CN109929072B - Antifreeze polysaccharide composite starch hydrogel and preparation method and application thereof - Google Patents
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Abstract
The invention discloses antifreeze polysaccharide composite starch hydrogel and a preparation method and application thereofN-isopropylacrylamide (NIPAM) as crosslinking monomer,N’N'the hydrogel with the tensile property is prepared by a photochemical crosslinking method by taking Methylene Bisacrylamide (MBA) as a crosslinking agent and 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone as an initiator, and the elongation of the hydrogel reaches 600 percent. The hydrogel has the advantages of frost resistance, good flexibility at-70 ℃, strong responsiveness to stress stimulation, high response sensitivity (0-1 s), conductivity, capability of outputting stress as an electric signal, stretchable resilience, capability of being used as a material for preparing bionic skin and wearable devices, and application in extremely cold environments.
Description
Technical Field
The invention relates to the technical field of anti-freezing hydrogel materials, in particular to a hydrogel sensing device responding to stress stimulation in a low-temperature environment, and a preparation method and application thereof.
Background
Stress sensors based on hydrogel are mainly applied to bionic skin, wearable devices, bionic robots and the like, however, due to the special water-retaining property of hydrogel, the materials can only be used in the environment above zero degree, and when the temperature is lower than zero degree, water in the gel freezes and solidifies and loses the stress induction performance. In response to this problem, there is a need to develop new hydrogel systems.
The method successfully extracts the flammulina velutipes antifreeze polysaccharide for the first time in KANEKA and the like in 2014, and experiments prove that the antifreeze mechanism is mainly to inhibit the growth of ice crystals. The flammulina velutipes polysaccharide mainly comprises glucan and a small amount of polysaccharide components such as galactose, xyloglucan or xylomannan. Owing to its good freezing resistance, Flammulina velutipes polysaccharide has been used in the field of food preservation. If the flammulina velutipes polysaccharide can be applied to a hydrogel system, the antifreeze hydrogel still has better flexibility and stress induction performance below zero. The antifreeze hydrogel is reported to mainly utilize antifreeze agents (such as ethylene glycol, glycerol and the like) to reduce the freezing point of water, inhibit the growth of ice crystals and realize the antifreeze performance of the hydrogel, but the mechanical integrity of the hydrogel cannot be ensured through physical hybridization of the antifreeze agents and the hydrogel.
Disclosure of Invention
The invention aims to provide an antifreeze polysaccharide composite starch hydrogel which can be prepared in batch and can realize industrialization, and preparation and application of stress sensing at low temperature. According to the invention, the antifreeze hydrogel is prepared by compounding antifreeze polysaccharide and starch, and by introducing a conductive element into the hydrogel, stress is quantitatively output as an electric signal, so that quantitative evaluation parameters are provided for the stress induction performance of the hydrogel in a low-temperature environment.
The specific technical scheme for realizing the purpose of the invention is as follows:
an antifreeze polysaccharide composite starch hydrogel responding to stress stimulation is characterized in that: the hydrogel has obvious frost resistance, namely can keep good flexibility and stretchability at the temperature of 70 ℃ below zero, has strong responsiveness to stress stimulation and high response sensitivity (0-1 s), has conductivity, can output stress as an electric signal, and quantitatively detects the stress strength; the antifreeze polysaccharide and the commercial starch are compounded to prepare the hydrogel with the tensile property by a photochemical crosslinking method, wherein the crosslinking monomer is as follows:N-isopropylacrylamide (NIPAM), the crosslinking agent being:N’N'-Methylenebisacrylamide (MBA), photoinitiator: 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone.
A preparation method of antifreeze polysaccharide composite starch hydrogel comprises the following specific steps:
step 1: preparation of antifreeze polysaccharides
Filtering with filter screen, washing with water for 2-3 times, collecting precipitate, freeze drying, and pulverizing into powder; adding distilled water into the powder, extracting in water bath at 100 deg.C for 1-10 hr, repeating for three times, centrifuging, collecting supernatant, concentrating, and precipitating with ethanol; collecting the solid and drying; wherein the mass ratio of the mycelium solid powder to the distilled water is 1: 5-80; the volume ratio of the supernatant to the ethanol is = 1: 1-10;
step 2: adding commercial starch into deionized water, stirring at room temperature to obtain 10.0-50.0% starch milk, adjusting pH to 10.0-14.0 with 0.1mol/L NaOH solution, and adding NaCl 1.0-10.0% of starch to inhibit starch granule expansion; adding 1, 6-hexanediol diglycidyl ether accounting for 3.0-10.0% of the mass of the starch and tetrabutylammonium bromide accounting for 0.6-1.0% of the mass of the starch into the prepared starch milk, heating to 50 ℃, and stirring for reacting for 10-24 hours; adjusting pH to 5.0-8.0 with 0.1mol/L HCl solution, respectively centrifuging and washing with 2-5 times of water and ethanol, vacuum drying the solid to obtain starch powder modified by 1, 6-hexanediol diglycidyl ether, grinding, and storing for later use;
and step 3: taking two cleaned glass slides, and measuring: cutting a silica gel sheet with the thickness of 0.2-2.0 mm into the size of glass slides and covering one of the glass slides, wherein the thickness of the silica gel sheet is 12 cm x 1.5 cm x 1 mm; cutting off the middle part of the silica gel sheet, leaving a blank area with the area of 1cm x 1.3 cm, covering the other clean glass slide with the silica gel sheet to form a glass slide/silica gel sheet/glass slide sandwich structure device with aligned edges; extracting air in the sandwich structure device by using an injector, and injecting inert gas; wherein the inert gas is nitrogen or argon;
and 4, step 4: adding the starch powder modified by the 1, 6-hexanediol diglycidyl ether prepared in the step 2 into deionized water, and stirring for 1.5-3.5 h at 60-90 ℃ to form starch paste with the mass concentration of 1.0-20.0%; mixing Flammulina velutipes Fr antifreeze polysaccharide 1.0-20.0% and Flammulina velutipes Fr 50.0-90.0% of starch pasteNIsopropyl acrylamide, 0.1-10.0%N’ N'-methylenebisacrylamide, 0.1-10.0% of photoinitiator 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone and 1.0-10.0% of NaCl are uniformly mixed with the starch paste; injecting the mixed solution into the closed sandwich structure device prepared in the step 3, and preparing hydrogel by ultraviolet light irradiation crosslinking polymerization; the light intensity is as follows: 10-100 mW/cm2(ii) a Illumination time: 0.5-5.5 h; and preparing the antifreeze polysaccharide composite starch hydrogel.
The antifreeze polysaccharide component comprises glucose, galactose, xyloglucan, xylomannan and trehalose.
The starch is sweet potato starch, glutinous rice starch, corn starch, wild acorn starch or radix Puerariae starch.
An antifreeze polysaccharide composite starch hydrogel prepared by the method.
The antifreeze polysaccharide composite starch hydrogel is cut into two strip shapes with the same size, wherein the two strip shapes are as follows: 2cm x 1cm x (0.5-2.0) mm; one of the two materials is placed in an environment at the temperature of 70 ℃ below zero and kept for 5 to 50 min, and after being taken out, three-point bending and mechanical tensile tests are immediately carried out, and the mechanical properties of the frozen material and the unfrozen material are compared, so that the mechanical elongation of the frozen material is still kept at 800% and the flexibility; the hydrogel has gel freezing resistance.
The antifreeze polysaccharide composite starch hydrogel is characterized in that the antifreeze polysaccharide composite starch hydrogel is cut into a strip shape with the size of 2cm x 1cm x (0.5-2.0) mm, two ends of the antifreeze polysaccharide composite starch hydrogel are connected with electrodes of a universal meter, and when the hydrogel deforms under stress, the resistance value recorded by the universal meter changes; the hydrogel is stress stimulus responsive.
The antifreeze polysaccharide composite starch hydrogel is applied to the preparation of materials of bionic skin and wearable devices.
The hydrogel prepared by the method has wide raw material source and simple process, and has the basis of mass production; the prepared hydrogel has high tensile elongation and conductivity, shows resistance change to external stress stimulation, has freezing resistance, still keeps good flexibility and mechanical tensile property in an environment of 70 ℃ below zero, and can be used for preparing bionic skin and wearable flexible devices suitable for extremely cold environments.
Compared with the prior art, the invention has the following outstanding advantages:
the invention is characterized in that the antifreeze gel material different from the reported antifreeze gel material is developed, natural antifreeze polysaccharide and starch are used as main raw materials, stress stimulus response gel which can show high flexibility, stretch and conductivity in an extremely cold environment is prepared through chemical crosslinking, and the application potential of the gel as a bionic skin and a wearable material is preliminarily verified through a stimulus response test of an external force.
The technical innovation of the invention is mainly reflected in that the antifreeze polysaccharide composite starch hydrogel is prepared by a one-pot method, the method is simple, and the method is easy for repeated and mass production and is suitable for industrialization.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) picture of the stress-sensitive antifreeze hydrogel prepared by the embodiment of the invention, which shows a three-dimensional network structure of the hydrogel.
FIG. 2 is a drawing of a tensile test of a stress-sensitive antifreeze hydrogel prepared according to an embodiment of the present invention, showing a better mechanical tensile property.
FIG. 3 shows that the antifreeze polysaccharide composite starch hydrogel prepared by the embodiment of the invention can still maintain high stress sensitivity performance in a subzero environment and convert stress into an electric signal when applied to stress sensing.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and examples.
Example 1
Step 1: filtering with a needle mushroom mycelium filter screen, washing with water for two to three times, collecting precipitate, freeze-drying, and pulverizing into powder with a small laboratory pulverizer; adding distilled water (mass ratio of mycelium solid powder: distilled water = 1: 20) into the powder of the mycelium of the needle mushroom, extracting in water bath at 100 ℃ for 3h, repeating for three times, centrifuging, collecting supernatant, concentrating, precipitating with ethanol at the volume ratio of supernatant to ethanol = 1: 3, collecting solid, and drying.
And step 3: taking two cleaned glass slides, and measuring: cutting a silica gel sheet with the thickness of 0.5 mm into the size of glass slides, and covering one of the glass slides with the size of 12 cm x 1.5 cm x 1 mm; and cutting off the middle part of the silica gel sheet, leaving a blank area with the area of 1cm x 1.3 cm, and covering the other clean glass slide on the silica gel sheet to form a glass slide/silica gel sheet/glass slide sandwich structure with aligned edges. The air in the apparatus was evacuated by a syringe and nitrogen gas was injected.
And 4, step 4: adding the starch powder modified by the 1, 6-hexanediol diglycidyl ether prepared in the step 2 into deionized water, and stirring at 85 ℃ for 2.0 h to form starch paste (quality)Concentration 40.0%); mixing needle mushroom antifreeze polysaccharide 10.0% and needle mushroom antifreeze polysaccharide 70.0% of starch pasteN-isopropylacrylamide, 1.0%N’ N'-methylenebisacrylamide, 1.0% of photoinitiator 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone and 3.0% of NaCl were mixed uniformly with the starch paste; injecting the mixed solution into the closed sandwich structure device prepared in the step 3, and preparing hydrogel by ultraviolet light irradiation crosslinking polymerization; the light intensity is as follows: 20 mW/cm2The illumination time is as follows: 3 h; and preparing the antifreeze polysaccharide composite starch hydrogel. The scanning electron microscope observation shows that the prepared antifreeze hydrogel has a three-dimensional network physical structure as shown in figure 1.
And 5: cutting hydrogel into two strips with same size (size: 2cm x 1cm x 0.5 mm), placing one strip in-70 deg.C environment, holding for 30 min, taking out, immediately performing three-point bending and mechanical tensile test, and comparing the mechanical property difference between the frozen and non-frozen gels. The results show that the frozen gel still maintains better mechanical elongation (600%) and flexibility (shown in figure 2), and the flammulina velutipes polysaccharide component plays a good anti-freezing effect on the gel.
Step 6: and testing the stress sensing performance of the flammulina velutipes polysaccharide composite starch antifreeze hydrogel. The hydrogel, 2cm x 1cm x 0.5 mm in size, was connected at both ends to multimeter electrodes. When the hydrogel is deformed under a force, the resistance of the gel is changed, and the resistance change value is recorded by using a multimeter (Agilent 34401A) (shown in figure 3).
Example 2
Step 1: filtering with a needle mushroom mycelium filter screen, washing with water for two to three times, collecting precipitate, freeze-drying, and pulverizing into powder with a small laboratory pulverizer; adding distilled water (mass ratio of mycelium solid powder: distilled water = 1: 30) into the powder of the mycelium of the needle mushroom, extracting for 4h in a water bath at 100 ℃, repeating for three times, centrifuging, collecting supernatant, concentrating, precipitating with ethanol at the volume ratio of supernatant to ethanol = 1: 5, collecting solid, and drying.
Step 2: adding commercially available glutinous rice starch into deionized water, stirring at room temperature to obtain 20.0% starch milk, adjusting pH to 12.0 with 0.1mol/L NaOH solution, and adding NaCl (5.0% of starch mass) to inhibit expansion of starch granules; adding 1, 6-hexanediol diglycidyl ether (5.0 percent of the mass of the starch) and tetrabutylammonium bromide (0.7 percent of the mass of the starch) into the prepared starch milk, heating to 50 ℃, and stirring for reacting for 20 hours; adjusting pH to 7.0 with 0.1mol/LHCl solution, respectively centrifuging and washing with 3 times of water and ethanol, vacuum drying solid to obtain 1, 6-hexanediol diglycidyl ether modified commercially available glutinous rice starch, grinding, and storing for later use.
And step 3: taking two cleaned glass slides, and measuring: cutting a silica gel sheet with the thickness of 1.5 mm into the size of glass slides, and covering one glass slide with the size of the glass slides, wherein the thickness of the silica gel sheet is 12 cm x 1.5 cm x 1 mm; and cutting off the middle part of the silica gel sheet, leaving a blank area with the area of 1cm x 1.3 cm, and covering the other clean glass slide on the silica gel sheet to form a glass slide/silica gel sheet/glass slide sandwich structure with aligned edges. The air in the apparatus was evacuated by a syringe and nitrogen gas was injected.
And 4, step 4: adding the starch powder modified by the 1, 6-hexanediol diglycidyl ether prepared in the step 2 into deionized water, and stirring at 85 ℃ for 3.0 h to form starch paste (the mass concentration is 20.0%);
adding needle mushroom antifreeze polysaccharide 15.0 wt% and needle mushroom antifreeze polysaccharide 80.0 wt% of starch pasteNIsopropyl acrylamide, 2.0%N’ N'-methylenebisacrylamide, 2.0% of photoinitiator 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone, and 5.0% of NaCl were mixed uniformly with the starch paste; injecting the mixed solution into the closed sandwich structure device prepared in the step 3, and preparing hydrogel by ultraviolet light irradiation crosslinking polymerization; the light intensity is as follows: 40 mW/cm2The illumination time is as follows: 2 h; and preparing the antifreeze polysaccharide composite starch hydrogel.
And 5: cutting hydrogel into two strips with same size (size: 2cm x 1cm x 1.5 mm), placing one strip in-70 deg.C environment, maintaining for 40 min, taking out, immediately performing three-point bending and mechanical tensile test, and comparing the mechanical property difference between the frozen and non-frozen gels. The result shows that the frozen gel still keeps better mechanical elongation (700%) and flexibility, and the flammulina velutipes polysaccharide component plays a good anti-freezing effect on the gel.
Step 6: and testing the stress sensing performance of the flammulina velutipes polysaccharide composite starch antifreeze hydrogel. The hydrogel, 2cm x 1cm x 1.5 mm in size, was connected at both ends to multimeter electrodes. When the hydrogel is deformed under stress, the resistance of the gel is changed, and the resistance change value is recorded by using a multimeter (Agilent 34401A).
Example 3
Step 1: filtering with a needle mushroom mycelium filter screen, washing with water for two to three times, collecting precipitate, freeze-drying, and pulverizing into powder with a small laboratory pulverizer; adding distilled water (mass ratio of mycelium solid powder: distilled water = 1: 50) into the powder of the mycelium of the needle mushroom, extracting for 2h in a water bath at 100 ℃, repeating for three times, centrifuging, collecting supernatant, concentrating, precipitating with ethanol at the volume ratio of supernatant: ethanol = 1: 6, collecting solid, and drying;
step 2: adding commercial corn starch into deionized water, stirring at room temperature to obtain 10.0% starch milk, adjusting pH to 13.0 with 0.1mol/L NaOH solution, and adding NaCl (8.0% of starch mass) to inhibit starch granule expansion; adding 1, 6-hexanediol diglycidyl ether (3.0 percent of the mass of the starch) and tetrabutylammonium bromide (0.6 percent of the mass of the starch) into the prepared starch milk, heating to 50 ℃, and stirring for reacting for 24 hours; adjusting the pH value to 7.0 by using 0.1mol/L HCl solution, respectively centrifuging and washing by using 3 times of water and ethanol, drying the solid in vacuum to obtain the commercial corn starch modified by the 1, 6-hexanediol diglycidyl ether, grinding and storing for later use;
and step 3: taking two cleaned glass slides, and measuring: cutting a silica gel sheet with the thickness of 1.0 mm into the size of glass slides, and covering one glass slide with the size of the glass slides, wherein the thickness of the silica gel sheet is 12 cm x 1.5 cm x 1 mm; and cutting off the middle part of the silica gel sheet, leaving a blank area with the area of 1cm x 1.3 cm, and covering the other clean glass slide on the silica gel sheet to form a glass slide/silica gel sheet/glass slide sandwich structure with aligned edges. Pumping out air in the device by using an injector, and injecting nitrogen;
and 4, step 4: adding the starch powder modified by the 1, 6-hexanediol diglycidyl ether prepared in the step 2 into deionized water, and stirring at 90 ℃ for 3.0 h to form starch paste (the mass concentration is 20.0%);
mixing needle mushroom antifreeze polysaccharide 10.0% and needle mushroom antifreeze polysaccharide 70.0% of starch pasteN-isopropylacrylamide, 1.0%N’ N'-methylenebisacrylamide, 1.0% of photoinitiator 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone, and 6.0% of NaCl were mixed uniformly with the starch paste; injecting the mixed solution into the closed sandwich structure device prepared in the step 3, and preparing hydrogel by ultraviolet light irradiation crosslinking polymerization; the light intensity is as follows: 100mW/cm2The illumination time is as follows: 1.0 h; preparing the antifreeze polysaccharide composite starch hydrogel;
and 5: cutting hydrogel into two strips with same size (size: 2cm x 1cm x 1 mm), placing one strip in-70 deg.C environment, holding for 30 min, taking out, immediately performing three-point bending and mechanical tensile test, and comparing the mechanical property difference between the frozen and unfrozen gels. The result shows that the frozen gel still keeps better mechanical elongation (700%) and flexibility, and the flammulina velutipes polysaccharide component plays a good anti-freezing effect on the gel.
Step 6: and testing the stress sensing performance of the flammulina velutipes polysaccharide composite starch antifreeze hydrogel. Two ends of hydrogel with the size of 2cm x 1cm x 1mm are connected with electrodes of a multimeter. When the hydrogel is deformed under stress, the resistance of the gel is changed, and the resistance change value is recorded by using a multimeter (Agilent 34401A).
Claims (4)
1. A preparation method of antifreeze polysaccharide composite starch hydrogel is characterized by comprising the following specific steps:
step 1: preparation of antifreeze polysaccharides
Filtering with filter screen, washing with water for 2-3 times, collecting precipitate, freeze drying, and pulverizing into powder; adding distilled water into the powder, extracting in water bath at 100 deg.C for 1-10 hr, repeating for three times, centrifuging, collecting supernatant, concentrating, and precipitating with ethanol; collecting the solid and drying; wherein the mass ratio of the mycelium powder to the distilled water is 1: 5-80; the volume ratio of the supernatant to the ethanol is = 1: 1-10;
step 2: adding commercial starch into deionized water, stirring at room temperature to obtain 10.0-50.0% starch milk, adjusting pH to 10.0-14.0 with 0.1mol/L NaOH solution, and adding NaCl 1.0-10.0% of starch to inhibit starch granule expansion; adding 1, 6-hexanediol diglycidyl ether accounting for 3.0-10.0% of the mass of the starch and tetrabutylammonium bromide accounting for 0.6-1.0% of the mass of the starch into the prepared starch milk, heating to 50 ℃, and stirring for reacting for 10-24 hours; adjusting pH to 5.0-8.0 with 0.1mol/L HCl solution, respectively centrifuging and washing with 2-5 times of water and ethanol, vacuum drying the solid to obtain starch powder modified by 1, 6-hexanediol diglycidyl ether, grinding, and storing for later use;
and step 3: taking two cleaned glass slides, and measuring: cutting a silica gel sheet with the thickness of 0.2-2.0 mm into the size of glass slides and covering one of the glass slides, wherein the thickness of the silica gel sheet is 12 cm x 1.5 cm x 1 mm; cutting off the middle part of the silica gel sheet, leaving a blank area with the area of 1cm x 1.3 cm, covering the other clean glass slide with the silica gel sheet to form a glass slide/silica gel sheet/glass slide sandwich structure device with aligned edges; extracting air in the sandwich structure device by using an injector, and injecting inert gas; wherein the inert gas is nitrogen or argon;
and 4, step 4: adding the starch powder modified by the 1, 6-hexanediol diglycidyl ether prepared in the step 2 into deionized water, and stirring for 1.5-3.5 h at 60-90 ℃ to form starch paste with the mass concentration of 1.0-20.0%; mixing Flammulina velutipes Fr antifreeze polysaccharide 1.0-20.0% and Flammulina velutipes Fr 50.0-90.0% of starch pasteNIsopropyl acrylamide, 0.1-10.0%N’ N'-methylenebisacrylamide, 0.1-10.0% of photoinitiator 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone and 1.0-10.0% of NaCl are uniformly mixed with the starch paste; injecting the mixed solution into the closed sandwich structure device prepared in the step 3, and preparing hydrogel by ultraviolet light irradiation crosslinking polymerization; the light intensity is as follows: 10-100 mW/cm2(ii) a Illumination time: 0.5-5.5 h; and preparing the antifreeze polysaccharide composite starch hydrogel.
2. The method of claim 1, wherein the starch is sweet potato starch, glutinous rice starch, corn starch, wild acorn starch, or kudzu starch.
3. An antifreeze polysaccharide composite starch hydrogel prepared by the method of claim 1.
4. Use of the antifreeze polysaccharide-starch hydrogel of claim 3 in the preparation of materials for biomimetic skin and wearable devices.
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| CN110922612B (en) * | 2019-12-02 | 2022-10-28 | 哈尔滨工程大学 | Preparation method of ionic conductive anti-freezing supramolecular hydrogel |
| CN111139187A (en) * | 2019-12-30 | 2020-05-12 | 华东师范大学 | Flammulina velutipes fungus antifreeze polysaccharide and preparation method and application thereof |
| CN111548428A (en) * | 2020-04-29 | 2020-08-18 | 华东师范大学 | Extraction method of flammulina velutipes antifreeze polysaccharide |
| CN111704677B (en) * | 2020-06-18 | 2021-09-24 | 南京农业大学 | Method for separating wheat bran antifreeze polysaccharide by using ice hull method |
| CN114456746A (en) * | 2021-12-30 | 2022-05-10 | 国科温州研究院(温州生物材料与工程研究所) | Composite hydrogel patch and preparation method thereof |
| CN115386259B (en) * | 2022-09-28 | 2023-11-14 | 中国科学院兰州化学物理研究所 | Dry-proof and freeze-proof photosensitive hydrogel ink, preparation method thereof, high-precision photo-curing hydrogel and application thereof |
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