Fabrication strategies and application fields of novel 2D Ti3C2Tx (MXene) composite hydrogels: A mini-review

Ti₃C₂T_x (MXene), a new kind of 2D ceramic nanosheets, is receiving more and more attention in the fields of medicine, biology, energy, electronics, etc. However, the preparation and application of MXene in hydrogel is still in its infancy period. Here, we review the latest progress (after 2018) related to MXene hydrogels in time. Aiming at the key issue of the dispersion stability of MXene in hydrogel systems, the preparation strategy, mechanism, advantages and disadvantages of MXene hydrogels are sorted out in detail, and the potential application prospects of MXene composite hydrogel are introduced. Finally, future viewpoints are put forward for the dispersion stability challenges that need solving in the design of MXene hydrogel.     

Concurrent effect of microporosity and chemical structure on the equilibrium sorption properties of cellulose-based hydrogels

Polyelectrolite hydrogels are crosslinked polymers which display high sorption capacity in water and water solutions. They are widely used in the marked of personal hygiene products, as well as in other biomedical and industrial applications. In the most industrial application they are not biodegradable and prepared starting from acrylamide.In this work, the chemical-physical analysis of a novel class of natural polymers-based microporous superabsorbent hydrogels has been presented. The main focus is the definition of the relationship between material's chemical-physical structure and its equilibrium sorption properties.The effect of the variation of the degree of crosslinking, the polyelectrolyte nature of the backbone and the hydrogel microporosity on its swelling properties has been analysed, and a good agreement with the theoretical statements has been displayed.The effect of the ionic strength and the pH of the external solution in contact with the hydrogel on its equilibrium sorption properties has also been assessed, and an high sensitivity to these variations was detected for all the tested chemical compositions and physical structures.This work have to be considered part of the efforts towards the reduction of the environmental impact of the large scale consumption industrial polymer based products.     

Dye adsorption characteristics of alginate/polyaspartate hydrogels

This study examined the removal of some basic dyes, such as Methylene Blue, Malachite Green and Methyl Orange, using alginate or alginate/polyaspartate composite gel beads. The adsorption of dyes from aqueous solutions at 25 °C was examined using a batch sorption technique. The effects of CaCl₂ and the dye concentration on the adsorption were examined. Type-S adsorption isotherms were obtained, which is characteristic of a weak solute–solid interaction. The ionic interaction between the dye molecule and gel matrix appears to be responsible for the efficient adsorption of cationic dyes in this system. These results suggest that an alginate/polyaspartate gel can be used as an effective sorbent for water pollutants such as dyes, and the immobilization of these organic contaminants in the hydrogels from wastewater can solve one of the most important environmental problems in the related industry.     

The microscopy cell (MicCell), a versatile modular flowthrough system for cell biology, biomaterial research, and nanotechnology

We describe a novel microfluidic perfusion system for high-resolution microscopes. Its modular design allows pre-coating of the coverslip surface with reagents, biomolecules, or cells. A poly(dimethylsiloxane) (PDMS) layer is cast in a special molding station, using masters made by photolithography and dry etching of silicon or by photoresist patterning on glass or silicon. This channel system can be reused while the coverslip is exchanged between experiments. As normal fluidic connectors are used, the link to external, computer-programmable syringe pumps is standardized and various fluidic channel networks can be used in the same setup. The system can house hydrogel microvalves and microelectrodes close to the imaging area to control the influx of reaction partners. We present a range of applications, including single-molecule analysis by fluorescence correlation spectroscopy (FCS), manipulation of single molecules for nanostructuring by hydrodynamic flow fields or the action of motor proteins, generation of concentration gradients, trapping and stretching of live cells using optical fibers precisely mounted in the PDMS layer, and the integration of microelectrodes for actuation and sensing.     

Microscale analysis of patterning reactions via FTIR imaging: Application to intelligent hydrogel systems

A novel application of FTIR imaging for real-time characterization of patterning polymerization processes with microscale spatial resolution is presented. These methods will enable the microscale analysis of the reactions of polymeric systems with various substrates and devices. Specifically, intelligent hydrogels containing ionic groups (pH responsive) and poly(ethylene glycol) have been micropatterned onto gold surfaces, and the free-radical polymerization reaction has been characterized. It was demonstrated that differences in the reaction rates across a patterned region could be successfully resolved and characterized. This novel characterization method based on FTIR imaging will facilitate the optimization of integration processes of patterned polymeric films leading to enhanced (and reproducible) application of these materials as functional components in a variety of microdevices.     

Effect of composition on gelation kinetics of unfilled and nanoapatite-filled poly(lactide-ethylene oxide-fumarate) hydrogels

Oscillatory shear rheometry at small strains was used to investigate the effects of composition (concentration of macromer, crosslinker, initiator/accelerator, and filler) on the gel point and ultimate storage modulus of poly(l-lactide-co-ethylene oxide-co-fumarate) (PLEOF) hydrogels. PLEOF in situ polymerizing hydrogels can be used as biodegradable scaffolds for cell encapsulation and tissue regeneration. The time evolution of the viscoelastic properties of the polymerizing mixture during the sol-gel transition was monitored using mechanical rheometry. According to the results, while the ultimate storage modulus linearly increased with the concentration of methylene bisacrylamide (BISAM) crosslinker, the values of the storage and loss moduli at the gel point were insensitive to the concentration of BISAM. Similar behavior was observed for PLEOF hydrogels reinforced with hydroxyapatite nanoparticles.     

Water structure and improved mechanical properties of phospholipid polymer hydrogel with phosphorylcholine centered intermolecular cross-linker

We investigated the water structure and the mechanical properties of 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer hydrogels cross-linked with a novel hydrophilic 2-(methacryloyloxy)ethyl-[N-(2-methacryloyloxy)ethyl]phosphorylcholine (MMPC) for soft contact lenses (SCL) applications and commercial methacrylic cross-linkers were in addition used for comparison with MMPC. Water structure in hydrogels, which influences the protein adsorption by dehydration was determined by differential scanning calorimetry. MMPC increased the freezing water content of the MPC polymer hydrogel compared with hydrophilic N,N′-methylenebisacrylamide (BIS) at the same water content. MMPC also improved fracture strength of the MPC polymer hydrogel to 120 kPa in tensile, which was considerably higher than that hydrogel cross-linked with BIS. It is suggested that MMPC shows higher cross-linking reactivity with MPC than BIS. We concluded that the MMPC increase both the free water content and the tensile properties. The MPC polymer hydrogel cross-linked with MMPC can be a useful SCL biomaterial.     

Poly(N-vinyl-2-pyrrolidone) hydrogel production by ultraviolet radiation: new methodologies to accelerate crosslinking

Poly(N-vinyl-2-pyrrolidone) hydrogels produced by high-energy radiation relies on water radiolysis as a primary process leading to crosslinks. Conversely, ultraviolet direct irradiation into PVP leads to crosslinking trough pyrrolidinone moiety photolysis. However, this process showed to be rather inefficient. This work describes the crosslinking of poly(N-vinyl-2-pyrrolidone) based on hydrogen peroxide photolysis, therefore mimicking water radiolysis, using UV-C (e.g. low pressure Hg lamp) or UV-A radiation sources. The process efficiency and the properties of the hydrogel formed are discussed and compared with other methods of hydrogel production.     

Biomimetic strain hardening in interpenetrating polymer network hydrogels

In this paper, we present the systematic development of mechanically enhanced interpenetrating polymer network (IPN) hydrogels with Young's moduli rivaling those of natural load-bearing tissues. The IPNs were formed by synthesis of a crosslinked poly(acrylic acid) (PAA) network within an end-linked poly(ethylene glycol) (PEG) macromonomer network. The strain-hardening behavior of these PEG/PAA IPNs was studied through uniaxial tensile testing and swelling measurements. The interaction between the independently crosslinked networks within the IPN was varied by (1) changing the molecular weight of the PEG macromonomer, (2) controlling the degree of PAA ionization by changing pH, and (3) increasing the polymer content in the PAA network. Young's moduli and the maximum stress-at-break of the swollen hydrogels were normalized on the basis of their polymer content. Strain hardening in the IPNs exhibited a strong dependence on the molecular weight of the first network macromonomer, the pH of the swelling buffer, as well as the polymer content of the second network. The results indicate that the mechanical enhancement of these IPNs is mediated by the strain-induced intensity of physical entanglements between the two networks. The strain can be applied either by mechanical deformation or by changing the pH to modulate the swelling of the PAA network. At pHs below the pK_a of PAA (4.7), entanglements between PEG and PAA are reinforced by interpolymer hydrogen bonds, yielding IPNs with high fracture strength. At pHs above 4.7, a “pre-stressed” IPN with dramatically enhanced modulus is formed due to ionization-induced swelling of the PAA network within a static PEG network. The modulus enhancement ranged from two-fold to over 10-fold depending on the synthesis conditions used. Variation of the network parameters and swelling conditions enabled “tuning” of the hydrogels' physical properties, yielding materials with water content between 58% and 90% water, tensile strength between 2.0 MPa and 12.0 MPa, and initial Young's modulus between 1.0 MPa and 19.0 MPa. Under physiologic pH and salt concentration, these materials attain “biomimetic” values for initial Young's modulus in addition to high tensile strength and water content. As such, they are promising new candidates for artificial replacement of natural tissues such as the cornea, cartilage, and other load-bearing structures.     

Preparation and characterization of mesostructured polymer-functionalized sol–gel-derived thin films

The present study attempts to incorporate methacrylate-based polymers into ordered lamellar organic/inorganic nanocomposite films composed of alternating SiO₂/polymer layers. The films are prepared by dip-coating from a solution containing the monomers and silica precursors, thus leading to composite lamellar mesostructured materials through evaporation-induced self-assembly (EISA). A polymerizable coupling agent is added to covalently link the polymers to the silica matrix. The final polymer/SiO₂ hybrid material is obtained by a separate free-radical polymerization step, initiated by UV exposure or thermal treatment. Using trimethoxy(7-octen-1-yl)silane as a coupling agent, a procedure was established that preserved the mesostructure and maintained the swelling properties of the polymers, while acrylate-based coupling agents lead to a significant distortion of the film mesostructure. Structure and composition of the films were studied by X-ray diffraction, NMR and IR.