Microwave‐assisted preparation of temperature sensitive poly(N‐isopropylacrylamide) hydrogels in poly(ethylene oxide)‐600

In this article, a series of poly(N‐isopropylacrylamide) (PNIPAM)‐based hydrogels were prepared under microwave irradiation using poly(ethylene oxide)‐600 (PEO‐600) as reaction medium and microwave‐absorbing agent as well as pore‐forming agent. All of the temperature measurements, gel fractions, and FTIR analyses proved that the PNIPAM hydrogels were successfully synthesized. Within 1 min, the PNIPAM hydrogel with a 98% yield was obtained under microwave irradiation. The PNIPAM hydrogels thus prepared exhibited controllable properties such as pore size, equilibrium swelling ratios, and swelling/deswelling rates when changing the feed weight ratios of monomer (N‐isopropylacrylamide, NIPAM) to PEO‐600. These properties are well adapted to the different requirements for their potential application in many fields such as biomedicine. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:4177–4184, 2006     

Bioinspired Stimuli-Responsive Hydrogel with Reversible Switching and Fluorescence Behavior Served as Light-Controlled Soft Actuators

Stimuli-responsive materials with multiple functions occupy a significant position in the research of bionic artificial intelligence materials. It is a challenge to integrate rapid shape deformation and color change synergistically by a simple method in the same system. Herein, an effective strategy to develop an anisotropic bilayer hydrogel actuator with unified complex deformation and color change is proposed via combining the near-infrared (NIR) light-responsive graphene oxide/poly(N-isopropylacrylamide) (GO-PNIPAM) active hydrogel layer and an UV light-responsive fluorescent poly(acrylic acid [4-(1,2,2-triphenylvinyl)] benzyl ester/N-isopropylacrylamide) passive hydrogel layer. The actuator can undergo light-controlled sapphire fluorescence color change and complex shape deformation simultaneously or separately under light irradiation. It can be remotely manipulated without the requirement for additional reagents, and the irradiation dosage can be accurately modulated through adjusting the irradiation parameters. This work provides new perspectives of intelligent systems with synergistic multiple functions, including smart robots, environmental sensors, and intelligent biomimetic devices.     

近红外光响应氧化石墨烯/微凝胶复合智能水凝胶

设计合成了一种包含氧化石墨烯（GO）片层、聚（N-异丙基丙烯酰胺）（PNIPAM）微凝胶球体和PNIPAM链段的复合结构水凝胶。通过控制聚合时间得到负载双键且粒径不同的PNIPAM微凝胶,将其作为交联点与N-异丙基丙烯酰胺（NIPAM）聚合,GO作为纳米填料掺入水凝胶体系,GO片层上的含氧基团与NIPAM上的胺基产生氢键物理交联。此方法制备的复合水凝胶同时具有温度敏感和近红外光敏感特性,通过改变GO浓度、微凝胶的合成时间、NIPAM浓度等条件,水凝胶的光敏感性和温度敏感性得到提升。相比于传统PNIPAM水凝胶,此种复合水凝胶能够对光响应,实现非接触式控制形变,且响应速率快、响应程度高,可应用于光控开关等领域。     

Preparation and Characterization of Temperature‐Sensitive Poly(Styrene‐Butadiene‐Styrene)/Poly(N‐Isopropylacrylamide) Hydrogel Elastomer with Interpenetrating Polymeric Networks

A poly(styrene‐butadiene‐styrene)/poly(N‐isopropylacrylamide) (SBS/PNIPAM) hydrogel elastomer with interpenetrating polymeric network structure is prepared by using solution free radical polymerization in benzene/tetrahydrofuran solvent mixture. The characterizations of hydrogel elastomers are investigated by Fourier transform infrared spectroscopy, scanning electron microscope, rheology, equilibrium swelling studies, and oscillatory swelling study. Results show that these hydrogel elastomers exhibit a temperature‐sensitivity inherited from PNIPAM component at the temperature around 30 °C. Besides, change with tetrahydrofuran to different proportion in solvent mixtures, constituent, and properties as gel content, swelling capacity, mechanical strength and volume phase transition degree are affected deeply.     

PNIPAM/锂藻土纳米复合凝胶微球的制备及其弹性力学性能

利用微流控技术,以锂藻土作为交联剂,成功制备得到温度响应型聚（N-异丙基丙烯酰胺）（PNIPAM）与锂藻土的纳米复合凝胶微球,并利用一种简单的微步进单轴压缩装置,分别在25℃和37℃下对具有不同锂藻土含量的PNIPAM/锂藻土纳米复合凝胶微球的弹性力学性能进行系统研究。该微步进单轴压缩装置主要包括三个部分：一个程控进样器用以实现对凝胶微球的微步进压缩,一套配有高分辨率数码相机的侧视光学系统用以记录凝胶微球受压时发生的形变,一台精密电子天平作为力传感器用来记录凝胶微球在特定形变下所受的外力。研究结果表明,纳米复合凝胶微球在25℃和37℃下的形变量H与所受压力F的实验数据与Hertz弹性接触理论方程呈现良好的拟合关系,证明了PNIPAM/锂藻土纳米复合凝胶微球在25℃和37℃下均具有弹性形变行为。同时,随着锂藻土含量的增加,PNIPAM/锂藻土纳米复合凝胶微球的温敏性降低,但其杨氏模量增大。具有相同锂藻土含量的纳米复合凝胶微球,由于温度升高凝胶体积收缩、凝胶结构变得致密,因此在37℃下的杨氏模量大于其在25℃下的杨氏模量。研究结果可为PNIPAM/锂藻土纳米复合凝胶微球的设计与实际应用提供指导。     

Near‐Infrared Light‐Triggered Dual Drug Release Using Gold Nanorod‐Embedded Thermosensitive Nanogel‐Crosslinked Hydrogels

Gold nanorod (AuNR)‐embedded poly(N‐isopropylacrylamide) (PNIPAM) hydrogels offer the possibility of achieving near‐infrared (NIR) light‐triggered drug release. In addition, using nanoparticles as a crosslinker can enhance the mechanical properties of PNIPAM hydrogels, and nanoparticle‐crosslinked hydrogels provide an important approach for dual drug release. Here, NIR light‐triggered dual drug release using AuNR‐embedded thermosensitive nanogel‐crosslinked hydrogels is reported for the first time. Two kinds of drugs are encapsulated, one in the nanogel and the other in the hydrogel. The volume phase transition of the PNIPAM hydrogels is induced by NIR light by utilizing the photothermal effect of AuNRs. By changing the number of embedded AuNRs and the intensity of NIR light, the release rate and drug quantity can be adjusted for on‐demand release. Because of its NIR light‐triggering and nanoparticle‐crosslinking capabilities, AuNR‐embedded thermosensitive nanogel‐crosslinked hydrogels may expand the application scope of hydrogels and provide enhanced properties in their applications.     

A Novel NIR Laser Switched Nanocomposite Hydrogel as Remote Stimuli Smart Valve

Thermosensitive nanocomposite (NC) hydrogels are considered as a significant kind of intelligent material to be utilized as sensor, biomaterial, drug carrier, etc. Recently, preparation of remotely controlled NC hydrogel with high‐performance attracts more and more concern. To produce facile remote‐stimuli thermosensitive NC hydrogel, a novel near‐infrared (NIR) laser switched CuS/clay/poly(OEGMA‐co‐MEO₂MA) hydrogel is demonstrated, which can be precisely remote‐stimulated by NIR irradiation based on the excellent NIR photothermal conversion property of CuS nanoparticle. The temperature change of hydrogel is related to the NIR intensity, CuS content, and crosslinking density. Moreover, the influences on dimensional variation of hydrogel on macroscale are systematically studied, and the hydrogel as smart liquid valve is further utilized which can be remotely controlled by NIR switch on/off successfully. Cyclic test illustrates that this novel CuS/clay/poly(OEGMA‐co‐MEO₂MA) hydrogel exhibits stable cyclic volume transition property which has promising applications in the areas of sensors, valves, and intelligent switches.     

A Composite Thermo‐Responsive Membrane System for Improved Controlled‐Release

A novel composite thermo‐responsive membrane system for improved controlled‐release is successfully developed. The membrane is composed of a porous membrane with grafted poly(N‐isopropylacrylamide) (PNIPAM) gates acting as functional valves, and a cross‐linked PNIPAM hydrogel inside the reservoir acting as the solute carrier. The thermo‐responsive controlled‐release characteristics of the proposed system are studied when the ambient temperature is continuously increased from 20 to 45 °C (across the LCST of PNIPAM) at a constant rate of 1.5 °C/min. The experimental results show that the prepared system exhibits significantly better performance for thermo‐responsive controlled‐release than single‐functional systems currently in existence, due to the cooperative action of the gating membrane and the inner cross‐linked hydrogel. Furthermore, due to the distinctive composite architecture, the proposed system can overcome some inherent disadvantages of current systems, such as the drug security problem of the reservoir‐type systems and the mechanical strength problem of the hydrogel matrix‐type systems. The system proposed in this study provides a new mode for thermo‐responsive controlled‐release.     

温度感应复合型控制释放膜系统的性能研究

采用等离子诱导填孔接枝聚合法将聚N-异丙基丙烯酰胺(PNIPAM)开关接枝到聚偏氟乙烯膜(PVDF)膜孔上,同自由基聚合法制备的PNIPAM交联水凝胶结合,成功地组成了一种温度感应复合型控制释放膜系统。在该膜系统中,PNIPAM接枝PVDF膜作为控制释放开关,PNIPAM交联水凝胶作为药物载体。通过改变交联水凝胶和开关膜的微观结构,研究了该复合膜系统的温度感应控制释放特性。结果表明,该复合膜系统具有良好的温度感应特性,优于单独的开关膜控制释放系统或是单独的交联水凝胶控制释放系统。研究结果将为温度感应型控制释放系统或给药系统的设计与开发提供理论基础。     

Electrical sensitivity behavior of a hydrogel composed of polymethacrylic acid/poly(vinyl alcohol)

An interpenetrating polymer network (IPN) composed of polymethacrylic acid (PMAA) and poly(vinyl alcohol) (PVA) was prepared and exhibited electrical sensitivity behavior. The swelling behavior of the PMAA/PVA IPN hydrogel was studied by immersion of the gel in aqueous NaCl solutions at various concentrations and pH values. The stimuli response of the PMAA/PVA IPN hydrogel in electric fields was also investigated. When swollen IPN hydrogel was placed between a pair of electrodes, the PMAA/PVA IPN hydrogel exhibited bending behavior upon the application of an electric field. The PMAA/PVA IPN hydrogel also showed stepwise bending behavior depending on the electric stimulus. Also, for biomedical applications, the bending behavior of PMAA/PVA IPN hydrogel in Hank's solution at pH 7.4 was studied. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91:3613–3617, 2004     

Multi‐Wavelength Light Drivable Oscillatory Actuator on Graphene‐Based Bilayer Film

A multi‐wavelength light drivable bilayer actuator is fabricated by depositing a thin layer of reduced graphene oxide (RGO) onto a flexible poly(dimethyl siloxane) (PDMS) substrate. The RGO/PDMS bilayer film shows fast and reversible bending/unbending motions upon exposure to UV light, visible light, or near‐infrared light (NIR). The photo‐thermal effect of the pump lights is studied by measuring and comparing the light induced temperature rises on RGO/PDMS film. The results demonstrate that the RGO absorbs and converts the light into heat. Thus the bilayer film undergoes thermal expansion under light irradiation. The calculated thermal expansion of the RGO thin layer is smaller than that of the PDMS layer, which results in the bilayer actuator bending towards the layer on the RGO side. Oscillational motion on the bilayer film is successfully achieved using continuous light irradiation on an offset sandwiched RGO/PDMS bilayer cantilever. Light induced motion on the RGO based film provides a new strategy for absorbing light energy and outputting photomechanical work.

     

Electroactive characteristics of interpenetrating polymer network hydrogels composed of poly(vinyl alcohol) and poly(N‐isopropylacrylamide)

An interpenetrating polymer network (IPN) composed of poly(vinyl alcohol) (PVA) and poly(N‐isopropylacrylamide) (PNIPAAm) was prepared by the sequential IPN method. The equilibrium swelling ratio and bending behavior under electric fields of the IPN hydrogel were measured in an aqueous NaCl solution. The IPN exhibited a high equilibrium swelling ratio, in the range 280–380%. When the IPN in aqueous NaCl solution was subjected to an electric field, the IPN showed significant and quick bending toward the cathode. The IPN hydrogel also showed stepwise bending behavior, depending on the electric stimulus. In addition, the ionic conductivity of the IPN hydrogel was measured using dielectric analysis, and its conductive behavior followed the Arrhenius equation. The conductivity of the IPN hydrogel and the activation energy for the form of the IPN were 1.68 × 10^?5 S/cm at 36°C and 61.0 kJ/mol, respectively. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 890–894, 2003     

Effect of poly(ethylene glycol)-derived crosslinkers on the properties of thermosensitive hydrogels

Three crosslinkers, poly(ethylene glycol) diacrylate (PEGDA), glycerol ethoxylate triacrylate (GETA) and citric acid-(PEG acrylate)₃ (CA-PEGTA) derived from poly(ethylene glycol) (PEG) were synthesized at first. The three series of poly (N-isopropylacrylamide) (PNIPAAm) hydrogels were prepared by photopolymerization with the crosslinkers and compared with a hydrogel based on commercial crosslinker, N,N′-methylene bis-acrylamide (NMBA). The influence of the crosslinker structures and contents on the swelling behaviour, mechanical properties, and drug release of the hydrogels was investigated. The results showed that the hydrogels based on PEGDA and NMBA exhibited the highest and the lowest swelling ratio, respectively. The content of crosslinker of all hydrogel series showed good thermosensitivity and thermo-reversibility. The critical gel transition temperature (CGTT) appeared at 32 °C for the hydrogel based on NMBA, but appeared at about 34 °C for other hydrogels due to higher hydrophilicity of the crosslinker. In the mechanical properties, three-arms crosslinker GETA and CA-PEGTA led to higher mechanical strength than a linear crosslinker PEGDA. A hydrogel based on GETA (NG6) showed the highest shear modulus of 656.9 kPa and Young’s modulus of 1655.0 kPa. The hydrogels containing higher content of crosslinker revealed lower swelling ratio and higher mechanical strength. In the drug release, the hydrogels with higher swelling ratios showed higher drug absorbed. The highest release percentage of caffeine and vitamin B12 for hydrogel based on PEGDA (NP6) could reach 68.3% and 75.4%, respectively. In addition, the bound water and toxicity of the hydrogels were also investigated.

     

The composite hydrogel with “2D flexible crosslinking point” of reduced graphene oxide for strain sensor

Intelligent hydrogels with excellent flexibility, biocompatibility, and stimulus responsivity can mimic the functions of the skin to detect human motions. However, the low mechanical strength limits its application in the field of biomimetic materials. In this work, polyacrylamide-reduced graphene oxide (PAM-rGO) composite hydrogels were prepared by the combination of PAM and partially rGO, and their biomimetic strain sensors were studied. The rGO played the role of “2D flexible crosslinking point” in the composite hydrogel. Through the H-bonds between rGO and hydrogels, the toughness and strength of the composite hydrogel were enhanced. The maximum strain of the hydrogel changed from 751% to 1097%, and the maximum stress changed from 0.065 to 0.20 MPa. On the other hand, the interaction between the PAM backbone and the rGO provided a credible resistance response to the stimulation of strain. The better linear relationship between resistance and length was built, with R² of 0.992. Furthermore, the composite hydrogels were assembled into wearable devices to monitor human-motion, including fingers bending, elbows bending and walking. The experimental results showed that the PAM-rGO composite hydrogel had great potential in the field of bionic skin.     

Novel Thermoreversible Injectable Hydrogel Formulations Based on Sodium Alginate and Poly(N-Isopropylacrylamide)

Novel injectable thermoreversible hydrogel compositions with semi-interpenetrating network structure were prepared through the addition of sodium alginate (SA) to poly(N-isopropylacrylamide) (PNIPAM) aqueous solutions. The addition of the hydrophilic alginate strongly improved the stability against syneresis of the 15 wt% PNIPAM hydrogels formed at 37°C from less than 15 min in the absence of alginate to more than 7 days in the presence of 4 wt% SA. Besides the SA concentration, the hydrogel stability depended on the molecular weight and polydispersity of PNIPAM, being lower when a high molecular weight fraction was present. The phase transition temperature (T_ph) of the PNIPAM aqueous solutions decreased with alginate concentration, while the dynamic viscosity and elastic modulus of the hydrogels increased. By decreasing the PNIPAM molecular weight and polydispersity, the dynamic viscosity and elastic modulus of the PNIPAM–alginate hydrogels formed above T_ph diminished, while their viscoelastic behavior changed from predominantly elastic to predominantly viscous.     

Preparation of Ag/reduced graphene oxide reinforced copper matrix composites through spark plasma sintering: An investigation of microstructure and mechanical properties

The reduced graphene oxide (rGO) decorated with Ag nanoparticles was synthesized by the chemical reduction of graphene oxide in an aqueous solution containing AgNO₃, in the presence of hydrazine hydrate as a reducing agent. The reduction of graphene oxide was confirmed by FT-IR and raman spectroscopy analyses. The x-ray diffraction pattern and UV–visible investigations demonstrated the formation of Ag particles on the surface of rGO sheets. After successful decoration, the Ag/rGO nano-composite was used as the reinforcement in the copper matrix composite. Cu–Ag/rGO composites with different percentages of Ag/rGO (0.4, 0.8, 1.6 and 3.2 vol%.) were prepared by mechanical milling and spark plasma sintering (SPS). The effects of the Ag/rGO content on the consolidation process, micro-hardness, bending strength and also, fracture surface of the prepared samples were then investigated. The three-point bending strength of the sintered samples was increased from 285 to 472 MPa by the addition 0.8 vol%. of Ag/rGO, as compared to the pure Cu. Moreover, increasing the reinforcement content to the 3.2 vol%. Ag/rGO led to decreasing the bending strength to 433 MPa. The highest micro-hardness (81 Hv) was obtained for the composite sample containing the 1.6 vol%. Ag/rGO. By increasing Ag/r-GO as the reinforcement (3.2 vol%.), the Vickers hardness was decreased to 69 Hv. Also, investigation of the fracture surface morphology showed transformation of fracture mechanism from plastic changes to brittle ones by raising the Ag/rGO content volume from 0.8 to 1.6 vol %.     

自交联法合成相转变温度范围窄的聚(N-异丙基丙烯酰胺)水凝胶微球

在不使用交联剂的情况下,采用无皂乳液聚合法合成自交联聚(N-异丙基丙烯酰胺)(PNIPAM)水凝胶微球。固体13C NMR分析结果表明,PNIPAM水凝胶微球中存在因链转移反应形成的自交联点。自交联PNIPAM水凝胶微球的相转变温度范围很窄,接近非连续体积相转变行为。合成过程中反应温度、反应时间、引发剂用量对微球粒径和溶胀比有比较明显的影响,这些因素对微球的相转变温度及其范围的影响均很小。     

PEG-based hydrogel membrane coatings

As a first step towards preparing fouling-resistant coatings for water purification membranes, three series of copolymer hydrogel networks were synthesized using poly(ethylene glycol) diacrylate (PEGDA) as the crosslinker and acrylic acid (AA), 2-hydroxyethyl acrylate (HEA), or poly(ethylene glycol) acrylate (PEGA) as comonomers. Copolymers containing varying amounts of PEGDA with each of these comonomers were prepared. Glass transition temperatures obeyed the Fox equation. Crosslink density strongly influenced water uptake and water permeability for materials of constant chemical composition. For example, the volume fraction of water sorbed by a 100 mol% PEGDA hydrogel was 0.61. However, introducing comonomers into the network reduced hydrogel crosslink density, and in hydrogels having the same ethylene oxide content, water sorption increased as crosslink density decreased. The highest water volume fraction observed was 0.72, obtained in a copolymer containing 80 mol% PEGA and 20 mol% PEGDA. Water permeability increased systematically with increasing water sorption, and water permeability coefficients ranged from 10 to 26 L μm/(m² h bar). NaCl partition coefficients ranged from 0.36 to 0.53 (g NaCl/cm³ hydrogel)/(g NaCl/cm³ solution). NaCl diffusion coefficients varied little with polymer composition; in this regard, diffusion coefficient values ranged from 4.3 × 10⁻⁶ to 7.4 × 10⁻⁶ cm²/s. Based on contact angle measurements using n-decane in water, oil exhibited a low affinity for the surfaces of these polymers, suggesting that coatings prepared from such materials might improve the fouling resistance of membranes towards oily wastewater.     

Fabrication of thermo-responsive hydrogels from star-shaped copolymer with a biocompatible β-cyclodextrin core

A thermally reversible hydrogel composed of a three-arm star copolymer with a specific host β-cyclodextrin (β-CD) center has been developed. The synthesis of this star copolymer initiates with β-CD core, from which sequential polymerization of a temperature-responsive poly(N-isopropylacrylamide) (PNIPAM) block and a hydrophilic poly(N,N-dimethylacrylamide) (PDMA) block as asymmetric arms (named β-CD-g-(PNIPAM-b-PDMA)₃) is performed via RAFT protocol. Below the lower critical solution temperature (LCST) of PNIPAM segment, the polymer is of good water-solubility and exhibits a sol state. Upon thermal stimulus, free-standing hydrogels can be formed rapidly at sufficiently high concentrations. By comparing the sol–gel transition of the star polymer with that of its linear counterpart without this feature, we concluded that the special star-shape topology and the thermal-collapsed PNIPAM chains were responsible for this gelation behavior. The rheology measurements indicate the mechanical properties of the polymer hydrogels and the thermal reversibility of the sol–gel transition. Using Rhodamine B as a molecule to model a typical drug, we realize the favorable encapsulation and releasing process from the hydrogel, demonstrating that this star polymer has the potential to function as an injectable hydrogel for drug delivery and gene transport.     

Synthesis and Characterization of Injectable Photocrosslinking Poly (ethylene glycol) Diacrylate based Hydrogels

The poly (ethylene glycol) diacrylate (PEGDA)-based hydrogels were prepared by UV radiation under nitrogen, using PEGDA and 2-hydroxyethyl methacrylate (HEMA) as precursors. The PEGDA and HEMA precursors were respectively added into distilled water at a predetermined feed ratio. 2-Hydroxy-1-[4-(hydroxyethoxy)phenyl]-2-methyl-1-propanone (Irgacure2959) was used as a photoinitiator. The PEGDA-based hydrogels were characterized by FT-IR spectra, interior morphology, equilibrium swelling ratio, and Dynamic contact angle (DCA). The results showed: (1) -C=C- bonds of PEGDA and HEMA disappeared after photocrosslinking, which indicated hydrogel formation by consuming -C=C- bonds; (2) swelling ratio of the hydrogels were greatly influenced by the additive precursor ratios and microporous net; (3) with HEMA content increasing in PEGDA-based hydrogels, equilibrium water content (EWC) increased and the contact angle decreased, which resulted from the strong H-bonding interactions of HEMA between the polymer and water.