导电水凝胶在柔性可穿戴传感器的应用研究进展

目的 概述导电水凝胶在柔性可穿戴传感器方面的研究情况,挖掘其作为传感器件的应用潜能。方法 查阅大量相关的文献,对导电水凝胶在柔性可穿戴传感领域的最新进展进行归纳与总结。按水凝胶网络分类的4种导电水凝胶,总结归纳其设计、合成、结构和潜在应用。讨论导电水凝胶的导电性、力学性能、黏附性、防冻性能、自愈性能和各式响应性等功能性能的影响因素,总结自黏性、防冻性、自修复和其他多种优秀性能的柔性可穿戴传感器。结论 导电水凝胶是一种具有多功能的独特刺激响应性的功能材料,在柔性可穿戴传感领域进行深入探究具有重大意义。     

高强度离子导电凝胶研究进展

近年来,柔性可穿戴电子产品在人机交互、传感器等方面应用越来越广泛。离子导电凝胶具有高导电性、生物相容性、自愈合、良好的机械性能以及对可见光透明度高等特点,力学性能对离子导电凝胶的应用影响较大,通过添加纳米填料、无机盐和有机盐、聚电解质可以提升离子导电凝胶的力学性能。综述了纳米复合离子导电凝胶、盐离子导电凝胶、聚电解质离子导电凝胶的研究进展,对离子导电凝胶在传感器、柔性皮肤、生物医药等领域中的应用以及面临的困难和挑战进行了探讨,并展望了其未来发展方向。     

导电水凝胶中交联剂含量对综合性能的影响

以丙烯酰胺（AM）为基体原料,N, N’-亚甲基双丙烯酰胺（MBAA）为交联剂,氯化钠（NaCl）为导电填料,采用自由基聚合的方法制备了聚丙烯酰胺（PAM）导电水凝胶,详细探究了交联剂含量对导电水凝胶力学行为和电学行为的影响。分别采用拉伸试验机和电化学工作站等手段对PAM导电水凝胶的力学性能及其导电行为进行了研究。结果表明：随着MBAA含量的增加,导致凝胶断裂伸长率及电导率下降,但回复性能提高。当将其组装成柔性传感器时,制备的导电水凝胶表现出了良好的传感性能（GF=1.76,ε=100%）,并能够有效监测人体手指和膝盖的运动,表明导电水凝胶在人体健康监测领域具有良好的应用前景。     

聚乙烯醇导电水凝胶增强剂的研究进展

聚乙烯醇是一种应用极为广泛的水溶性材料，能过通过交联形成水凝胶。聚乙烯醇导电水凝胶具有良好的亲水性、生物可降解性、生物相容性、高结晶性和与纳米纤维素混合的可行性。聚乙烯醇导电水凝胶同时也具有较好的导电性，使得其在生物医学、柔性传感等领域具有广泛的应用前景。综述了聚乙烯醇导电水凝胶在柔性传感领域的最新发展，重点了介绍了导电填料和增强剂，包括聚合物多交联、纳米复合材料、甘油及乙二醇。进一步介绍了此类水凝胶的力学性能和电性能。最后，讨论了聚乙烯醇水凝胶在柔性传感领域面临的挑战和未来展望。     

高强度聚苯胺-聚丙烯酸/聚丙烯酰胺导电水凝胶的制备与性能

将导电聚合物引入到水凝胶网络中的导电高分子基导电水凝胶,因结合了水凝胶的三维网络结构、良好的生物相容性、优异的力学性能等和导电高分子良好电学性能等优点而被广泛研究,特别是以聚苯胺(PANI)为导电高分子的导电水凝胶.但PANI不溶于水,因此很难制备PANI基导电水凝胶.本文以制备高强度PANI基导电水凝胶为目的,尝试将...     

抗冻高分子水凝胶的设计策略及应用进展

高分子水凝胶具有优异的生物相容性、延展性和变形能力,在诸多领域显示出巨大的应用前景。然而,在低温下水分子冻结,水凝胶会失去其优异的性能。近年来抗冻水凝胶材料受到广大研究者的青睐。文中主要综述了抗冻高分子水凝胶的设计策略与方法,重点介绍了3类抗冻水凝胶,即基于离子水合作用的抗冻水凝胶、基于氢键作用的抗冻水凝胶及基于离子水合与氢键协同作用的抗冻水凝胶,并阐述了抗冻水凝胶材料在软致动器、超级电容器/电池和传感器等领域的应用进展,最后讨论了抗冻水凝胶在未来发展中仍然需要解决的关键性问题和发展方向。     

室温下羧甲基纤维素导电水凝胶的快速制备及在柔性应变传感器的应用

导电水凝胶由于具有足够的灵活性、耐用性和功能多样化的独特特性,在柔性应变传感器领域具有巨大的发展前景。然而,制备水凝胶的聚合过程大多耗时、耗能且会使用有毒的交联剂,严重阻碍了其在这一新兴领域的实际应用。文中通过木质素磺酸钠/Fe³⁺组成的新型动态氧化还原体系,以羧甲基纤维素钠(CMC)和丙烯酸(AA)为基本原料,在室温快速制备了具有良好力学性能(拉伸强度435 kPa、断裂伸长率1043%)、较高离子电导率(2.23 S/m)、良好传感灵敏度(GF=2.76)及电自修复能力的CMC/PAA/Fe³⁺导电水凝胶。基于该凝胶所制备的应变传感器可以通过稳定且可重复的电信号检测人体大幅度或细微的运动,展现出了其在个人健康监测、人体运动检测和人机交互中的潜在应用价值。在室温快速制备水凝胶的方法为构建用于各种传感应用的导电水凝胶提供了新的思路。     

导电复合水凝胶的分类及其在柔性可穿戴设备中的应用

近年来，基于水凝胶的导电材料及其作为柔性可穿戴设备的应用引起了人们的广泛关注。柔性可穿戴设备不仅可以采集人体生理信号用于远程健康监测，还在人机界面、软机器人等方面展示出巨大的应用潜力。导电水凝胶所具有的良好导电性、高延伸性、可调柔韧性、生物兼容性和多重刺激响应性等优点使其成为制备柔性可穿戴设备的理想材料。到目前为止，各种导电材料被广泛用于制作导电复合水凝胶。本文根据导电材料对导电复合水凝胶进行分类，包括离子导电水凝胶(基于盐离子、离子液体、聚电解质等导电物质)、电子导电水凝胶(基于导电聚合物基、碳材料、MXene和金属等导电物质)两大类，并介绍了导电水凝胶在人体运动监测、健康监测、人机界面等柔性可穿戴设备中的应用进展。     

智能纳米水凝胶的应用研究进展

智能纳米水凝胶既有尺寸小、比表面积大的特点,又有生物相容性好、可响应外界刺激发生体积和亲水—疏水性等物理化学性能变化的特性,还有响应速度比智能水凝胶快得多的优点,因此它在许多领域呈现出诱人的应用前景.该篇文章介绍了智能纳米水凝胶在药物输送与可控释放、医学诊断、生物传感器、生物材料、微反应器、催化剂载体、吸附与分离和水处理等方面的应用研究情况.最后对智能纳米水凝胶未来的应用研究前景提出了一些粗浅的看法.     

增韧抗冻水凝胶柔性应变传感器研究进展

水凝胶作为一种结构与生物组织类似的柔性材料，被广泛地应用在柔性传感器等领域。但其内部含水量较大导致力学性能较差，且在低温环境下易结冰失效。本文从增韧机理、抗冻方法以及疲劳特性等方面对增韧抗冻水凝胶进行了综述。首先，对不同增韧机理水凝胶的力学性能以及内部结构进行了对比；其次，讨论了低温环境下水凝胶的抗冻方法；最后，总结了水凝胶在长时间静态或循环加载情况下的疲劳损伤特性。未来应致力于增加水凝胶的保水抗冻性能，深入研究水凝胶疲劳失效机理，以期为耐低温、抗疲劳水凝胶传感器的应用提供理论基础。     

Characterization of Mass and Swelling of Hydrogel Microstructures using MEMS Resonant Mass Sensor Arrays

The use of hydrogels for biomedical engineering, and for the development of biologically inspired cellular systems at the microscale, is advancing at a rapid pace. Microelectromechanical system (MEMS) resonant mass sensors enable the mass measurement of a range of materials. The integration of hydrogels onto MEMS resonant mass sensors is demonstrated, and these sensors are used to characterize the hydrogel mass and swelling characteristics. The mass values obtained from resonant frequency measurements of poly(ethylene glycol)diacrylate (PEGDA) microstructures match well with the values independently verified through volume measurements. The sensors are also used to measure the influence of fluids of similar and greater density on the mass measurements of microstructures. The data show a size-dependent increase in gel mass when fluid density is increased. Lastly, volume comparisons of bulk hydrogels with a range polymer concentration (5% to 100% (v/v)) show a non-linear swelling trend.     

Dynamic Coordination of Eu–Iminodiacetate to Control Fluorochromic Response of Polymer Hydrogels to Multistimuli

New fluorochromic materials that reversibly change their emission properties in response to their environment are of interest for the development of sensors and light‐emitting materials. A new design of Eu‐containing polymer hydrogels showing fast self‐healing and tunable fluorochromic properties in response to five different stimuli, including pH, temperature, metal ions, sonication, and force, is reported. The polymer hydrogels are fabricated using Eu–iminodiacetate (IDA) coordination in a hydrophilic poly(N,N‐dimethylacrylamide) matrix. Dynamic metal–ligand coordination allows reversible formation and disruption of hydrogel networks under various stimuli which makes hydrogels self‐healable and injectable. Such hydrogels show interesting switchable ON/OFF luminescence along with the sol–gel transition through the reversible formation and dissociation of Eu–IDA complexes upon various stimuli. It is demonstrated that Eu‐containing hydrogels display fast and reversible mechanochromic response as well in hydrogels having interpenetrating polymer network. Those multistimuli responsive fluorochromic hydrogels illustrate a new pathway to make smart optical materials, particularly for biological sensors where multistimuli response is required.     

Wetting-Enabled Three-Dimensional Interfacial Polymerization (WET-DIP) for Bioinspired Anti-Dehydration Hydrogels

Anti-dehydration hydrogels have attracted considerable attention due to their promising applications in stretchable sensors, flexible electronics, and soft robots. However, anti-dehydration hydrogels prepared by conventional strategies inevitably depend on additional chemicals or suffer from cumbersome preparation processes. Here, inspired by the succulent Fenestraria aurantiaca a one-step wetting-enabled three-dimensional interfacial polymerization (WET-DIP) strategy for constructing organogel-sealed anti-dehydration hydrogels is developed. By virtue of the preferential wetting on the hydrophobic-oleophilic substrate surfaces, the organogel precursor solution can spread on the three-dimensional (3D) surface and encapsulate the hydrogel precursor solution, forming anti-dehydration hydrogel with 3D shape after in situ interfacial polymerization. The WET-DIP strategy is simple and ingenious, and accessible to discretionary 3D-shaped anti-dehydration hydrogels with a controllable thickness of the organogel outer layer. Strain sensors based on this anti-dehydration hydrogel also exhibit long-term stability in signal monitoring. This WET-DIP strategy shows great potentialities for constructing hydrogel-based devices with long-term stability.     

Electrochemical and optical sugar sensors based on phenylboronic acid and its derivatives

Recent progress in electrochemical and optical sugar sensors based on phenylboronic acid (PBA) and its derivatives as recognition components is reviewed. PBAs are known to bind diol compounds including sugars to form cyclic boronate esters that are negatively charged as a result of the addition of OH^? ions from solution. Based on the formation of PBA charged species, sugars and their derivatives can be detected by means of electrochemical and optical techniques. For the development of PBA-based electrochemical sensing systems or sensors, PBA is modified with a redox-active marker, because PBA itself is electrochemically inactive, and ferrocene derivatives are often employed for this purpose. Ferrocene-modified PBAs have been used as redox-active additives in solution for the electrochemical detection of sugars and derivatives. PBA-modified electrodes have also been constructed as reagentless electrochemical sensors, where PBAs are immobilized on the surface of metal and carbon electrodes through mainly two routes: as a self-assembled monolayer film and as a polymer thin film. PBA-modified electrodes can be successfully used to detect sugars and derivatives through potentiometric and voltammetric responses. In addition, PBA-modified electrodes can be used for the immobilization of glycoenzymes on an electrode surface by the formation of boronate esters with carbohydrate chains in the glycoenzymes, thus resulting in enzyme biosensors. For the development of PBA-based optical sensors, a variety of chromophores and fluorophores have been coupled with PBA. Azobenzene dyes have been most frequently used for the preparation of colorimetric sugar sensors, in which the absorption wavelength and intensity of the dye are dependent on the type and concentration of added sugars. The sensitivity of the sensors is significantly improved based on multi-component systems in which alizalin red S, pyrocatechol violet, starch–iodine complex, and cyclodextrin are employed as indicators. Anthracene, pyranine, fluorescein, and rhodamine dyes have been used as fluorophores for fluorescence sensors. These dyes have been used in solution or immobilized in films, hydrogels, nanospheres, and quantum dots (QDs) to enhance the sensitivity. QDs-based sensors have been successfully applied for continuous monitoring of glucose in cells. Holographic glucose sensors have also been developed by combining PBA-immobilized hydrogels and photonic crystal colloidal arrays.     

Hydrogel machines

As polymer networks infiltrated with water, hydrogels constitute the major components of the human body; and hydrogels have been widely used in applications that closely interact with biological organisms, such as tissue engineering, drug delivery, and biological research. More recently, owing to their superior softness, wetness, responsiveness, biocompatibility, and bioactivity, hydrogels are being intensively investigated for versatile functions in devices and machines including sensors, actuators, coatings, optics, electronics, and water harvesters. A nascent field named hydrogel machines rapidly evolves, exploiting hydrogels as key components for devices and machines. While there are reviews on individual categories of hydrogel machines in literature, a comprehensive discussion on various categories of hydrogel machines that systematically correlate hydrogels’ properties and machines’ functions is still missing in the field. This review is aimed to provide such a panoramic overview. We first classify various hydrogel machines into a number of categories according to their applications. For each category, we discuss (i) the working principles of the hydrogel machines, (ii) the specific properties of hydrogels that enable the key functions of the machines, and (iii) challenges faced by hydrogel machines and recent developments to address them. The field of hydrogel machines will not only translate fundamental understanding of hydrogels into new applications, but also shift the paradigm in machine design by integrating hydrogels that can potentially minimize physical and physiological mismatches with biological organisms.     

基于离子交联复合水凝胶的易制备、高性能的可穿戴应变传感器

可响应多种机械激励模式且具有较高灵敏度的柔性传感器在电子皮肤、健康监测等领域具有重要意义.而模仿皮肤的多信号响应,如应变和温度,仍然是一个重要的挑战.因此,本文设计了具有韧性与导电性的多功能离子交联水凝胶.通过将丙烯酰胺与N,N’-亚甲基双丙烯酰胺、过硫酸铵交联,可制备出具有高力学强度特性的化学凝胶,交联时加入Ca^(...     

Hydrogels in Biology and Medicine: From Molecular Principles to Bionanotechnology

Hydrophilic polymers are the center of research emphasis in nanotechnology because of their perceived “intelligence”. They can be used as thin films, scaffolds, or nanoparticles in a wide range of biomedical and biological applications. Here we highlight recent developments in engineering uncrosslinked and crosslinked hydrophilic polymers for these applications. Natural, biohybrid, and synthetic hydrophilic polymers and hydrogels are analyzed and their thermodynamic responses are discussed. In addition, examples of the use of hydrogels for various therapeutic applications are given. We show how such systems' intelligent behavior can be used in sensors, microarrays, and imaging. Finally, we outline challenges for the future in integrating hydrogels into biomedical applications.     

How to Construct DNA Hydrogels for Environmental Applications: Advanced Water Treatment and Environmental Analysis

With high binding affinity, porous structures, safety, green, programmability, etc., DNA hydrogels have gained increasing recognition in the environmental field, i.e., advanced treatment technology of water and analysis of specific pollutants. DNA hydrogels have been demonstrated as versatile potential adsorbents, immobilization carriers of bioactive molecules, catalysts, sensors, etc. Moreover, altering components or choosing appropriate functional DNA optimizes environment‐oriented hydrogels. However, the lack of comprehensive information hinders the continued optimization. The principle used to fabricate the most suitable hydrogels in terms of the requirements is the focus of this Review. First, different fabrication strategies are introduced and the ideal characteristic for environmental applications is in focus. Subsequently, recent environmental applications and the development of diverse DNA hydrogels regarding their synthesis mechanism are summarized. Finally, the Review provides an insight into the remaining challenging and future perspectives in environmental applications.     

Electrostatically directed visual fluorescence response of DNA-functionalized monolithic hydrogels for highly sensitive Hg²+ detection

Hydrogels are cross-linked hydrophilic polymer networks with low optical background and high loading capacity for immobilization of biomolecules. Importantly, the property of hydrogel can be precisely controlled by changing the monomer composition. This feature, however, has not been investigated in the rational design of hydrogel-based optical sensors. We herein explore electrostatic interactions between an immobilized mercury binding DNA, a DNA staining dye (SYBR Green I), and the hydrogel backbone. A thymine-rich DNA was covalently functionalized within monolithic hydrogels containing a positive, neutral, or negative backbone. These hydrogels can be used as sensors for mercury detection since the DNA can selectively bind Hg(2+) between thymine bases inducing a hairpin structure. SYBR Green I can then bind to the hairpin to emit green fluorescence. For the neutral or negatively charged gels, addition of the dye in the absence of Hg(2+) resulted in intense yellow background fluorescence, which was attributed to SYBR Green I binding to the unfolded DNA. We found that, by introducing 20% positively charged allylamine monomer, the background fluorescence was significantly reduced. This was attributed to the repulsion between positively charged SYBR Green I by the gel matrix as well as the strong binding between the DNA and the gel backbone. The signal-to-background ratio and detection limit was, respectively, improved by 6- and 9-fold using the cationic gel instead of neutral polyacrylamide gel. This study helps understand the electrostatic interaction within hydrogels, showing that hydrogels can not only serve as a high capacity matrix for sensor immobilization but also can actively influence the interaction between involved molecules.