CN113248734A - Functional double-network hydrogel and application thereof - Google Patents
Functional double-network hydrogel and application thereof Download PDFInfo
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Abstract
The invention discloses a functionalized double-network hydrogel and application thereof, belonging to the field of materials science. The calcium alginate/polyacrylamide interpenetrating double-network hydrogel can effectively dissipate loaded stress and has excellent elasticity and flexibility; the carboxylated carbon nanotube is introduced, so that the material shows excellent mechanical properties, has good electrical capacity, restorability, strain sensing performance, swelling behavior of pH response, tissue adhesion performance and sustainable drug release behavior at low temperature, expands the application range of the material in flexible wearable technology, and is expected to realize potential application in wearable medical integration.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a functionalized double-network hydrogel and application of low-temperature strain sensing of the functionalized double-network hydrogel in flexible wearable equipment and a drug low-temperature delivery carrier.
Background
Hydrogels are polymers of three-dimensional network structures formed by hydrophilic polymer chains embedded in an aqueous environment. A variety of naturally derived and synthetic polymers can be processed into hydrogels, from polymers formed by physical entanglement to polymers stabilized by covalent cross-linking. Therefore, hydrogels have become a class of multifunctional soft materials due to their unique tunable physicochemical and structural properties. Hydrogels are now widely used in the biotechnology and biomedical fields, including artificial muscle, drug delivery, tissue engineering, and the like. Since the single-network hydrogel is highly stretchable, has low toughness and poor restorability, the practical application of the single-network hydrogel in the field of intelligent materials is limited. Based on this, the problem is solved by constructing a multi-system composition method to synthesize an interpenetrating double-network structure, and the generation of the functional hydrogel with high mechanical properties, low-temperature strain sensing and other diverse properties is receiving more and more attention from researchers.
So far, functionalized hydrogels with high mechanical, electrical and low temperature strain sensing have attracted great interest to researchers. For example, ion-conductive cellulose hydrogels are Applied to flexible electrodes, sensors and wearable devices at low temperatures (Yang, et al. ACS Applied Materials & Interfaces 2019, 11(44): 41710-. The main disadvantage of the hydrogel is that the mechanical property and the electrical property are poor, and the high stretchability and the good conductivity are key elements for realizing the flexible wearable technology. Therefore, CN112280092A discloses a composite hydrogel composed of sodium alginate, cellulose nanofibers and ferric chloride, which has excellent stretchability and flexibility. CN112225913A discloses a double-network hydrogel composed of acrylamide and agar, which has good tensile strength and elongation at break. However, when the temperature drops below the freezing point of water, the conventional hydrogel freezes and loses stretchability and original elasticity, and electrical sensing function, so that the application range of the conventional hydrogel in flexible wearable technology and the like under certain extreme conditions (such as below zero degree) is limited. Therefore, the development of the functional hydrogel which monitors human physiological signals and has excellent integration performance has great application potential in flexible materials.
Disclosure of Invention
The invention aims to provide a functionalized double-network hydrogel and application of low-temperature strain sensing thereof in flexible wearable equipment and a drug low-temperature delivery carrier. The synthesized hydrogel has flexibility and excellent mechanical properties, can keep good conductive capability and restorability at low temperature, has low-temperature strain sensing performance, and is expected to become a flexible electronic material applied to the fields of wearable equipment, electronic skin and the like in some extreme environments. Meanwhile, the compound has pH response swelling behavior, tissue adhesion performance and sustainable drug release behavior, and is expected to realize potential application in wearable medical integration.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the functionalized double-network hydrogel comprises the following steps:
(1) adding distilled water into two mixed powders of sodium alginate (Alg) and Acrylamide (AM) to form an aqueous solution, and fully stirring the solution until all the powders are dissolved to obtain a solution S1;
(2) dissolving the carboxylated carbon nanotube powder into the solution S1, and performing ultrasonic dispersion in a water bath to obtain a solution S2 containing the carboxylated carbon nanotubes;
(3) adding N, N' -Methylene Bisacrylamide (MBA), Tetramethylethylenediamine (TEMED), Ammonium Persulfate (APS) and calcium sulfate dihydrate (CaSO) in this order4·2H2O) in the stirred solution S2, fully stirring and mixing to obtain a pre-polymerization solution S3;
(4) and quickly transferring the prepolymerization solution S3 into a glass mold, placing the sealed mold into ultraviolet light, and initiating by the ultraviolet light to complete polymerization to obtain the ionic-covalent double-crosslinked low-temperature strain-sensing calcium alginate/polyacrylamide/carboxylated carbon nanotube-based (Alg-Ca/PAM/CNT) functionalized double-network hydrogel.
Preferably, the concentration of AM in the step (1) is 0.14-0.25 g/mL, the concentration of Alg is 0.01-0.06 g/mL, and the stirring time is 3-24 h.
Preferably, the concentration of the carboxylated carbon nanotubes in the step (2) is 0.20-1.20 mg/mL.
Preferably, in the step (3), the concentration of MBA is 0.05-0.20 mg/mL, the concentration of TEMED is 0.1-0.6 mg/mL, the concentration of APS is 1.50-2.00 mg/mL, and CaSO4·2H2The concentration of O is 13.00-17.00 mg/mL, and the stirring time is 1-12 h.
Preferably, the ultraviolet irradiation time in the step (4) is 1-6 h.
Preferably, the time for completing the polymerization of the hydrogel in the step (4) is 3-24 h.
The application of the Alg-Ca/PAM/CNT functionalized double-network hydrogel comprises the following steps:
1) as a strain sensor for monitoring the bending motion of the human body, the human joint motion is monitored under the low temperature condition. When the joint was slowly flexed at a step-wise increasing amplitude, the rate of change of resistance of the Alg-Ca/PAM/CNT hydrogel strain sensor was completely synchronized with the joint motion, showing its sensitivity. In addition, the bending angle of the human body joint is monitored by analyzing the peak value output by | Δ R |/R0, and the motion frequency is monitored by calculating the number of peak values.
2) As a strain sensor for monitoring the stretching and bending movements of the human body, the repeated movements of the finger joints are monitored under the low-temperature condition. The Alg-Ca/PAM/CNT hydrogel strain sensor performs the cyclic action of repeatedly bending the finger at the temperature of-20 ℃ with the same amplitude, and the ionic conductivity and the mechanical property of the Alg-Ca/PAM/CNT hydrogel strain sensor can be kept relatively stable. In addition, when the same strain value is 400% or the changed strain range is 100-400%, the hydrogel strain sensor has high sensitivity and good reproducibility.
3) As the electronic skin, it is used as a stretchable human motion detector by being attached to an arm or a hand in an environment of-20 ℃. Hydrogel-based strain sensors co-track the strain of the skin (glove) and accurately record the skin deformation in a resistance map, enabling monitoring of real-time and in-situ force signals from bending and stretching.
4) The hydrogel as a drug carrier has ideal performance, encapsulates the drug in a low-temperature environment of-80 ℃, not only maintains the low-temperature drug effect of the drug, but also shows sustained drug release behavior as an ideal storage carrier, is expected to overcome the limitation of the conventional hydrogel as a drug carrier, and greatly increases the potential of a range of deliverable drug types, especially for certain anticancer drugs (such as lomustine) which need to be preserved at subzero temperature to maintain biological activity. The hydrogel provides a new idea for the development of wearable medical monitoring integrated application of the hydrogel serving as a low-temperature delivery carrier loaded with an anti-cancer drug and combined with a flexible sensor.
The invention has the beneficial effects that: compared with the prior art, the invention optimizes Alg, AM, MBA, TEMED, APS and CaSO4·2H2The concentration of O improves the restorability and mechanical property of the hydrogel; the low-temperature strain sensing Alg-Ca/PAM/CNT functional interpenetrating double-network hydrogel obtained by introducing certain mass fraction of carboxylated carbon nanotube powder effectively realizes the monitoring of the flexible wearable technology on human activities and personal health under extreme conditionsThe purpose of (1). The preparation method is simple, and the obtained low-temperature strain sensing functional interpenetrating polymer network hydrogel has good overall performance. Due to the fact that the conductive Alg-Ca/PAM/CNT interpenetrating double-network hydrogel has tensile strain, even under the low-temperature condition of 20 ℃ below zero, the resistance change and the strain change can be synchronized, and when the same strain value is 400% or the changed strain range is 400%, the sensor has high sensitivity and good reproducibility. As the average distance between CNTs increases during stretching, the resistance also increases, which can be attributed to the tunneling effect of charge transfer. As a wearable strain sensor, the strain sensor is used for detecting the stretching and bending motion of a human body, such as a finger joint at subzero temperature, and when the finger is repeatedly bent and stretched, the attached Alg-Ca/PAM/CNT hydrogel strain sensor has the corresponding response behavior that the resistance change rate is completely synchronous with the motion of the finger joint. The sensor has excellent repeatability, processing power and easy integration properties, so that the motion of the finger can be accurately monitored and applied to the skin (glove). As a stretchable human motion detector, hydrogel-based strain sensors collectively track the strain of the skin (glove) and accurately record the deformation of the skin in a resistance map. The Alg-Ca/PAM/CNT functional double-network hydrogel taking the lomustine as a drug model for release shows a controlled release and sustained release mode for low molecular weight substances, and has excellent low-temperature drug sustained release capability, pH response swelling behavior (between 1 and 13) and low temperature resistance. In addition, the hydrogel is easy to adhere to animal tissues and organs, presents strong tissue adhesion with pigskin, pork liver and pork heart, and can effectively reduce the loss of the drug in the delivery process. The penetration of the drug to the inflamed tissue part is increased, the degree of adverse reaction is reduced, and the effective load efficiency of the drug is improved. Therefore, the Alg-Ca/PAM/CNT based hydrogel strain sensor shows great application potential in the field of wearable devices, is expected to become a promising hydrogel concept in chemotherapy under low-temperature conditions, may have great application prospect in the field of drug delivery in tissue engineering or clinical operation, and particularly has human health monitoringThe wearable medical monitoring integration of the combination of the functional flexible sensors becomes possible.
Drawings
FIG. 1 is a schematic diagram of a process for preparing an Alg-Ca/PAM/CNT functionalized double-network hydrogel according to the present invention;
FIG. 2 is a graph of the quantitative analysis of mechanical properties of the Alg-Ca/PAM/CNT functionalized double-network hydrogel prepared in example 8;
FIG. 3 is a recoverable performance test of the Alg-Ca/PAM/CNT functionalized double-network hydrogel prepared in example 8;
FIG. 4 is a low-temperature electrical property verification of the Alg-Ca/PAM/CNT functionalized double-network hydrogel prepared in example 8;
FIG. 5 is a low-temperature strain sensing performance verification of the Alg-Ca/PAM/CNT functionalized double-network hydrogel prepared in example 8;
FIG. 6 is a low-temperature wearable device application validation of the Alg-Ca/PAM/CNT functionalized dual-network hydrogel strain sensor prepared in example 8;
FIG. 7 is a low-temperature pH response performance verification of the Alg-Ca/PAM/CNT functionalized double-network hydrogel prepared in example 8;
FIG. 8 is a cryotissue adhesion performance validation of Alg-Ca/PAM/CNT functionalized double-network hydrogel prepared in example 8;
FIG. 9 is a low-temperature drug sustained-release property verification of the Alg-Ca/PAM/CNT functionalized double-network hydrogel prepared in example 8.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
The preparation method of the functionalized double-network hydrogel comprises the following steps:
(1) adding distilled water into two mixed powders of sodium alginate (Alg) and Acrylamide (AM) to form an aqueous solution, and fully stirring the solution until all the powders are dissolved to obtain a solution S1;
(2) dissolving the carboxylated carbon nanotube powder into the solution S1, and performing ultrasonic dispersion in a water bath to obtain a solution S2 containing the carboxylated carbon nanotubes;
(3) adding N, N' -Methylene Bisacrylamide (MBA), Tetramethylethylenediamine (TEMED), Ammonium Persulfate (APS) and calcium sulfate dihydrate (CaSO) in this order4·2H2O) in the stirred solution S2, fully stirring and mixing to obtain a pre-polymerization solution S3;
(4) and quickly transferring the prepolymerization solution S3 into a glass mold, placing the sealed mold into ultraviolet light, and initiating by the ultraviolet light to complete polymerization to obtain the ionic-covalent double-crosslinked calcium alginate/polyacrylamide/carbon nanotube-based (Alg-Ca/PAM/CNT) functionalized double-network hydrogel with low-temperature strain sensing.
In the present invention, first, Alg and AM powders were dissolved in deionized water to obtain polymer solution S1. The concentration of Alg is 0.01-0.06 g/mL, the concentration of AM is 0.14-0.25 g/mL, and the stirring time is 3-24 h. More preferably, the concentration of Alg is 0.02-0.05 g/mL, the concentration of AM is 0.15-0.20 g/mL, and the stirring time is 6-18 h.
After obtaining a solution S2, MBA, TEMED, APS and CaSO were added in sequence during stirring4·2H2And O, fully and uniformly stirring to obtain the prepolymerization solution S3. The concentration of MBA is 0.05-0.20 mg/mL, the concentration of TEMED is 0.1-0.6 mg/mL, the concentration of APS is 1.50-2.00 mg/mL, CaSO4·2H2The concentration of O is 13.00-17.00 mg/mL, and the stirring time is 1-12 h. More preferably, the concentration of MBA is 0.08-0.13 mg/mL, the concentration of TEMED is 0.25-0.55 mg/mL, the concentration of APS is 1.60-1.90 mg/mL, CaSO4·2H2The concentration of O is 13.50-16.50 mg/mL, and the stirring time is 2-6 h.
And (3) quickly transferring the prepolymerization solution S3 to a glass mold, placing the sealed mold in ultraviolet light, and initiating by the ultraviolet light to obtain the ionic-covalent double-crosslinked low-temperature strain sensing Alg-Ca/PAM/CNT functionalized double-network hydrogel. The illumination is ultraviolet illumination, and the illumination time is 1-6 h. More preferably, the illumination time is 2-5 h.
The sample was held at room temperature for a period of time to complete the polymerization. The time for completing polymerization of the hydrogel is 3-24 hours. More preferably, the polymerization time is 6 to 18 hours.
The concentration of the carboxylated carbon nano tube is 0.20-1.20 mg/mL. More preferably 0.50 to 1.00 mg/mL.
For further understanding of the present invention, the following examples are provided to illustrate the preparation method of the functionalized double-network hydrogel for low temperature strain sensing, and the scope of the present invention is not limited by the following examples.
Example 1
(1) Adding distilled water into two mixed powders of Alg (0.01 g/mL) and AM (0.14 g/mL) to form an aqueous solution, and fully stirring the solution until all the powders are dissolved to obtain a solution S1;
(2) dissolving carboxylated carbon nanotube powder (0.20 mg/mL) in the solution S1, and performing ultrasonic dispersion in a water bath to obtain a solution S2 containing carboxylated carbon nanotubes;
(3) MBA (0.05 mg/mL), TEMED (0.10 mg/mL), APS (1.50 mg/mL) and CaSO were added in that order4·2H2O (13.00 mg/mL) in the stirred solution S2 for 1 h, and the mixture is completely mixed to obtain a prepolymerization solution S3;
(4) and (3) quickly transferring the prepolymerization solution S3 into a glass mold, placing the sealed mold in ultraviolet light for 1 h, carrying out polymerization on the sample at room temperature for 3 h, and carrying out polymerization under ultraviolet light initiation to obtain the ionic covalent double-crosslinked low-temperature strain sensing Alg-Ca/PAM/CNT functionalized double-network hydrogel.
Example 2
(1) Adding distilled water into two mixed powders of Alg (0.02 g/mL) and AM (0.15 g/mL) to form an aqueous solution, and fully stirring the solution until all the powders are dissolved to obtain a solution S1;
(2) dissolving carboxylated carbon nanotube powder (0.30 mg/mL) in the solution S1, and performing ultrasonic dispersion in a water bath to obtain a solution S2 containing carboxylated carbon nanotubes;
(3) MBA (0.06 mg/mL), TEMED (0.20 mg/mL), APS (1.60 mg/mL) and CaSO were added in that order4·2H2O (14.00 mg/mL) in the stirred solution S2 for 2h, and the pre-polymerization solution S3 is obtained after complete mixing;
(4) and (3) quickly transferring the prepolymerization solution S3 into a glass mold, placing the sealed mold in ultraviolet light for 2h, carrying out polymerization on the sample at room temperature for 4h, and carrying out polymerization under ultraviolet light initiation to obtain the ionic covalent double-crosslinked low-temperature strain sensing Alg-Ca/PAM/CNT functionalized double-network hydrogel.
Example 3
(1) Adding distilled water into two mixed powders of Alg (0.03 g/mL) and AM (0.16 g/mL) to form an aqueous solution, and fully stirring the solution until all the powders are dissolved to obtain a solution S1;
(2) dissolving carboxylated carbon nanotube powder (0.40 mg/mL) in the solution S1, and performing ultrasonic dispersion in a water bath to obtain a solution S2 containing carboxylated carbon nanotubes;
(3) MBA (0.07 mg/mL), TEMED (0.30 mg/mL), APS (1.70 mg/mL) and CaSO were added in that order4·2H2O (15.00 mg/mL) in the stirred solution S2 for 3 h, and the pre-polymerization solution S3 is obtained after complete mixing;
(4) and (3) quickly transferring the prepolymerization solution S3 into a glass mold, placing the sealed mold in ultraviolet light for 3 h, carrying out polymerization on the sample at room temperature for 5 h, and carrying out polymerization under ultraviolet light initiation to obtain the ionic covalent double-crosslinked low-temperature strain sensing Alg-Ca/PAM/CNT functionalized double-network hydrogel.
Example 4
(1) Adding distilled water into two mixed powders of Alg (0.04 g/mL) and AM (0.25 g/mL) to form an aqueous solution, and fully stirring the solution until all the powders are dissolved to obtain a solution S1;
(2) dissolving carboxylated carbon nanotube powder (0.50 mg/mL) in the solution S1, and performing ultrasonic dispersion in a water bath to obtain a solution S2 containing carboxylated carbon nanotubes;
(3) MBA (0.08 mg/mL), TEMED (0.40 mg/mL), APS (1.80 mg/mL) and CaSO were added in that order4·2H2Solution of O (17.00 mg/mL) in stirringS2, stirring for 6 hours, and mixing completely to obtain a prepolymerization solution S3;
(4) and (3) quickly transferring the prepolymerization solution S3 into a glass mold, placing the sealed mold in ultraviolet light for 6h, carrying out polymerization on the sample at room temperature for 18 h, and carrying out polymerization under ultraviolet light initiation to obtain the ionic covalent double-crosslinked low-temperature strain sensing Alg-Ca/PAM/CNT functionalized double-network hydrogel.
Example 5
(1) Adding distilled water into two mixed powders of Alg (0.06 g/mL) and AM (0.25 g/mL) to form an aqueous solution, and fully stirring the solution until all the powders are dissolved to obtain a solution S1;
(2) dissolving carboxylated carbon nanotube powder (1.20 mg/mL) in the solution S1, and performing ultrasonic dispersion in a water bath to obtain a solution S2 containing carboxylated carbon nanotubes;
(3) MBA (0.08 mg/mL), TEMED (0.40 mg/mL), APS (1.80 mg/mL) and CaSO were added in that order4·2H2O (17.00 mg/mL) in the stirred solution S2 for 6h, and the pre-polymerization solution S3 is obtained after complete mixing;
(4) and (3) quickly transferring the prepolymerization solution S3 into a glass mold, placing the sealed mold in ultraviolet light for 6h, carrying out polymerization on the sample at room temperature for 18 h, and carrying out polymerization under ultraviolet light initiation to obtain the ionic covalent double-crosslinked low-temperature strain sensing Alg-Ca/PAM/CNT functionalized double-network hydrogel.
Example 6
(1) Adding distilled water into two mixed powders of Alg (0.06 g/mL) and AM (0.25 g/mL) to form an aqueous solution, and fully stirring the solution until all the powders are dissolved to obtain a solution S1;
(2) dissolving carboxylated carbon nanotube powder (1.20 mg/mL) in the solution S1, and performing ultrasonic dispersion in a water bath to obtain a solution S2 containing carboxylated carbon nanotubes;
(3) MBA (0.13 mg/mL), TEMED (0.55 mg/mL), APS (1.90 mg/mL) and CaSO were added in that order4·2H2O (17.00 mg/mL) in a stirred solution S2 for 6h, and mixing completely to obtain a prepolymerMixing the solution S3;
(4) and (3) quickly transferring the prepolymerization solution S3 into a glass mold, placing the sealed mold in ultraviolet light for 6h, carrying out polymerization on the sample at room temperature for 18 h, and carrying out polymerization under ultraviolet light initiation to obtain the ionic covalent double-crosslinked low-temperature strain sensing Alg-Ca/PAM/CNT functionalized double-network hydrogel.
Example 7
(1) Adding distilled water into two mixed powders of Alg (0.06 g/mL) and AM (0.25 g/mL) to form an aqueous solution, and fully stirring the solution until all the powders are dissolved to obtain a solution S1;
(2) dissolving carboxylated carbon nanotube powder (1.20 mg/mL) in the solution S1, and performing ultrasonic dispersion in a water bath to obtain a solution S2 containing carboxylated carbon nanotubes;
(3) MBA (0.13 mg/mL), TEMED (0.55 mg/mL), APS (1.90 mg/mL) and CaSO were added in that order4·2H2O (17.00 mg/mL) in the stirred solution S2 for 3 h, and the pre-polymerization solution S3 is obtained after complete mixing;
(4) and (3) quickly transferring the prepolymerization solution S3 into a glass mold, placing the sealed mold in ultraviolet light for 4h, carrying out polymerization on the sample at room temperature for 12 h, and carrying out polymerization under ultraviolet light initiation to obtain the ionic covalent double-crosslinked low-temperature strain sensing Alg-Ca/PAM/CNT functionalized double-network hydrogel.
Example 8
(1) Adding distilled water into two mixed powders of Alg (0.03 mg/mL) and AM (0.17 g/mL) to form an aqueous solution, and fully stirring the solution until all the powders are dissolved to obtain a solution S1;
(2) dissolving carboxylated carbon nanotube powder (0.85 mg/mL) in the solution S1, and performing ultrasonic dispersion in a water bath to obtain a solution S2 containing carboxylated carbon nanotubes;
(3) MBA (0.08 mg/mL), TEMED (0.42 mg/mL), APS (1.69 mg/mL) and CaSO were added in that order4·2H2O (14.86 mg/mL) in the stirred solution S2 for 3 h, and the pre-polymerization solution S3 is obtained after complete mixing;
(4) and (3) quickly transferring the prepolymerization solution S3 into a glass mold, placing the sealed mold in ultraviolet light for 4h, carrying out polymerization on the sample at room temperature for 12 h, and carrying out polymerization under ultraviolet light initiation to obtain the ionic covalent double-crosslinked low-temperature strain sensing Alg-Ca/PAM/CNT functionalized double-network hydrogel.
Fig. 2 is a graph of quantitative analysis of mechanical properties of the Alg-Ca/PAM/CNT functionalized double-network hydrogel of example 8, which is obtained by testing elongation at break, compressive strain rate, maximum tensile strength, maximum compressive strength and young's modulus of the above materials, respectively, and it can be clearly seen that the hydrogel can exhibit good tensile and compressive properties, and the tensile strength, elongation at break and young's modulus of the hydrogel in a tensile state are respectively: 271.68 kPa, 4200.00%, 22.12 kPa; the compressive strength, compressive strain and Young modulus of the hydrogel in a compressed state are respectively as follows: 151.18 kPa, 80.50% and 29.07 kPa.
FIG. 3 is a recoverable property verification of the Alg-Ca/PAM/CNT functionalized double-network hydrogel prepared in example 8, which confirms that the hydrogel shows a rapid recovery capability at either-20 ℃ or 25 ℃ and does not undergo a large permanent deformation.
FIG. 4 is a low-temperature electrical property verification of the Alg-Ca/PAM/CNT functionalized double-network hydrogel prepared in example 8, which confirms that the hydrogel maintains excellent electrical properties at-20 ℃, has a high current value of about 4 mA, and when a circuit design is performed by using the hydrogel, the logo of 'FZU' can be displayed by connecting the hydrogel in series with a Light Emitting Diode (LED) after being connected with two electrodes.
Fig. 5 is a low-temperature strain sensing performance verification of the Alg-Ca/PAM/CNT functionalized double-network hydrogel prepared in example 8, and confirms that the resistance change of the hydrogel can be synchronized with the strain change under the low-temperature condition of-20 ℃, and the hydrogel strain sensor has higher sensitivity and good reproducibility when the same strain value is 400% or 100%, 200%, 300% and 400% strain is applied under continuous stretching/releasing cycles.
Fig. 6 is a low-temperature wearable device application verification of the Alg-Ca/PAM/CNT functionalized dual-network hydrogel strain sensor prepared in example 8, which confirms that the hydrogel is attached to the finger joint for detecting joint movement, the resistance change rate of the hydrogel strain sensor is completely synchronized with the finger movement, and the hydrogel strain sensor is used as a stretchable human body movement detector to track the strain of the skin (glove) together by being attached to the arm or hand under the environment of-20 ℃, and accurately record the deformation of the skin in a resistance diagram, thereby demonstrating the application potential of the low-temperature strain sensing wearable device.
Fig. 7 is a low-temperature pH response performance verification of the Alg-Ca/PAM/CNT functionalized double-network hydrogel prepared in example 8, and confirms that the swelling performance of the hydrogel is changed with the environmental pH, the swelling degree is small below pH = 3, and the swelling rate is slightly increased when the pH value is increased until pH = 7; when the pH was increased from 11 to 13, the swelling ratio increased sharply from 1200% up to 2000%.
FIG. 8 is a low-temperature tissue adhesion performance verification of the Alg-Ca/PAM/CNT functionalized double-network hydrogel prepared in example 8, which confirms that the hydrogel exhibits strong tissue adhesion to pigskin, pork liver and pork heart on animal tissue and organs, and the values thereof are respectively 91.79 + -14.34, 83.23 + -14.14 and 81.28 + -4.40 Pa by calculation.
FIG. 9 is a low-temperature drug sustained-release property verification of the Alg-Ca/PAM/CNT functionalized double-network hydrogel prepared in example 8, and confirms that the hydrogel has prolonged release time for Lomustine, wherein the release behavior of the drug is mainly dependent on the expansion rate of the hydrogel. Specifically, the drug located on the surface and shallow layer of the hydrogel is rapidly released on the first day. Then, the hydrogel was gradually swollen to saturation by absorbing the PBS solution, and a difference in drug concentration was formed between the inner and outer layers. On day 5, the release of the drug was accelerated by hydrogel surface disruption until day 29, which tended to stabilize. This indicates that the hydrogel exhibits controlled and sustained release patterns for low molecular weight substances.
Example 9
(1) Adding distilled water into two mixed powders of Alg (0.03 mg/mL) and AM (0.20 g/mL) to form an aqueous solution, and fully stirring the solution until all the powders are dissolved to obtain a solution S1;
(2) dissolving carboxylated carbon nanotube powder (0.85 mg/mL) in the solution S1, and performing ultrasonic dispersion in a water bath to obtain a solution S2 containing carboxylated carbon nanotubes;
(3) MBA (0.08 mg/mL), TEMED (0.42 mg/mL), APS (1.69 mg/mL) and CaSO were added in that order4·2H2O (14.86 mg/mL) in the stirred solution S2 for 3 h, and the pre-polymerization solution S3 is obtained after complete mixing;
(4) and (3) quickly transferring the prepolymerization solution S3 into a glass mold, placing the sealed mold in ultraviolet light for 4h, carrying out polymerization on the sample at room temperature for 12 h, and carrying out polymerization under ultraviolet light initiation to obtain the ionic covalent double-crosslinked low-temperature strain sensing Alg-Ca/PAM/CNT functionalized double-network hydrogel.
Example 10
(1) Adding distilled water into two mixed powders of Alg (0.05 mg/mL) and AM (0.17 g/mL) to form an aqueous solution, and fully stirring the solution until all the powders are dissolved to obtain a solution S1;
(2) dissolving carboxylated carbon nanotube powder (0.85 mg/mL) in the solution S1, and performing ultrasonic dispersion in a water bath to obtain a solution S2 containing carboxylated carbon nanotubes;
(3) MBA (0.08 mg/mL), TEMED (0.42 mg/mL), APS (1.69 mg/mL) and CaSO were added in that order4·2H2O (14.86 mg/mL) in the stirred solution S2 for 3 h, and the pre-polymerization solution S3 is obtained after complete mixing;
(4) and (3) quickly transferring the prepolymerization solution S3 into a glass mold, placing the sealed mold in ultraviolet light for 4h, carrying out polymerization on the sample at room temperature for 12 h, and carrying out polymerization under ultraviolet light initiation to obtain the ionic covalent double-crosslinked low-temperature strain sensing Alg-Ca/PAM/CNT functionalized double-network hydrogel.
The above embodiments are merely provided to aid understanding of the method of the present invention and its core ideas. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A preparation method of a functional double-network hydrogel is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing sodium alginate and acrylamide, adding distilled water, and stirring uniformly to obtain a solution S1;
(2) adding carboxylated carbon nanotube powder into the solution S1, and performing ultrasonic dispersion to obtain a solution S2;
(3) adding N, N' -methylene bisacrylamide, tetramethylethylenediamine, ammonium persulfate and calcium sulfate dihydrate into the solution S2 while stirring, and uniformly stirring to obtain a prepolymerization solution S3;
(4) and (3) polymerizing the prepolymerization solution S3 by ultraviolet light initiation to obtain the functionalized double-network hydrogel.
2. The method of claim 1, wherein: the concentration of the sodium alginate in the solution S1 in the step (1) is 0.01-0.06 g/mL, the concentration of the acrylamide is 0.14-0.25 g/mL, and the stirring time is 3-24 h.
3. The method of claim 1, wherein: the concentration of the carboxylated carbon nanotubes in the solution S2 in the step (2) is 0.20-1.20 mg/mL.
4. The method of claim 1, wherein: n, N' -methylenedipropylenesulfide in the prepolymerization solution S3 in the step (3)The concentration of the enamide is 0.05-0.20 mg/mL, the concentration of the tetramethyl ethylene diamine is 0.1-0.6 mg/mL, the concentration of the ammonium persulfate is 1.50-2.00 mg/mL, and the concentration of the CaSO is4·2H2The concentration of O is 13.00-17.00 mg/mL, and the stirring time is 1-12 h.
5. The method of claim 1, wherein: the ultraviolet irradiation time in the step (4) is 1-6 h; the polymerization time is 3-24 h.
6. A functionalized double-network hydrogel prepared by the preparation method of claim 1, wherein: the hydrogel is ion covalent double cross-linked calcium alginate/polyacrylamide/carboxylated carbon nanotube-based functionalized double-network hydrogel.
7. Use of a functionalized double-network hydrogel prepared by the preparation method according to claim 1, wherein: the hydrogel is used as a low-temperature delivery carrier of the drug.
8. Use of a functionalized double-network hydrogel prepared by the preparation method according to claim 1, wherein: the hydrogel is applied to flexible wearable equipment for carrying out human body movement and health monitoring by low-temperature strain sensing.
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