has no adhesiveness and self-healing performance, mainly because KGM does not contain aldehyde group, cannot react with amino on AAm by Schiff base, cannot form an interpenetrating network structure, and has no adhesiveness and self-healing performance. Moreover, when KGM is dissolved in water at a mass fraction of 2%, the viscosity is extremely high and dissolution is difficult.
The preparation method of the oxidized konjac glucomannan composite hydrogel provided by the invention selects natural polysaccharide konjac glucomannan which is wide in source, low in price and environment-friendly and high-molecular monomer acrylamide as raw materials, the preparation process is green and environment-friendly, the gel performance is excellent, and the gel has adhesion property to the surfaces of various materials, wherein the adhesion strength to aluminum, rubber and glass can reach 40.52 +/-1.52 kPa to 46.69 +/-2.33 kPa, which shows that the gel has good adhesion capability, and meanwhile, the gel has self-healing capability and good biocompatibility, and can be used as an adhesive in the fields of medical treatment, industry and the like.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention.
Claims (7)
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