Muscle‐Inspired Highly Anisotropic,Strong, Ion‐Conductive Hydrogels

Biological tissues generally exhibit excellent anisotropic mechanical properties owing to their well‐developed microstructures. Inspired by the aligned structure in muscles, a highly anisotropic, strong, and conductive wood hydrogel is developed by fully utilizing the high–tensile strength of natural wood, and the flexibility and high‐water content of hydrogels. The wood hydrogel exhibits a high–tensile strength of 36 MPa along the longitudinal direction due to the strong bonding and cross‐linking between the aligned cellulose nanofibers (CNFs) in wood and the polyacrylamide (PAM) polymer. The wood hydrogel is 5 times and 500 times stronger than the bacterial cellulose hydrogels (7.2 MPa) and the unmodified PAM hydrogel (0.072 MPa), respectively, representing one of the strongest hydrogels ever reported. Due to the negatively charged aligned CNF, the wood hydrogel is also an excellent nanofluidic conduit with an ionic conductivity of up to 5 × 10^?4 S cm^–1 at low concentrations for highly selective ion transport, akin to biological muscle tissue. The work offers a promising strategy to fabricate a wide variety of strong, anisotropic, flexible, and ionically conductive wood‐based hydrogels for potential biomaterials and nanofluidic applications.     

基于高缠结纤维素水凝胶的力学作用机制研究

采用丙烯酰胺（AM）和羧甲基纤维素（CMC）构建高力学性能双网络（DN）水凝胶,探讨第一网络聚丙烯酰胺（PAM）的交联与缠结以及第二网络CMC的氢键作用,对水凝胶力学性能的作用机制。研究结果表明：对于第一网络,PAM在C=10-5（C=n交联剂/n单体为水凝胶的交联度）下能形成显著的缠结结构,在应力作用下能通过滑动分子链逐渐形成缠结结构来实现能量耗散;PAM在C=10-2下会形成高交联网络,在应力作用下通过化学键的断裂来耗散能量。对于第二网络,当水凝胶中CMC的质量分数Q=5.0%时,通过冻融能形成显著的氢键,并有效提高网络的作用力,从而提高水凝胶的力学性能。在C=10-5、Q=5.0%时,水凝胶的应力达到0.328 MPa。CMC较大的渗透压会引起凝胶的溶胀,降低聚合物密度。此外,引入CMC还会影响第一网络PAM的缠结结构。     

Study on graphene-oxide-based polyacrylamide composite hydrogels

In this paper, graphene oxide (GO) is added into poly(acrylamide) (PAM) hydrogels to modify their mechanical and thermal properties. The original PAM hydrogels, which are commonly crosslinked by N,N-methylenebisacrylamide (BIS), generally exhibit pronounced weakness and brittleness. After adding the GO into the hydrogel (BIS-gel), the GO–BIS-gels become very tough and exhibit fairly good tensile properties. The mechanical and thermal properties of GO–BIS-gels vary greatly by changing GO or BIS content. This phenomenon is probably caused by the microstructure, which related to the specific combination of GO sheets and BIS, acting as multifunctional crosslinking agents in the GO–BIS-gels. However, the BIS-gels have higher equilibrium swelling ratio than that of corresponding GO–BIS-gels. Contents of GO and BIS can be adjusted for preparing hydrogels with different applications.     

Graphene/TiO<Subscript>2</Subscript> hydrogel: a potential catalyst to hydrogen evolution reaction

In this study, graphene was synthesized from graphite. Graphite was oxidized via modified Hummer’s method and sonicated to form graphene oxide (GO). Infrared spectroscopy revealed the successful oxidation of graphite by the emergence of oxygen functionalities. The spectrum of GO showed peaks at 3270, 1629, 1227 and 1096 cm^?1, indicating O–H, C=O, C–OH and C–O–C functional groups, respectively. Graphene hydrogels were prepared by the addition of L-ascorbic acid to GO suspensions and subsequent heating at 90^°C. Composite hydrogels of graphene and titanium (IV) oxide (TiO₂) were synthesized with various TiO₂ to GO mass ratios. Composites were applied to photocatalytic hydrogen evolution reaction (HER) and the hydrogen gas produced was analysed by gas chromatography with thermal conductivity detector. Highest HER yield was 66.00% H₂.     

Composite Microgels Created by Complexation between Polyvinyl Alcohol and Graphene Oxide in Compressed Double‐Emulsion Drops

Microgels, microparticles made of hydrogels, show fast diffusion kinetics and high reconfigurability while maintaining the advantages of hydrogels, being useful for various applications. Here, presented is a new microfluidic strategy for producing polymer‐graphene oxide (GO) composite microgels without chemical cues or a temperature swing for gelation. As a main component of microgels, polymers that are able to form hydrogen bonds, such as polyvinyl alcohol (PVA), are used. In the mixture of PVA and GO, GO is tethered by PVA through hydrogen bonding. When the mixture is rapidly concentrated in the core of double‐emulsion drops by osmotic‐pressure‐driven water pumping, PVA‐tethered GO sheets form a nematic phase with a planar alignment. In addition, the GO sheets are linked by additional hydrogen bonds, leading to a sol–gel transition. Therefore, the PVA–GO composite remains undissolved when it is directly exposed to water by oil‐shell rupture. These composite microgels can be also produced using poly(ethylene oxide) or poly(acrylic acid), instead of PVA. In addition, the microgels can be functionalized by incorporating other polymers in the presence of the hydrogel‐forming polymers. It is shown that the multicomponent microgels made from a mixture of polyacrylamide, PVA, and GO show an excellent adsorption capacity for impurities.     

Photodetachable Adhesion

Peeling from strong adhesion is hard, and sometimes painful. Herein, an approach is described to achieve both strong adhesion and easy detachment. The latter is triggered, on‐demand, through an exposure to light of a certain frequency range. The principle of photodetachable adhesion is first demonstrated using two hydrogels as adherends. Each hydrogel has a covalent polymer network, but does not have functional groups for bonding, so that the two hydrogels by themselves adhere poorly. The two hydrogels, however, adhere strongly when an aqueous solution of polymer chains is spread on the surfaces of the hydrogels and is triggered to form a stitching polymer network in situ, in topological entanglement with the pre‐existing polymer networks of the two hydrogels. The two hydrogels detach easily when the stitching polymer network is so functionalized that it undergoes a gel–sol transition in response to a UV light. For example, two pieces of alginate–polyacrylamide hydrogels achieve adhesion energies about 1400 and 10 J m^?2, respectively, before and after the UV radiation. Experiments are conducted to study the physics and chemistry of this strong and photodetachable adhesion, and to adhere and detach various materials, including hydrogels, elastomers, and inorganic solids.     

Effect of Multiwalled Carbon Nanotubes on the Conductivity and Swelling Properties of Porous Polyacrylamide Hydrogels

Multiwalled carbon nanotubes (MWCNTs) were added to polyacrylamide (PAM) hydrogels in different proportions to tune their electrical and mechanical properties. The choice of MWCNTs as a reinforcement is justified by the fact that these are highly conducting, fairly stable and flexible particles. A series of MWCNT/PAM hydrogels were prepared by freezing method. The characteristic absorption peaks at 1480 and 1213 cm^?1 in the FTIR spectra reveal that MWCNTs are embedded in the PAM hydrogels. Powder x-ray diffractograms and thermogravimetric analysis (TGA) images show that the MWCNT/PAM hydrogels are crystalline, more thermally stable and have a higher electrical conductivity than a traditional PAM hydrogel. Scanning electron micrographs reveal about reduced pore size, homogeneous and denser texture. The swelling properties of all these hybrid hydrogels were found to be better than those of the parent PAM hydrogel. The Li–Tanaka equation was employed to produce the swelling parameters. The diffusion coefficients (D _c ) of PAM hydrogel is 10 times higher than the literature value. 0.8% MWCNTs reinforced PAM hydrogel has excellent τ_c and electrical conductivity (0.76 mS/cm) with improvements in all properties. Lower D _c of 0.8% MWCNTs/PAM hydrogel reveal that extent of crosslinking is much important than density of the system for a better collective diffusion of the respective solvent.     

Graphene oxide-filled conducting polyaniline composites as methanol-sensing materials

Polyaniline/graphene oxide (PANI/GO) composites were prepared by polymerization of aniline monomer in the presence of GO under acidic conditions. The synthesized samples were characterized by Fourier transform infra red spectroscopy, ultraviolet–visible absorption, Raman spectroscopy, X-ray diffraction, scanning electron microscopy, transmission electron microscopy and thermogravimetric analysis. The direct current electrical conductivity of the composite was calculated by a four-probe technique. It is found that the conductivity dramatically increased to 241 S m^?1 for PANI/GO (5 wt%) composite at 110 °C compared to pure PANI (7.5 S m^?1). The composite material was investigated as a methanol vapour sensor and compared with pure PANI. The methanol-sensing characteristics of the prepared composite was monitored by measuring the change in electrical resistivity on exposure to methanol vapour at different concentrations. The resistivity of PANI increases on exposure to methanol vapour because of strong hydrogen bonding between methanol with the polymer chain. A density functional theory study was carried out to verify the proposed concept of hydrogen bonding between the polymer chains and methanol. The presence of GO in PANI/GO composite increases the sensitivity towards methanol as compared with the pure PANI.     

Preparation and characterization of pH- and temperature-responsive nanocomposite double network hydrogels

A methodology is described for the preparation of pH- and temperature-responsive double network (DN) hydrogels with poly(N-isopropylacrylamide) (PNIPAM) as a tightly crosslinked 1st network, polyacrylic acid (PAA) as a loosely crosslinked 2nd network and graphene oxide (GO) as an additive. GO sheets were first prepared via an oxidation reaction and then dispersed in NIPAM aqueous solution via silanization. Free-radical polymerization of NIPAM was carried out at 20 °C in a water bath, and then subjected to UV light, leading to the formation of pH- and temperature-responsive PNIPAM/AA/GO DN hydrogels. The effects of GO sheets and AA contents on various physical properties were investigated. Results show that PNIPAM/AA/GO hydrogels undergo a large volumetric change in response to temperature. It also exhibits significantly fast swelling/deswelling compared with conventional PNIPAM hydrogel. Moreover, the PNIPAM/AA/GO hydrogels have a much better mechanical property than the conventional PNIPAM hydrogels.     

Ultralight,Heat-Insulated,and Tough PVA Hydrogel Hybridized with SiO2@cellulose Nanoclaws Aerogel via the Synergy of Hydrophilic and Hydrophobic Interfacial Interactions

Lightweight porous hydrogels provide a worldwide scope for functional soft mateirals. However, most porous hydrogels have weak mechanical strength, high density (>1 g cm⁻³), and high heat absorption due to weak interfacial interactions and high solvent fill rates, which severely limit their application in wearable soft-electronic devices. Herein, an effective hybrid hydrogel-aerogel strategy to assemble ultralight, heat-insulated, and tough polyvinyl alcohol (PVA)/SiO₂@cellulose nanoclaws (CNCWs) hydrogels (PSCG) via strong interfacial interactions with hydrogen bonding and hydrophobic interaction is demonstrated. The resultant PSCG has an interesting hierarchical porous structure from bubble template (≈100 µm), PVA hydrogels networks introduced by ice crystals (≈10 µm), and hybrid SiO₂ aerogels (<50 nm), respectively. PSCG shows unprecedented low density (0.27 g cm⁻³), high tensile strength (1.6 MPa) & compressive strength (1.5 MPa), excellent heat-insulated ability, and strain-sensitive conductivity. This lightweight porous and tough hydrogel with an ingenious design provides a new way for wearable soft-electronic devices.     

Oxygen vacancies facilitated photocatalytic detoxification of three typical contaminants over graphene oxide surface embellished BiOCl photocatalysts

A conventional solvothermal way was used to synthesize graphene oxide (GO)/BiOCl photocatalytic nanomaterials with enhanced photocatalytic performance. Due to the introduction of GO, there are intuitive changes in morphology, indicating that GO can guide the growth of GO/BiOCl catalysts. The results of X-ray photoelectron spectroscopy (XPS) and Raman show that a strong chemical interaction occurs around GO and BiOCl. The results of trapping experiments show that O₂^– is the major active species. XPS analysis confirms that the 0.75% GO/BiOCl produces the highest level of oxygen vacancies (OVs). All the GO/BiOCl photocatalysts possess better photocatalytic properties than the neat BiOCl, and 0.5% GO/BiOCl exhibits the highest photoactivity. The photocatalytic activity of 0.5% GO/BiOCl composite for detoxification of rhodamine B (RhB) and tetracycline (TC) under visible light illumination is 4.6 and 6.3 times of that on the reference BiOCl, separately, the photocatalytic activity of 0.5% GO/BiOCl for detoxication of perfluorooctanoic acid (PFOA) is 1.25 times of that of the single BiOCl under UV light illumination, which can be credited to the high separation rate of carriers and the strong interaction between GO and BiOCl. Combining with the results, a separation and transfer mechanism of carriers was revealed.     

Amorphous Ruthenium‐Sulfide with Isolated Catalytic Sites for Pt‐Like Electrocatalytic Hydrogen Production Over Whole pH Range

Electrocatalytic hydrogen evolution reaction (HER) is an efficient way to generate hydrogen fuel for the storage of renewable energy. Currently, the widely used Pt‐based catalysts suffer from high costs and limited electrochemical stability; therefore, developing an efficient alternative catalyst is very urgent. Herein, one pot hydrothermal synthesis is reported of amorphous ruthenium‐sulfide (RuS_x) nanoparticles (NPs) supported on sulfur‐doped graphene oxide (GO). The as‐obtained composite serves as a Pt‐like HER electrocatalyst. Achieving a current density of ?10 mA cm^?2 only requires a small overpotential (?31, ?46, and ?58 mV in acidic, neutral, and alkaline electrolyte, respectively) with high durability. The isolated Ru active site inducing Volmer–Heyrovsky mechanism in the RuS_x NPs is demonstrated by the Tafel analysis and X‐ray absorption spectroscopy characterization. Theoretical simulation indicates the isolated Ru site exhibits Pt‐like Gibbs free energy of hydrogen adsorption (?0.21 eV) therefore generating high intrinsic HER activity. Moreover, the strong bonding between the RuS_x and S–GO, as well as pH tolerance of RuS_x are believed to contribute to the high stability. This work shows a new insight for amorphous materials and provides alternative opportunities in designing advanced electrocatalysts with low‐cost for HER in the hydrogen economy.     

聚丙烯酰胺/氧化石墨纳米复合材料的研究

氧化石墨具有良好的层状结构，其层间具有丰富的官能团，能与有机聚合物形成插层纳米复合材料进而改善材料的性能．采用层离吸收-原位聚合法制备了聚丙烯酰胺／氧化石墨纳米复合材料，并采用XRD、HREM及DSC等对其结构和性能进行了表征。结果表明，聚丙烯酰胺与氧化石墨两者之间存在着较强的相互作用，材料的玻璃化转变温度得到提高，层离吸收-原位聚合法是获得聚丙烯酰胺／氧化石墨层纳米复合材料的有效途径，聚丙烯酰胺在氧化石墨中存在着多种排列方式，不同层间距(1．6nm和2．8nm)的聚丙烯酰胺／氧化石墨纳米复合结构同时存在。     

Microfluidic-Assisted Self-Assembly of 2D Nanosheets toward in situ Generation of Robust Nanofiber Film

Methods allow the enhancement of nanofibers via self-assembly are potentially important for new disciplines with many advantages, including multi-anchor interaction, intrinsic mechanical properties and versatility. Herein, a microfluidic-assisted self-assembly process to construct hydroxyl functionalized boron nitride nanosheets (OH−BNNS)/graphene oxide (GO)/thermoplastic polyurethane (TPU) composite nanofiber film, in which stable and precisely controlled self-assembly is fulfilled by the confined ultra-small-volume chip is demonstrated. Multiple fine structural analyses alongside with the density-functional theory (DFT) calculations are implemented to confirm the synergistic effect of noncovalent interactions (hydrogen bonding interaction, π – π stacking interaction, and van der Waals attraction) plays a critical role in the robust micro-structure and a massive 700% enhancement of mechanical strength via adding only 0.3 wt% OH−BNNS and GO. Importantly, profiled from broadband optical absorption ability, robust mechanical properties and outstanding flexibility, the self-assembled 3D OH−BNNS/GO/TPU nanofiber film reveals an adorable evaporation rate of 4.04 kg m⁻² h⁻¹ under one sun illumination with stable energy transfer efficiency (93.2%) by accompanying hydrogen bonding interaction. This microfluidic-assisted self-assembly strategy will provide a constructive entry point for the rational design of nanofibers and beyond.     

疏水缔合聚丙烯酰胺水凝胶的研制及自愈机理

采用疏水缔合的物理交联方式,将十二烷基硫酸钠(SDS)、氯化钠(NaCl)、甲基丙烯酸十八烷酯(SMA)反应所得的可聚合胶束与丙烯酰胺(AM)共聚缩合,制备出具有自愈合特性的聚丙烯酰胺(PAM)水凝胶,采用动态光散射测试、扫描电镜、红外光谱、热分析等表征手段对其理化性能进行了研究,并对其自愈合机理进行分析探讨。结果表明,制备所得PAM水凝胶含水率可达95%左右;SMA含量对PAM水凝胶含水率影响不明显,但SMA含量越高,所得水凝胶网络结构越紧密,孔隙尺寸越小,抗压强度、韧性和自愈率越高,但拉伸强度却随之下降。优选出的最佳工艺参数为:7%g/mL SDS溶液加入0.9 mol/L NaCl溶液中所得胶束尺寸最大,且疏水单体SMA的摩尔分数为AM单体的2%时,所得PAM水凝胶的抗拉强度和自愈率均最佳。     

Incorporating Chaotropic/Kosmotropic Chemistries onto Plasmonic Nanoheater to Boost Steam Generation Beyond its Photothermal Property

Photothermal steam generation promises decentralized water purification, but current methods suffer from slow water evaporation even at high photothermal efficiency of ≈98%. This drawback arises from the high latent heat of vaporization that is required to overcome the strong and extensive hydrogen bonding network in water for steam generation. Here, light-to-vapor conversion is boosted by incorporating chaotropic/kosmotropic chemistries onto plasmonic nanoheater to manipulate water intermolecular network at the point-of-heating. The chaotropic-plasmonic nanoheater affords rapid light-to-vapor conversion (2.79 kg m⁻² h⁻¹ kW⁻¹) at ≈83% efficiency, with the steam generation rate up to 6-fold better than kosmotropic platforms or emerging photothermal designs. Notably, the chaotropic-plasmonic nanoheater also lowers the enthalpy of water vaporization by 1.6-fold when compared to bulk water, signifying that a correspondingly higher amount of steam can be generated with the same energy input. Simulation studies unveil chaotropic surface chemistry is crucial to disrupt water hydrogen bonding network and suppress the energy barrier for water evaporation. Using the chaotropic-plasmonic nanoheater, organic-polluted water is purified at ≈100% efficiency, a feat otherwise challenging in conventional treatments. This study offers a unique chemistry approach to boost light-driven steam generation beyond a material photothermal property.     

Radiation synthesis of PVP/alginate hydrogel containing nanosilver as wound dressing

Hydrogels with polyvinyl pyrrolidone (PVP) and alginate were synthesized and silver nanoparticles were incorporated in hydrogel network using gamma radiation. PVP (10?and 15?%) in combination with 0.5?and 1?% alginate was gamma irradiated at different doses of 25?and 40?kGy. Maximum gel percent was obtained with 15?% PVP in combination with 0.5?% alginate. The fluid absorption capacity for the PVP/alginate hydrogels was about 1881–2361?% at 24?h. Moisture vapour transmission rate (MVTR) of hydrogels containing nanosilver at 24?h was 278.44?g/(m²h). The absorption capacity and moisture permeability of the PVP/alginate–nanosilver composite hydrogel dressings show the ability of the hydrogels to prevent fluid accumulation in exudating wound. The hydrogels containing nanosilver demonstrated strong antimicrobial effect and complete inhibition of microbial growth was observed with 70?ppm nanosilver dressings. PVP/alginate hydrogels containing nanosilver with efficient fluid handling capacity and antimicrobial activity was found suitable for use as wound dressing.     

Interfacial stability of graphene-based surfaces in water and organic solvents

The mass production of graphene and graphene oxide (GO) is essential for its use in commercial products. To improve its processing in the solution, dispersion behavior of graphene-based materials and their colloidal stability must be further understood. This study used all-atom molecular dynamics simulations to understand how electrostatics, van der Waals interactions, and hydrogen bonding affect the exfoliation and stability of three-layered graphene as a function of oxidation and solvent. Water, methanol, and ethanol were chosen as solvents due to their various dispersion behaviors. Our study indicated that (1) both surface oxidation level and solvent type can heavily influence the stability and (2) a decrease in interlayer vdW interactions, an increase in GO–solvent electrostatic interactions, and an increase in GO–solvent hydrogen bonding are important factors that can facilitate the dissolution of GO.     

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...     

Biomimetic patterning of polymer hydrogels with hydroxyapatite nanoparticles

We report here an in situ process to produce nano-composite polymer hydrogels having surfaces patterned with hydroxyapatite (HA) nanoparticles (100 nm). Poly (vinyl alcohol) (PVA) has been used as a hydrogel forming medium. A three step process, comprising precipitation of HA nanoparticles in presence of PVA molecules and freeze thawing of obtained PVA-HA emulsion, followed by critical point drying, has been devised to produce three dimensional nanocomposite hydrogels. Interaction of Ca²⁺ with oxygen atoms of PVA and the hydrogen bonding characteristic of the polymer have been exploited to have controlled size distribution of HA in a continuous and macroporous network of PVA. A systematic variation in the polymer concentration could be correlated with microstructural features of the hydrogel.