Natural polymers-enhanced double-network hydrogel as wearable flexible sensor with high mechanical strength and strain sensitivity

Conductive hydrogels have shown great prospects as wearable flexible sensors. Nevertheless, it is still a challenge to construct hydrogel-based sensor with great mechanical strength and high strain sensitivity. Herein, an ion-conducting hydrogel was fabricated by introducing gelatin-dialdehyde β-cyclodextrin (Gel-DACD) into polyvinyl alcohol-borax (PVA-borax) hydrogel network. Natural Gel-DACD network acted as mechanical deformation force through non-covalent cross-linking to endow the polyvinyl alcohol-borax/gelatin-dialdehyde β-cyclodextrin hydrogel (PGBCDH) with excellent mechanical stress (1.35 MPa), stretchability (400%), toughness (1.84 MJ/m³) and great fatigue resistance (200% strain for 100 cycles). Surprisingly, PGBCDH displayed good conductivity of 0.31 S/m after adding DACD to hydrogel network. As sensor, it showed rapid response (168 ms), high strain sensitivity (gage factor (GF) = 8.57 in the strain range of 200%-250%) and reliable sensing stability (100% strain for 200 cycles). Importantly, PGBCDH-based sensor can accurately monitor complex body movements (knee, elbow, wrist and finger joints) and large-scale subtle movements (speech, swallow, breath and facial expressions). Thus, PGBCDH shows great potential for human monitoring with high precision.     

Highly sensitive,stretchable and durable strain sensors based on conductive double-network polymer hydrogels

Hydrogel-based strain sensors have been attracting immense attention for wearable electronic devices owing to their intrinsic soft characteristics and flexibility. However, developing hydrogel sensors with hightensile strength, stretchability, and strain sensitivity remains a great challenge. Herein, we report a technique to synthesize highly sensitive hydrogel-based strain sensors by integrating carbon nanofibers (CNFs) with a double-network (DN) polymer hydrogel matrix comprising of a physically cross-linked agar network and a covalently cross-linked polyacrylamide (PAAm) network. The resultant nanocomposite sensors display superior piezoresistive sensitivity with a hightrue gauge factor (GF_T = 1.78) at an ultrahigh strain of 1,000%, a fast response time and linear correlation of ln(R/R₀) and ln(L/L₀) up to 1,000% strain. Most significantly, these sensors possess highmechanical strength (~0.6 MPa) and superb durability (>1,000 cycles at strain of 100%), stemming from the effective energy dissipation mechanism of the first agar network acting as sacrificial bonds and the CNFs serving as dynamic nanofillers. The combination of highstrain sensitivity and ultrahigh stretchability of hydrogel sensors makes it possible to sense both small mechanical deformations induced by human motions and large strain up to 1,000%.     

Application of sensitive hydrogels in chemical and pH sensors

In the present work, pH-sensitive poly(vinyl alcohol)/poly(acrylic acid) (PVA/PAA) blends as well as hydrogels based on poly(N-isopropylacrylamide) (PNIPAAm), which are sensitive to organic solvent concentration in aqueous solutions, were used in silicon micromachined sensors. A sensitivity of approximately 15 mV/pH was obtained for a pH sensor with a 50 μm thick PVA/PAA hydrogel layer in a pH range above the acid exponent of acrylic acid (pK_a=4.7). The output voltage versus pH-value characteristics and the long-term signal stability of hydrogel-based sensors were investigated and the measurement conditions necessary for high signal reproducibility were determined. The influence of the preparation conditions of the hydrogel films on the sensitivity and response time of the chemical and pH sensors is discussed.     

Non‐oxidized graphene/elastomer composite films for wearable strain and pressure sensors with ultra‐high flexibility and sensitivity

It remains challenging to prepare wearable strain and pressure sensors with excellent mechanical properties, ultra‐high flexibility and sensitivity. Electrically conductive graphene platelets (GnPs) with high structural integrity are used in making a composite film fabricated using robust fabrication techniques. The gauge factor for the strain is up to 100 at 0%‐5% strain and 50 at 5%‐30% strain, and the sensitivity to pressure is 2.7×10^‐2 kPa^‐1 between 0 and 10 kPa and 1.5×10^‐4 kPa^‐1 between 300 and 1000 kPa. In addition, the flexible sensor demonstrates good repeatability and durability after 1000 cycles of tensile and compression tests. The flexible sensor has fast response ability and a wide operating temperature range, suggesting the excellent response to temperature. The flexible sensor is applied in monitoring several human motions as a wearable device with high accuracy. The ability to detect strain, pressure and temperature of the flexible sensor extends its applications to multifunctional wearable devices.     

Strong and Ultra-tough Ionic Hydrogel Based on Hyperbranched Macro-Cross-linker: Influence of Topological Structure on Properties

The application of hydrogels often suffers from their inherent limitation of poor mechanical properties. Here, a carboxyl-functionalized and acryloyl-terminated hyperbranched polycaprolactone (PCL) was synthesized and used as a macro-cross-linker to fabricate a super strong and ultra-tough ionic hydrogel. The terminal acryloyl groups of hyperbranched PCL are chemically incorporated into the network to form covalent cross-links, which contribute to robust networks. Meanwhile, the hydrophobic domains formed by the spontaneous aggregation of PCL chains and coordination bonds between Fe³⁺ and COO⁻ groups serve as dynamic non-covalent cross-links, which enhance the energy dissipation ability. Especially, the influence of the hyperbranched topological structure of PCL on hydrogel properties has been well investigated, exhibiting superior strengthening and toughening effects compared to the linear one. Moreover, the hyperbranched PCL cross-linker also endowed the ionic hydrogel with higher sensitivity than the linear one when used as a strain sensor. As a result, this well-designed ionic hydrogel possesses high mechanical strength, superior toughness, and well ionic conductivity, exhibiting potential applications in the field of flexible strain sensors.     

Progress in hydrogels for sensing applications: a review

There are several developments taking place in the field of sensors driven by the world today requirements. One of the most important novelties of the last two decades in the field is represented by the hydrogel-based sensors which constitute a wide family of innovative smart sensing devices relevant for many different applications. Hydrogels in fact are hydrophilic, biocompatible and highly water swellable polymer networks able to convert chemical energy into mechanical energy, with the great peculiarity to be able to respond to external stimuli. These characteristics have ensured them considerable recognition as valuable tool for smart sensing and diagnostics. The aim of this review is to focus on the advances obtained in the field in the last ten years.     

Application of MXene in Electrochemical Sensors: A Review

Electroanalysis has obtained considerable progress over the past few years, especially in the field of electrochemical sensors. Broadly speaking, electrochemical sensors include not only conventional electrochemical biosensors or non-biosensors, but also emerging electrochemiluminescence (ECL) sensors and photoelectrochemical (PEC) sensors which are both combined with optical methods. In addition, various electrochemical sensing devices have been developed for practical purposes, such as multiplexed simultaneous detection of disease-related biomarkers and non-invasive body fluid monitoring. For the further performance improvement of electrochemical sensors, material is crucial. Recent years, a kind of two-dimensional (2D) nanomaterial MXene containing transition metal carbides, nitrides and carbonitrides, with unique structural, mechanical, electronic, optical, and thermal properties, have attracted a lot of attention form analytical chemists, and widely applied in electrochemical sensors. Here, we reviewed electrochemical sensors based on MXene from Nov. 2014 (when the first work about electrochemical sensor based on MXene published) to Mar. 2021, dividing them into different types as electrochemical biosensors, electrochemical non-biosensors, electrochemiluminescence sensors, photoelectrochemical sensors and flexible sensors. We believe this review will be of help to those who want to design or develop electrochemical sensors based on MXene, hoping new inspirations could be sparked.     

Hydrophobic association and ionic coordination dual crossed-linked conductive hydrogels with self-adhesive and self-healing virtues for conformal strain sensors

As a promising functional material, conductive hydrogel has attracted extensive attention, especially in flexible sensor field. Despite the recent developments, current hydrogels still experience several issues, such as limited stretchability, lack of self-recovery and self-healing capability, and insufficient self-adhesion. Herein, dual cross-linked (DC) poly (AA-co-LMA)_SDS/Fe³⁺ hydrogels are fabricated subtly on the basis of ionic coordination interactions and the poly (AA-co-LMA)_SDS hydrophobic association networks, which may provide one plausible routine to compensate the mentioned drawback of hydrogels. The hydrophobic association and ionic coordination networks work synergistically to endow the hydrogels remarkable stretchability (>1200%), high-fracture strength (≈ 820 kPa), and excellent self-healing capability. In addition, the DC hydrogel-based strain sensors displayed a broad sensing range (0 ∼ 900%), conspicuous sensitivity (strain 0% ∼ 200%, gauge factor = 0.53; strain 200% ∼ 500%, gauge factor = 1.23; strain 500% ∼ 900%, gauge factor = 2.09), and pronounced durability. What's more, the self-adhesive feature ensures the strain sensor always forming a good conformal contact with the skin during human movements and displaying remarkable bidirectional detection capability.     

Smart functionalized thin gel layers for electrochemical sensors,biosensors and devices

Combining hydrogels sensitive to external stimuli with conducting surfaces opens new possibilities in electrochemistry. Thin hydrogel layers as unique electrode-modifying materials provide highly permeable matrix for easy diffusion of analytes. In addition, larger individuals, for example, nanoparticles and enzymes, can be straightforwardly immobilized in the polymeric networks at electrode surfaces. Such properties are strongly desired for construction of sensors and biosensors. In addition, sensitivity to external stimuli allows to significantly enhance or weaken the electroanalytical signal. Recently, a significant number of articles concerning switchable sensors/biosensors, switchable electrochemical systems and signal–responsive interfaces have been published. This report is also focused on the construction of various devices based on electrode surfaces modified with smart hydrogel layers, for example, logic gates and electroresponsive hydrogel layers as potentially advanced drug delivery systems, artificial muscles and electrochemical valves.     

Flexible,stretchable and conductive PVA/PEDOT:PSS composite hydrogels prepared by SIPN strategy

Stretchable conductive hydrogels have received significant attention due to their possibility of being utilized in wearable electronics and healthcare devices. In this work, a semi-interpenetrating polymer network (SIPN) strategy was employed to fabricate a set of flexible, stretchable and conductive composite hydrogels composed of polyvinyl alcohol (PVA) in the presence of glutaraldehyde as the crosslinker, HCl as the catalyst and poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) as the conductive medium. The results from FTIR, Raman, SEM and TGA indicate that a chemical crosslinking network and interactions of PVA and PEDOT:PSS exist in the SIPN hydrogels. The swelling ratio of hydrogels decreased with increasing content of PEDOT:PSS. Due to the chemical crosslinking network and interactions of PVA and PEDOT:PSS, PVA networks semi-interpenetrated with PEDOT:PSS exhibited excellent tensile and compression properties. The tensile strength and elongation at breakage of the composite hydrogels with 0.14 wt% PEDOT:PSS were 70 KPa and 239%, respectively. The compression stress of the composite hydrogels with 0.14 wt% PEDOT:PSS at a strain of 50% was about 216 KPa. The electrical conductivity of the hydrogels increased with increasing PEDOT:PSS content. The flexible, stretchable and conductive properties endow the composite hydrogel sensor with a superior gauge factor of up to 4.4 (strain: 100%). Coupling the strain sensing capability to the flexibility, good mechanical properties and high electrical conductivity, we consider that the designed PVA/PEDOT:PSS composite hydrogels have promising applications in wearable devices, such as flexible electronic skin and sensitive strain sensors.     

Mechanical Properties of Bacterially Synthesized Nanocellulose Hydrogels

The mechanical characteristics of bacterially synthesized nano-cellulose (BNC) were studied with uniaxial compression and tensile tests. Compressive loads result in a release of water and the deformation of the water-saturated network corresponds approximately to the volume of released water. The BNC hydrogel exhibits a mainly viscous response under compression. The strain response under tensile loads has an elastic and a viscous component. This can be described with a Maxwell model, where the viscosity is strain rate-dependent. When the aqueous phase of the BNC hydrogel is stabilized with an additional alginate hydrogel matrix, the system exhibits an elastic response under compressive loads. The analysis of the ‘alginated’ BNC network with the Maxwell model shows that the alginate matrix increases the viscosity of the composite system. The results of the mechanical tests show that the water absorbed in the BNC hydrogel strongly influences its mechanical behavior.     

水凝胶仿生柔性电子学

水凝胶力学性质与生物组织相似,生物相容性好,在生物电子学领域具有独特的优势.受生物组织——如皮肤、神经、肌肉等启发,发展了具有仿生结构和功能的水凝胶材料.以这种水凝胶材料制作而成的柔性电子器件具有感知温度、压力、应变、电场等外界刺激的功能,可模拟生物组织的传感能力,在仿生电子皮肤,人工肌肉,人工神经等领域具有重要的应用...     

The influence of bending on the performance of flexible carbon black/polymer composite gas sensors

The performance of electronics on flexible substrates suffers under substrate bending leading to reduced device performance. In this article, we highlighted the influence of bending strain on a conductive polymer composite gas sensor and developed a model to investigate the influence of strain. We evaluated the strain influence on the resistance of a gas sensor with respect to sensitivity, filler content, cyclic loading, and electrode orientation. The sensitivity of gas sensors increased with decreasing tensile bending radii. The influence of strain was dominant for gas sensors with less carbon black concentration. Cyclic bending tests showed a decrease of sensor resistance versus time and a plastic deformation. A sensor geometry orientations effect to reduce the sensitivity to bending strain was achieved by aligning the electrode fingers parallel to the strain. A model was successfully implemented to simulate strain influences inside the polymer incorporating the Poisson ratio. We suggest a concept to achieve a strain insensitive gas sensor by creating an orientation between single particles inside the composite. Implementing this results into existing gas sensors will improve the measurement quality and reliability of sensors on flexible substrates. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Hofmeister效应辅助的蛋白质基水凝胶应变传感器

以酪蛋白酸钠和明胶为原料, 通过简单的在硫酸铵溶液中浸泡的方法, 借助Hofmeister效应制备了一种强韧导电的酪蛋白酸钠/明胶水凝胶, 克服了蛋白质基水凝胶柔软、 易碎的问题. 测试结果表明, 该水凝胶具有优异的机械性能, 最大拉伸应力为3.55 MPa, 最大拉伸应变为1375%; 水凝胶的最大电导率为0.0954 S/cm, 导电灵敏因子为0.53. 用该水凝胶制备的传感器对不同大小及不同速率的应变均具有分辨能力, 能够监测人体不同部位的运动, 且传感器的信号传输具有稳定性和准确性, 表明该水凝胶是监测人体健康和运动的理想材料. 该水凝胶还具有良好的形状记忆性能. 这一策略为制备全天然蛋白质基水凝胶开辟了新的思路, 扩展了水凝胶在生物医学和电子传感等相关领域的应用前景.     

Flexible,adhesive, strain-sensitive,and skin-matchable hydrogel strain sensors for human motion and handwritten signal monitoring

Flexible hydrogel strain sensors have made great progress in medical applications, human motion detection, and human-machine interactions. However, the design of hydrogels to realize the synergistic responses of excellent mechanical properties, robust adhesion, and stable sensing is still a highly challenging task. Herein, we report a multifunctional hydrogel (PAMT hydrogel) by crosslinking acrylic acid (AA), 2-methacryloyloxyethyl phosphorylcholine (MPC) and tannic acid (TA) to form a polymer network via a simple one-pot free radical polymerization. Among them, the dynamic bonding with hydrogen bonding between PAA chains and TA significantly improved the stretch ability of the hydrogels (700%), and the abundant catechol groups on TA endowed the hydrogels with strong and stable adhesion properties (the adhesion strength to glass reached 248 N m⁻¹). When applied to human skin, the hydrogel can be easily peeled off without leaving any residue. Furthermore, the strain sensor assembled using PAMT hydrogel could not only effectively detect the movement in different parts of the human body, but also be used for precise handwritten recognition and electric skin of silicone prosthetic hand. Due to the addition of MPC and TA, the conductive hydrogel has good biocompatibility and no harm to human body. Therefore, PAMT hydrogel has opened up a new vision for the development of intelligent detection and bionic intelligent robots.     

Pebax‐Based Membrane Filled with Two‐Dimensional Mxene Nanosheets for Efficient CO2 Capture

Mixed matrix membranes (MMMs) made from inorganic fillers and polymers is a kind of promising candidate for gas separation. In this work, two‐dimensional MXene nanosheets were synthesized and incorporated into a polyether‐polyamide block copolymer (Pebax) matrix to fabricate MMM for CO₂ capture. The physicochemical properties of MXene nanosheets and MXene/Pebax membranes were studied systematically. The introduction of MXene nanosheets provided additional molecular transport channels and meanwhile enhanced the CO₂ adsorption capacity, thereby enhancing both the CO₂ peremance and CO₂/N₂ selectivity of Pebax membrane. The optimized MXene/Pebax membrane with a MXene loading of 0.15 wt % displayed a high separation performance with a CO₂ permeance of 21.6 GPU and a CO₂/N₂ selectivity of 72.5, showing potential application in CO₂ capture.     

一种高透明、可拉伸导电水凝胶的制备及其在电容传感器中的应用

导电水凝胶由于具备良好的电学特性、可调节的机械性能、易于加工性和生物相容性等,是制备柔性电子设备的理想基材。本文使用马来酸与丙烯酰胺作为共聚单体,氯化锂作为导电离子,N,N'-二甲基双丙烯酰胺作为交联剂,使用光引发剂,采用原位光聚合的方式制备了一种导电水凝胶。制得的水凝胶可见光透过率高达93%,最大拉伸形变~380%,导电率最大为12 S/m。鉴于其优异的综合性能,实验中使用导电水凝胶制备了电容传感器并应用于人体活动监测。结果表明,制备的导电水凝胶电容传感器对不同程度的手指弯曲形变和不同力度的手指触碰均表现出灵敏的响应行为,为未来可穿戴柔性电子产品的发展起到了一定的推动作用。     

聚乙烯醇/聚吡咯复合导电水凝胶应变传感器的制备及性能

以聚乙烯醇(PVA)为原料, 植酸(PA)和氨基-聚倍半硅氧烷(NH₂-POSS, NP)为交联剂, 通过冻融循环法制得PVA/PA/NP复合水凝胶, 再以其为模板, 通过吡咯的原位聚合制得PVA/PA/NP-PPy复合导电水凝胶, 克服了聚吡咯材料易脆、 疏水的特性, 进一步改善了水凝胶的导电性和灵敏性. 循环拉伸实验结果表明该水凝胶具有良好的自回复能力, 电导率高达7.53 S/m, 从I-V曲线可知其作为柔性可穿戴应变传感器的最高检测电流可达 9.029 mA, 灵敏度因子可达6.796, I-T曲线表明该传感器可以准确地通过电流信号变化来监测人体的各种微小运动.     

Biomimetic Strain‐Stiffening Self‐Assembled Hydrogels

Supramolecular structures with strain‐stiffening properties are ubiquitous in nature but remain rare in the lab. Herein, we report on strain‐stiffening supramolecular hydrogels that are entirely produced through the self‐assembly of synthetic molecular gelators. The involved gelators self‐assemble into semi‐flexible fibers, which thereby crosslink into hydrogels. Interestingly, these hydrogels are capable of stiffening in response to applied stress, resembling biological intermediate filaments system. Furthermore, strain‐stiffening hydrogel networks embedded with liposomes are constructed through orthogonal self‐assembly of gelators and phospholipids, mimicking biological tissues in both architecture and mechanical properties. This work furthers the development of biomimetic soft materials with mechanical responsiveness and presents potentially enticing applications in diverse fields, such as tissue engineering, artificial life, and strain sensors.     

A hydrogel-based microfluidic device for the studies of directed cell migration

We have developed a hydrogel-based microfluidic device that is capable of generating a steady and long term linear chemical concentration gradient with no through flow in a microfluidic channel. Using this device, we successfully monitored the chemotactic responses of wildtype Escherichia coli (suspension cells) to alpha-methyl-DL-aspartate (attractant) and differentiated HL-60 cells (a human neutrophil-like cell line that is adherent) to formyl-Met-Leu-Phe (f-MLP, attractant). This device advances the current state of the art in microchemotaxis devices in that (1) it demonstrates the validity of using hydrogels as the building material for a microchemotaxis device; (2) it demonstrates the potential of the hydrogel based microfluidic device in biological experiments since most of the proteins and nutrients essential for cell survival are readily diffusible in hydrogel; (3) it is capable of applying chemical stimuli independently of mechanical stimuli; (4) it is straightforward to make, and requires very basic tools that are commonly available in biological labs. This device will also be useful in controlling the chemical and mechanical environment during the formation of tissue engineered constructs.