CN113698532B - Preparation method of multifunctional polymer dicationic hydrogel for wearable sensor - Google Patents

Preparation method of multifunctional polymer dicationic hydrogel for wearable sensor Download PDF

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CN113698532B
CN113698532B CN202110958937.XA CN202110958937A CN113698532B CN 113698532 B CN113698532 B CN 113698532B CN 202110958937 A CN202110958937 A CN 202110958937A CN 113698532 B CN113698532 B CN 113698532B
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hydrogel
dicationic
wearable sensor
multifunctional polymer
quaternary ammonium
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CN113698532A (en
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王荣民
刘晓晴
黄鹏
曹芃
王向原
何玉凤
李恬
郭文玲
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Northwest Normal University
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52Amides or imides
    • C08F220/54Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/60Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/46Polymerisation initiated by wave energy or particle radiation
    • C08F2/48Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/54Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Abstract

The invention relates to a preparation method of a multifunctional polymer dicationic hydrogel for a wearable sensor, which comprises the following steps: under the condition of ice-water bath, sequentially adding deionized water, ionic liquid and quaternary ammonium salt into a container, and stirring until a homogeneous solution of 40-300 g/L is formed; then, quickly adding a cross-linking agent and a photoinitiator, and stirring for 10 to 60 min to obtain a monomer mixture containing the initiator; and transferring the monomer mixture containing the initiator into a required mold, and reacting for 6-12 h under illumination to obtain the multifunctional polymer dicationic hydrogel for the wearable sensor. The invention has simple preparation process and good biocompatibility, can directly act on human skin, is safe and reliable, and has potential application value in the aspects of human-computer interaction and intelligent wearable equipment.

Description

Preparation method of multifunctional polymer dicationic hydrogel for wearable sensor
Technical Field
The invention relates to the technical field of hydrogel and the scientific field of conductive materials, in particular to a preparation method of multifunctional (excellent mechanical applicability, high sensitivity, antibacterial property, freezing resistance and the like) polymer dication hydrogel for a wearable sensor.
Background
With the development of intelligent terminals, the requirements of people on living quality are continuously improved, and the development of various sensor technologies and intelligent equipment makes it possible to conveniently acquire human behaviors in real time. In order to realize continuous monitoring of human body activities for a long time, it is necessary to mount an electronic device having conductive properties on the surface of the human body. The traditional electronic equipment mainly comprises hard high polymer materials and inorganic semiconductor materials, and is difficult to wear due to the brittleness and rigidity of the traditional electronic equipment.
To meet the requirements of complex human body movement, flexible and humanized designs are becoming important components of wearable electronic devices. The flexible wearable sensor is a device with a sensing function and prepared by imitating the characteristics of human skin, and shows huge application potential in the fields of artificial intelligence, machine sensing, human-computer interaction and the like in recent years, but most of flexible base materials as sensor materials face great difficulty in conductivity, so that the sensitivity and stability of the flexible base materials as the wearable sensors are influenced. The most common method for solving such problems is to fill conductive materials, wherein organic conductive polymers (polyaniline, polypyrrole and the like) are often filled to construct a conductive network, and a uniform conductive polymer elastomer can be prepared with good interfacial compatibility, but the inherent color of the filler affects the transparency of the flexible sensor, and limits the application of the flexible sensor in the field of visual electronic devices. The electrical conductivity of the flexible material filled with inorganic conductive particles (graphene, metal nanowires, etc.) is high, but the phase separation between the filler and the matrix generally reduces the strain, toughness and fatigue, and even influences the mechanical properties of the flexible material. Therefore, most of the wearable sensors reported at present still remain in a difficult choice of mechanical and electrical conductivity.
The hydrogel is a hydrophilic material with a network structure, and high water content can provide a transportation path for conductive ions and can obtain satisfactory elasticity and toughness through directional design. The conductive hydrogel can construct a conductive network with free ions, the ion conduction mode is visible everywhere in a biological system, and the conductive hydrogel also has excellent biocompatibility, and is a promising candidate of a wearable sensor. Therefore, developing hydrogel-based wearable materials is the best choice for human motion detection, health monitoring and soft robots at present.
However, hydrogel using water as solvent loses elasticity, ductility and conductivity below zero degree, thereby causing loss of sensing performance, and seriously hindering practical application in real life. Therefore, it is necessary to develop a hydrogel capable of functioning at subzero temperatures as a flexible wearable sensor. Many antifreeze methods have been devised to achieve this goal, for example, antifreeze conductive hydrogels are prepared by adding ionic compounds or organic solvents. Wangweihui et al (patent CN 110760152A) disclose a freeze-resistant hydrogel and a preparation method and application thereof, and lithium salt is added to endow the hydrogel with freeze resistance at low temperature, but the lithium salt has certain toxicity and is not beneficial to human health after long-term contact. Yuanwei loyalty et al (patent CN 112521630A) disclose the preparation and use of a green, flexible, electrically conductive, antifreeze hydrogel by introducing glycerol into the hydrogel to increase the antifreeze properties of the material, which, however, reduces the mechanical properties of the hydrogel. Therefore, the hydrogel for wearable sensors must have excellent mechanical properties and freeze resistance in the first place.
In addition, the flexible wearable electronic device needs to be attached to human skin or tissue for a long time, is easy to cause allergy or bacterial infection, and it is also necessary to develop a wearable electronic device capable of slowing or preventing the propagation of microorganisms or forming a biofilm on the surface. Commonly used antibacterial materials generally achieve the antibacterial purpose by combining with antibiotics, antibacterial metal ions or antibacterial peptides. Zhao Xuefeng et al (patent CN 108498543A) discloses a silver ion supermolecule antibacterial hydrogel and a preparation method and application thereof, silver ions are added into guanine derivatives to form the supermolecule hydrogel, so that the slow release of the silver ions is realized, and the aim of resisting bacteria is fulfilled. The patent CN 112480434A discloses a copper ion antibacterial hydrogel and a preparation method and application thereof, and the problems of slow release and uncontrollable release speed of a copper-containing antibacterial material are solved by adding copper salt to endow the hydrogel with antibacterial property. Chen (patent CN 112899331A) discloses a fermentation preparation method of antibacterial peptide, antibacterial peptide hydrogel and application thereof, and realizes the controlled release of lactic acid based on PEG nano-carrier. However, the wide use of antibiotics is liable to cause bacterial resistance, the release of metal ions is liable to cause metal poisoning, the synthetic process of antibacterial peptide is complicated and liable to cause hemolytic effect. Therefore, the hydrogel for wearable sensors must also have broad-spectrum antibacterial properties.
The development of multifunctional hydrogel with excellent mechanical applicability, high sensitivity, long-term antibacterial property and freezing resistance has important significance for wide application of wearable sensors. Polyionic liquids (polymers formed from ionic liquids) combine the properties of ionic liquids such as low volatility, thermal and electrochemical stability, and mechanical durability of polymers. Because of its charge in the structural unit, it has been widely used as biocompatible materials, anti-fouling, anti-frost coatings, and the like. The antibacterial polymer also attracts attention because its inherent antibacterial activity is longer than that of other antibacterial materials and has lower toxicity to human cells. The protonated primary amine (quaternary ammonium salt) as a cationic antibacterial agent can interact with a negatively charged bacterial membrane through electrostatic attraction, so that the charge distribution on the bacterial membrane is uneven, the charge balance of the bacterial membrane in a natural state is further broken, the bacterial membrane cannot bear osmotic pressure and is broken, and substances such as water, protein and the like can seep out of cells, so that the bacteria die. Zhang cleng et al (patent CN 107970488A) disclose a chitosan quaternary ammonium salt hydrogel antibacterial dressing and a preparation method thereof, and the growth inhibition to escherichia coli and staphylococcus aureus is tested by the matching use of chitosan quaternary ammonium salt, organosilicon quaternary ammonium salt and dandelion extract. Rongronmin et al (patent CN 111217956A) disclose a method for preparing cationic custard-like acrylate copolymer antibacterial microspheres, and the antibacterial microspheres prepared by using cationic quaternary ammonium salt as an antibacterial unit have broad-spectrum antibacterial property, and can be popularized and applied to antibacterial and antiseptic products such as plant antibacterial products, coatings, printing ink and the like. However, the application of quaternary ammonium salts as cationic antibacterial agents in wearable sensors has been rarely studied.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of the multifunctional polymer dicationic hydrogel for the wearable sensor, which has the advantages of simple process, good biocompatibility, safety and reliability.
In order to solve the problems, the preparation method of the multifunctional polymer dicationic hydrogel for the wearable sensor is characterized by comprising the following steps: under the condition of ice-water bath, sequentially adding deionized water, ionic liquid and quaternary ammonium salt into a container, and stirring until a homogeneous solution of 40-300 g/L is formed; then, quickly adding a cross-linking agent and a photoinitiator, and stirring for 10 to 60 min to obtain a monomer mixture containing the initiator; and transferring the monomer mixture containing the initiator into a required mold, and reacting for 6-12 h under illumination to obtain the multifunctional polymer dicationic hydrogel for the wearable sensor.
The temperature of the ice-water bath is-4 ℃ to 0 ℃.
The mass ratio of the ionic liquid to the quaternary ammonium salt to the cross-linking agent is 0.20 to 3.30:1.10 to 5.50:0.01 to 0.30.
The ionic liquid is one of 1-butyl-3-vinyl imidazole bromide, 1-propyl-3-vinyl imidazole sulfonate or 1-ethyl-3- (1-vinyl imidazole-3-hexyl) imidazole bromide.
The quaternary ammonium salt is N, N, N-trimethyl-3- (2-methallylamido) -1-propyl ammonium chloride or gamma- (methacrylamide) propyl trimethyl ammonium chloride.
The cross-linking agent is N, N' -methylene bisacrylamide or ethylene glycol diacrylate.
The photoinitiator is one of 2-hydroxy-2-methyl-1-phenyl acetone, 2,4, 6-trimethyl benzoyl phenyl ethyl phosphonate or 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, and the dosage of the photoinitiator is 2% -10% of the total mass of the ionic liquid and the quaternary ammonium salt.
The illumination condition is ultraviolet light of 250 to 400 nm.
Compared with the prior art, the invention has the following advantages:
1. the multifunctional polymer dicationic hydrogel for the wearable sensor is prepared by taking the ionic liquid and the quaternary ammonium salt as comonomers and performing photo-initiated free radical polymerization, has simple preparation process and good biocompatibility, can be directly acted on human skin, and is safe and reliable.
2. The addition of the quaternary ammonium salt can effectively inhibit the proliferation of bacteria in the long-term wearing process and reduce the replacement frequency of the sensor, thereby prolonging the service life of the wearable sensor.
3. The addition of the ionic liquid in the invention not only increases the conductivity of the hydrogel, but also endows the dication hydrogel with excellent frost resistance, and expands the application of the dication hydrogel in severe environment.
4. A large amount of hydrophobic association and electrostatic interaction exist in the multifunctional polymer dicationic hydrogel for the wearable sensor prepared by the invention, so that the mechanical property of the hydrogel can be further enhanced. Meanwhile, the double-cation hydrogel can accurately convert different motions of a human body into electric signals and realize stable transmission.
5. The multifunctional polymer dicationic hydrogel for the wearable sensor prepared by the invention can be designed into a required shape through a mould, and is convenient to carry and use.
6. The multifunctional polymer dicationic hydrogel for the wearable sensor prepared by the invention has excellent mechanical properties and conductivity sensitivity, and the characteristics determine that the multifunctional polymer dicationic hydrogel for the wearable sensor can sensitively realize real-time monitoring of human body movement. In addition, the dicationic hydrogel has good antibacterial performance on staphylococcus aureus and escherichia coli, still keeps transparent and flexible at low temperature, and can be subjected to cyclic distortion, bending and folding, and the characteristics enable the multifunctional polymer dicationic hydrogel for the wearable sensor to have comprehensive performance similar to intelligent skin, and have potential application value in the aspects of human-computer interaction and intelligent wearable equipment.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Fig. 1 is a macro photograph (left image) and an SEM image (right image) of the multifunctional polymer dicationic hydrogel for wearable sensor prepared in example 1 of the present invention.
Fig. 2 is an infrared spectrum of the multifunctional polymer dicationic hydrogel for a wearable sensor prepared in example 1 of the present invention.
Fig. 3 is a nuclear magnetic spectrum of the multifunctional polymer dicationic hydrogel for a wearable sensor prepared in example 1 of the present invention.
Fig. 4 is a mechanical property test chart of the multifunctional polymer dicationic hydrogel for a wearable sensor prepared in example 1 of the present invention.
Fig. 5 is a graph illustrating the conductivity test of the multifunctional polymer dicationic hydrogel for a wearable sensor prepared in example 1 of the present invention.
Fig. 6 is a graph showing a freezing resistance test of the multifunctional polymer dicationic hydrogel for a wearable sensor prepared in example 1 of the present invention.
Fig. 7 is an antibacterial comparison graph of the multifunctional polymer dicationic hydrogel for a wearable sensor prepared in example 1 of the present invention. Wherein: a is staphylococcus aureus (control); b is staphylococcus aureus (48 h); c is E.coli (control); d is Escherichia coli (48 h).
FIG. 8 is a diagram showing the behavior monitoring of the multifunctional polymer dicationic hydrogel for wearable sensor prepared in example 1 of the present invention.
Detailed Description
The preparation method of the multifunctional polymer dicationic hydrogel for the wearable sensor comprises the following steps: under the condition of ice-water bath at the temperature of-4-0 ℃, sequentially adding deionized water, ionic liquid and quaternary ammonium salt into a container, and stirring until a homogeneous solution of 40-300 g/L is formed; then, quickly adding a cross-linking agent and a photoinitiator, and stirring for 10 to 60 min to obtain a monomer mixture containing the initiator; and transferring the monomer mixture containing the initiator into a required mold, and reacting for 6 to 12 hours under the illumination of ultraviolet light of 250 to 400 nm to obtain the multifunctional polymer dicationic hydrogel for the wearable sensor.
Wherein: the mass ratio (g/g) of the ionic liquid, the quaternary ammonium salt and the cross-linking agent is 0.20 to 3.30:1.10 to 5.50:0.01 to 0.30.
The ionic liquid is one of 1-butyl-3-vinyl imidazole bromide, 1-propyl-3-vinyl imidazole sulfonate or 1-ethyl-3- (1-vinyl imidazole-3-hexyl) imidazole bromide.
The quaternary ammonium salt is N, N, N-trimethyl-3- (2-methyl allylamido) -1-propyl ammonium chloride or gamma- (isobutene amide) propyl trimethyl ammonium chloride.
The cross-linking agent is N, N' -methylene bisacrylamide or ethylene glycol diacrylate.
The photoinitiator is one of 2-hydroxy-2-methyl-1-phenyl acetone, 2,4, 6-trimethyl benzoyl phenyl ethyl phosphonate or 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, and the dosage of the photoinitiator is 2% -10% of the total mass of the ionic liquid and the quaternary ammonium salt.
Example 1 preparation of multifunctional polymer dicationic hydrogel for wearable sensor: under the ice-water bath condition of-4 ℃ to 0 ℃, sequentially adding deionized water, 2.16 g of 1-butyl-3-vinyl imidazole bromide salt and 2.21 g of N, N-trimethyl-3- (2-methallylamido) -1-ammonium chloride into a container, and stirring until 200 g/L of homogeneous solution is formed; then, 0.02 g of N, N' -methylene-bisacrylamide and 0.11 g of 2-hydroxy-2-methyl-1-phenyl acetone are rapidly added and stirred for 20 min to obtain a monomer mixture containing an initiator; and transferring the monomer mixture containing the initiator into a required mold, and reacting for 9 hours under the illumination of 254 nm ultraviolet light to obtain the multifunctional polymer dicationic hydrogel for the wearable sensor.
Performing structural characterization and performance analysis on the prepared multifunctional polymer dicationic hydrogel for the wearable sensor:
the method comprises the steps of firstly, analyzing a scanning electron microscope:
the macro morphology (left image) and the micro morphology (right image) of the multifunctional polymer dicationic hydrogel for the wearable sensor prepared by the invention were observed by a digital camera and a Scanning Electron Microscope (SEM), and the results are shown in fig. 1. It can be seen that the multifunctional polymer dicationic hydrogel for the wearable sensor has good plasticity and smooth and flexible surface, and can be easily designed into a required shape through a mold according to requirements.
As can be seen from SEM pictures, the material shows a typical porous structure, the pore size is uniform and is about 8 mu m, the structure can disperse and bear external force from all aspects, the dispersion of the material on stretching and extrusion force can be improved, and the porous structure is also favorable for the migration of ions. In addition, the porous structure is also favorable for increasing the contact area of the hydrogel and bacteria, and has a positive effect on the improvement of the antibacterial performance of the hydrogel.
And (2) infrared spectroscopic analysis:
the infrared spectrum of the multifunctional polymer dicationic hydrogel for the wearable sensor is shown in fig. 2. It can be seen from the figure that at 3438 cm -1 The absorption peak is the stretching vibration of-NH; 3032 cm -1 And 2956 cm -1 The nearby peaks are respectively unsaturated saturated stretching vibration absorption peaks of C-H; the telescopic vibration absorption peak of carbonyl (C = O) in amide is 1645 cm -1 At least one of (1) and (b); 1484 cm -1 Is represented by-CH 2 -N + (CH 3 ) 3 Characteristic absorption peaks of bending vibration of methylene. In addition, 3138 cm -1 The absorption peak is caused by C-H stretching vibration in imidazole, 1568 cm -1 And 1456 cm -1 The absorption peak at (a) is attributed to the skeleton vibration of imidazole. Therefore, all monomers participate in the reaction, and the multifunctional polymer dicationic hydrogel for the wearable sensor is successfully prepared.
Analyzing a nuclear magnetic spectrum:
the solid nuclear magnetic carbon spectrum of the multifunctional polymer dicationic hydrogel for the wearable sensor is shown in fig. 3. 176.70 The characteristic peaks at ppm and 161.06 ppm belong to the proton chemical shifts of the carbonyl groups; characteristic resonance peaks of imidazole ring appear at 137.36 ppm and 123.33 ppm; 53.83 The characteristic peak at ppm is the proton chemical shift of the terminal methyl group of the quaternary ammonium salt. Therefore, all monomers can participate in the polymerization reaction, and the success of the preparation of the multifunctional polymer dicationic hydrogel for the wearable sensor is further proved.
Mechanical properties:
the multifunctional polymer dicationic hydrogel for the wearable sensor is subjected to tensile property test on a universal tester.
First, the sample was cut into rectangular sections (length = 50 mm, width = 10 mm, thickness =2 mm) and the uniaxial stretching rate was set to 50 mm/min. Secondly, the cut gel rectangular slices are respectively fixed on an upper clamp and a lower clamp of a universal testing machine, the clamps are screwed, the force of screwing and clamping and the length of the two ends of the gel clamped into the clamps are taken into consideration, and the gel is prevented from being crushed or slipping out in the stretching process. The uniaxial tensile test was performed without interruption until the gel was broken. The test results are Stress-Strain (Stress-Strain) curves of the multifunctional polymer dicationic hydrogel for wearable sensors as shown in fig. 4.
The figure shows that the multifunctional polymer dicationic hydrogel for the wearable sensor has excellent mechanical properties, the maximum strain exceeds 500%, the stress can reach 900 kPa, and the requirements of elasticity (0.4 to 1.9 MPa) and flexibility (the elongation is more than 180%) of the flexible wearable sensor can be completely met.
Fifthly, function testing:
(1) conductivity:
the conductivity of the wearable sensor is verified by connecting the multifunctional polymer dicationic hydrogel used as a lead wire with an LED bulb and a 3V external power supply to form a complete circuit. The testing process comprises the following steps: the LED bulb was lit up by placing the biscationic hydrogel into the circuit (fig. 5 a), due to the good conductivity of the biscationic hydrogel. The dicationic hydrogel was cut, the circuit was broken and the LED bulb was immediately extinguished (fig. 5 b). The multifunctional polymer dicationic hydrogel for the wearable sensor is proved to have excellent electrical stability and sensitivity, and therefore, the multifunctional polymer dicationic hydrogel can be used as the wearable sensor for monitoring human body movement.
(2) The freezing resistance performance is as follows:
after the multifunctional polymer dicationic hydrogel for the wearable sensor is frozen at-10 ℃ for 24 h, the multifunctional polymer dicationic hydrogel still maintains transparency and flexibility, and further stretching experiments are carried out, so that the multifunctional polymer dicationic hydrogel can be stretched to 2 times of the original length (fig. 6). The addition of the ionic liquid enables the multifunctional polymer dicationic hydrogel for the wearable sensor to have good freezing resistance, and the application range of the hydrogel as a flexible wearable material is expanded.
(3) Antibacterial property:
and (3) testing process: staphylococcus aureus and Escherichia coli are respectively used as representatives of gram-positive bacteria and gram-negative bacteria, and the antibacterial performance of the multifunctional polymer dicationic hydrogel for the wearable sensor is tested by using a flat plate counting method. Firstly, cutting the material into wafers, and sterilizing the wafers to be tested before carrying out an antibacterial experiment. Secondly, adding the sterilized material wafer and the activated bacterial suspension into a phosphate buffer solution (PBS buffer solution) to serve as an experimental group; PBS buffer containing bacteria was used as a control group. Samples from both experimental and control groups were incubated for 4 h at 37 ℃ on a constant temperature shaker. Finally, the obtained bacterial suspension was spread on nutrient agar plates, incubated in a 37 ℃ incubator for 48 hours, and the growth of colonies was observed, and the experimental results are shown in fig. 7.
The viability of the bacterial colonies was clearly seen in the antimicrobial photographs of the plates (the small white dots grown on the plates represent viable bacterial colonies). On the control plates, both staphylococcus aureus (a) and escherichia coli (c) showed relatively dense colonies, indicating unrestricted growth of staphylococcus aureus and escherichia coli in the absence of the multi-functional polymer dicationic hydrogel. After the bacterial suspension is contacted with the multifunctional polymer dicationic hydrogel for a period of time, the growth of the bacterial colonies of staphylococcus aureus (b) and escherichia coli (d) on the culture plate is obviously limited, which shows that the multifunctional polymer dicationic hydrogel for the wearable sensor has good antibacterial activity on both staphylococcus aureus and escherichia coli.
The result shows that the material has obvious antibacterial property on gram-positive bacteria (staphylococcus aureus) and gram-negative bacteria (escherichia coli) and broad-spectrum antibacterial activity, so that the defect that the flexible wearable sensor is easily allergic and infected by bacteria when being attached to the skin or tissue of a human body for a long time is overcome.
(4) And (3) motion monitoring:
the multifunctional polymer dicationic hydrogel for the wearable sensor is attached to each part of a human body, two ends of the multifunctional polymer dicationic hydrogel are connected to the digital source meter through copper wires, the resistance change along with the strain change of the multifunctional polymer dicationic hydrogel for the wearable sensor is recorded through the digital source meter, a resistance-strain curve is obtained, and the accurate monitoring of the human body action can be realized through the resistance-strain curve shape and the strength change.
FIG. 8 shows the relative resistance (Δ R/R) of the multifunctional polymer dicationic hydrogel for wearable sensor during human body movement 0 ) A change in (c). As can be seen from the figure, when the joints of a human body start to move, the change of the relative resistance of the multifunctional polymer dicationic hydrogel starts to increase, the maximum value is reached when the movement amplitude of the joints is maximum, the change of the relative resistance of the multifunctional polymer dicationic hydrogel starts to decrease along with the recovery of the movement of the joints, the same movement is continuously repeated, and signals can also be continuously and repeatedly output, so that the high strain sensitivity, the quick movement responsiveness and the repeatability of the multifunctional polymer dicationic hydrogel for the wearable sensor are verified.
Example 2 preparation of multifunctional polymer dicationic hydrogel for wearable sensor: under the ice-water bath condition of-4 ℃ to 0 ℃, sequentially adding deionized water, 2.54 g of 1-propyl-3-vinyl imidazole sulfonate and 3.56 g of N, N-trimethyl-3- (2-methallylamido) -1-propyl ammonium chloride into a container, and stirring until 250 g/L of homogeneous solution is formed; then, 0.22 g of N, N' -methylene bisacrylamide and 0.32 g of ethyl 2,4, 6-trimethylbenzoylphenylphosphonate are quickly added and stirred for 30 min to obtain a monomer mixture containing an initiator; and transferring the monomer mixture containing the initiator into a mold, and reacting for 6 hours under the illumination of 254 nm ultraviolet light to obtain the multifunctional polymer dicationic hydrogel for the wearable sensor.
Example 3 preparation of multifunctional polymer dicationic hydrogel for wearable sensor: under the condition of ice-water bath at the temperature of-4 ℃ to 0 ℃, sequentially adding deionized water, 1.32 g of 1-ethyl-3- (1-vinyl imidazole-3-hexyl) imidazole bromide and 4.05 g of gamma- (methacrylamide) propyl trimethyl ammonium chloride into a container, and stirring until a homogeneous solution of 115 g/L is formed; then quickly adding 0.15 g of ethylene glycol diacrylate and 0.17 g of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, and stirring for 25 min to obtain a monomer mixture containing an initiator; and transferring the monomer mixture containing the initiator into a required mold, and reacting for 10 hours under the irradiation of 365 nm ultraviolet light to obtain the multifunctional polymer dicationic hydrogel for the wearable sensor.
Example 4 preparation of multifunctional polymer dicationic hydrogel for wearable sensor: under the ice-water bath condition of-4 ℃ to 0 ℃, sequentially adding deionized water, 0.98 g of 1-butyl-3-vinylimidazole bromine salt and 1.89 g of gamma- (methacrylamide) propyl trimethyl ammonium chloride into a container, and stirring until 180 g/L of homogeneous solution is formed; then, 0.18 g of ethylene glycol diacrylate and 0.33 g of 2-hydroxy-2-methyl-1-phenyl acetone are rapidly added and stirred for 50 min to obtain a monomer mixture containing an initiator; and transferring the monomer mixture containing the initiator into a required mold, and reacting for 10 hours under the illumination of 254 nm ultraviolet light to obtain the multifunctional polymer dicationic hydrogel for the wearable sensor.
Example 5 preparation of multifunctional polymer dicationic hydrogel for wearable sensor: under the ice-water bath condition of-4 ℃ to 0 ℃, sequentially adding deionized water, 3.01 g of 1-ethyl-3- (1-vinyl imidazole-3-hexyl) imidazole bromide and 2.88 g of N, N-trimethyl-3- (2-methyl allylamido) -1-propyl ammonium chloride into a container, and stirring until 70 g/L of homogeneous solution is formed; then, 0.29 g of N, N' -methylene bisacrylamide and 0.55 g of 2-hydroxy-2-methyl-1-phenyl acetone are quickly added and stirred for 40 min to obtain a monomer mixture containing an initiator; and transferring the monomer mixture containing the initiator into a required mold, and reacting for 12 hours under the irradiation of 365 nm ultraviolet light to obtain the multifunctional polymer dicationic hydrogel for the wearable sensor.

Claims (5)

1. The preparation method of the multifunctional polymer dicationic hydrogel for the wearable sensor is characterized by comprising the following steps: under the condition of ice-water bath, sequentially adding deionized water, ionic liquid and quaternary ammonium salt into a container, and stirring until a homogeneous solution of 40-300 g/L is formed; then, quickly adding a cross-linking agent and a photoinitiator, and stirring for 10 to 60 min to obtain a monomer mixture containing the initiator; transferring the monomer mixture containing the initiator into a required mold, and reacting for 6 to 12 hours under illumination to obtain the multifunctional polymer dicationic hydrogel for the wearable sensor; the ionic liquid is one of 1-butyl-3-vinyl imidazole bromide, 1-propyl-3-vinyl imidazole sulfonate or 1-ethyl-3- (1-vinyl imidazole-3-hexyl) imidazole bromide; the quaternary ammonium salt is N, N, N-trimethyl-3- (2-methallylamido) -1-propyl ammonium chloride or gamma- (methacrylamide) propyl trimethyl ammonium chloride; the cross-linking agent is N, N' -methylene bisacrylamide or ethylene glycol diacrylate.
2. The method for preparing the multifunctional polymer dicationic hydrogel for the wearable sensor according to claim 1, wherein: the temperature of the ice-water bath is-4 ℃ to 0 ℃.
3. The method for preparing the multifunctional polymer dicationic hydrogel for the wearable sensor according to claim 1, wherein: the mass ratio of the ionic liquid to the quaternary ammonium salt to the cross-linking agent is 0.20 to 3.30:1.10 to 5.50:0.01 to 0.30.
4. The method for preparing the multifunctional polymer dicationic hydrogel for the wearable sensor according to claim 1, wherein: the photoinitiator is one of 2-hydroxy-2-methyl-1-phenyl acetone, 2,4, 6-trimethyl benzoyl phenyl ethyl phosphonate or 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone, and the usage amount of the photoinitiator is 2% -10% of the sum of the mass of the ionic liquid and the mass of the quaternary ammonium salt.
5. The method for preparing the multifunctional polymer dicationic hydrogel for the wearable sensor according to claim 1, wherein: the illumination condition is that ultraviolet light of 250 to 400 nm is adopted.
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