Effects of Through-Bond and Through-Space Conjugations on the Photoluminescence of Small Aromatic and Aliphatic Aldimines.

Through-bond conjugation (TBC) and/or through-space conjugation (TSC) determine the photophysical properties of organic luminescent compounds. No systematic studies have been carried out to understand the transition from aromatic TBC to non-aromatic TSC on the photoluminescence of organic luminescent compounds. In this work, a series of small aromatic and aliphatic aldimines were synthesized. For the aromatic imines, surprisingly, N,1-diphenylmethanimine with the highest TBC is non-emissive, while N-benzyl-1-phenylmethanimine and N-cyclohexyl-1-phenylmethanimine emit bright fluorescence in aggregate states. The aliphatic imines are all emissive, and their maximum emission wavelength decreases while the quantum yield increases with a decrease in steric hindrance. The imines show concentration-dependent and excitation-dependent emissions. Theoretical calculations show that the TBC extents in the aromatic imines are not strong enough to induce photoluminescence in a single molecule state, while the intermolecular TSC becomes dominant for the fluorescence emissions of both aromatic and aliphatic imines in aggregate states, and the configurations and spatial conformations of the molecules in aggregate states play a key role in the formation of effective TSC. This study provides an understanding of how chemical and spatial structures affect the formation of TBC and TSC and their functions on the photoluminescence of organic luminescent materials.

Strong adhesion of poly(vinyl alcohol)-glycerol hydrogels onto metal substrates for marine antifouling applications.

Hydrogels can be used as an alternative coating material for ships against marine biofouling. However, the adhesion of wet and soft hydrogels onto solid metals remains a challenging problem. Here we report the adhesion of a typical hydrogel material, poly(vinyl alcohol) (PVA)-glycerol hydrogel, onto stainless steel substrates and the antifouling potency of the adhered PVA-glycerol hydrogels. Poly(allylamine hydrochloride) (PAH) hydrogel and ethyl α-cyanoacrylate (ECA) are used as the binders, and they are found to be able to firmly bond the PVA-glycerol hydrogels onto the stainless steel substrates. The PAH hydrogel does not affect the mechanical properties of the PVA-glycerol hydrogel during use, but it tends to lose the adhesive ability in a dehydrating environment. In contrast, the ECA adhesive can maintain strong bonding between PVA-glycerol hydrogels and substrates upon several water losing/water absorbing cycles, despite some negative effects on the strength of the PVA-glycerol hydrogel. Biological experiments show that the PVA-glycerol hydrogel has a strong settlement-inhibiting effect on the barnacle Balanus albicostatus, suggesting that combining the PVA-glycerol hydrogel with ECA adhesive may have promising applications in marine antifouling.

Dynamic Ag-N Bond Enhanced Stretchable Conductor for Transparent and Self-Healing Electronic Skin.

Stretchable conductors have been achieved by stacking conductive nanomaterials onto the surfaces of elastomeric substrates. However, many of them show a dramatic decrease in conductivity under strain without an efficient way for the conductive layer to release strain. Here, we report a transparent, stretchable, and self-healing conductor with excellent mechanoelectrical stability by introducing dynamic bonding between conductive nanomaterials and an elastomeric substrate. We prepare the conductor by semiembedding Ag nanowires (AgNWs) into a self-healing polydimethylsiloxane (PDMS)-based elastomer, which is modified with bipyridine (Bpy) ligand and further cross-linked by adding Zn2+ as coordinator (Zn-Bpy-PDMS). The dynamic Ag-N bonds not only improve the wettability of the substrate and facilitate the spreading of AgNWs but also reversibly break and reform to accommodate the deformation of AgNWs. As a result, the resistance increase of Zn-Bpy-PDMS/AgNWs is much smaller than that without the dynamic bonding (PDMS/AgNWs). Besides, this conductor exhibits excellent conductivity (76.2 Ω/sq) and transparency (86.6% @ 550 nm), as well as extraordinary self-healing property with a low resistance increase (ΔR/R0 ∼ 1.4) after healing at room temperature for 1 day. This work provides insights into the future design of integrated electronic skin with transparency, stretchability, conductivity, and self-healing capability for applications in wearable optoelectronic devices.

Super-strong and tough poly(vinyl alcohol)/poly(acrylic acid) hydrogels reinforced by hydrogen bonding.

Synthetic hydrogels or water-containing polymeric materials are much inferior to biological tissues and solid plastics in many aspects of mechanical properties; it is a great challenge to develop hydrogels with mechanical properties comparable with or even superior to those of biological tissues and plastics. Here, we report a type of super-strong and tough hydrogen-bonded poly(vinyl alcohol)/poly(acrylic acid) (PVA/PAA) hydrogel by immersing as-prepared PVA hydrogels in aqueous PAA solutions and then cold-drawing the hydrogels to different strains. The immersing process introduces PAA chains into the PVA hydrogels, which increases the cross-linking density by hydrogen bonding and hence, much improved mechanical properties and low water contents (35.9-40.2 wt%) are observed. The cold-drawing orients the polymer chains, which enables the formation of more and stronger hydrogen bonds. The mechanical properties of cold-drawn gels are dramatically enhanced, with tensile strength and elastic modulus up to 140 and 100 MPa, respectively; also, super-high toughness (117 MJ m-3) and fracture energy (101 kJ m-2) are obtained. Very impressively, the ultra-high tensile strengths of the cold-drawn hydrogels are superior to those of biological tissues and most solid engineered plastics. Characterizations and comparative studies prove that the enhancement of mechanical properties is mainly due to the formation of more hydrogen bonding rather than the loss of water or the change in crystallinity. This study provides a new strategy for preparing super-strong physically cross-linked hydrogels and other polymeric materials. This super-strong and tough hydrogel may find potential applications in biomedical and load-bearing fields.

Strong fluorescence of poly(N-vinylpyrrolidone) and its oxidized hydrolyzate.

Discovering fluorescence of existing compounds, which are generally regarded as non-fluorescent, is of important academic and technical significance. This article reports the fluorescence of common compounds containing pyrrolidone ring(s) and their oxidized hydrolyzates. Poly(N-vinylpyrrolidone) (PVP), polymerized from a very weak fluorescent monomer N-vinyl-2-pyrrolidone (NVP), exhibits strong intrinsic fluorescence. Moreover, the fluorescence of its "hydrolyzate" is dramatically enhanced by about 1000 times. The "hydrolyzate" of N-methyl-pyrrolidone (NMP) also exhibits significantly enhanced fluorescence. By studying the chemical structures and fluorescence of the hydrolyzates, the enhanced fluorescence is attributed to the formation of secondary amine oxide. The much stronger fluorescence of the polymers compared to the corresponding small molecular compounds is ascribed to the "aggregation-induced emission" (AIE) effect of the luminophores. PVP and its oxidized hydrolyzate also show some phenomena different to the common AIE effect. The fluorescence of PVP and its oxidized hydrolyzate shows stimuli response to metal ions and pH values. This study introduces novel fluorescent materials for various potential applications.

Nano-hydroxyapatite/polyacrylamide composite hydrogels with high mechanical strengths and cell adhesion properties.

Nano-hydroxyapatite/polyacrylamide composite hydrogels were successfully fabricated by physically mixing nano-hydroxyapatite (nHAp) particles into a peroxidized micelles initiated and cross-linked (pMIC) polyacrylamide (PAAm) hydrogel. The nanocomposite hydrogels exhibited excellent mechanical properties. The fracture tensile stresses of the gels were in the range of 0.21-0.86 MPa and the fracture tensile strains were up to 30 mm/mm, and the compressive strengths were up to 35.8 MPa. Meanwhile the introduction of nHAp endowed the composite hydrogels with good cell adhesion properties. This nHAp/PAAm nanocomposite hydrogel is expected to find potential applications in tissue engineering.

Interactions affecting the mechanical properties of macromolecular microsphere composite hydrogels.

Macromolecular microsphere composite (MMC) hydrogel is a kind of tough hydrogel fabricated by using peroxidized macromolecular microspheres as polyfunctional initiating and cross-linking centers (PFICC). The contribution of chemical cross-linking (covalent bonding) and physical cross-linking (chain entanglement and hydrogen bonding) to the mechanical properties are understood by testing the hydrogels, which were swollen in water or aqueous urea solutions to different water contents. The as-prepared MMC gels exhibited moderate moduli (60-270 kPa), high fracture tensile stresses (up to 0.54 MPa), high extensibilities (up to 2500%), and high fracture energies (270-770 J m(-2)). The moduli of the swollen gels decrease dramatically, but there are no significant changes in fracture tensile strength and fracture strain, even slight increases. More interestingly, the swollen gels show much-enhanced fracture energies, higher than 2000 J m(-2). A gradual decrease in the hysteresis ratio and residual strain is also found in the cyclic tensile testing of the hydrogels that were swollen to different water contents. The covalent bonding determines the tensile strength and fracture energy of the MMC gels, whereas the physical entanglement and hydrogen bonding among the polymer chains contributes mainly to the modulus of the MMC gels, and they are also the main reason for the presence of hysteresis in the loading-unloading cycles.

Self-healing in tough graphene oxide composite hydrogels.

Polymer hydrogels that are capable of spontaneously healing injury are being developed at a rapid pace because of their great potential in biomedical applications. Here, the self-healing property of tough graphene nanocomposite hydrogels fabricated by using graphene peroxide as polyfunctional initiating and cross-linking centers is reported. The hydrogels show excellent self-healing ability at ambient temperature or even lower temperatures for a short time and very high recovery degrees (up to 88% tensile strength) can be achieved at a prolonged healing time. The healed gels exhibit very high tensile strengths (up to 0.35 MPa) and extremely high elongations (up to 4900%). The strong interactions between the polyacrylamide chains and the graphene oxide sheets are essential to the mechanical strengths of the healed gels.

A tough hydrogel-hydroxyapatite bone-like composite fabricated in situ by the electrophoresis approach.

Mechanically strong hydrogel-HAp composites have been successfully fabricated through in situ formation of hydroxyapatite (HAp) in a tough polyacrylamide (PAAm) hydrogel with a modified electrophoretic mineralization method. The pre-swelling of the PAAm hydrogels in CaCl2 buffer solutions makes the electrophoresis method able to produce large area (10 × 8 cm2) hydrogel-HAp composites. At the same time the CaCl2 solution with different concentrations could control the HAp contents. The obtained hydrogel-HAp composites exhibit enhanced mechanical properties, namely higher extensibility (>2000%), tensile strength (0.1-1.0 MPa) and compressive strength (up to 35 MPa), in comparison to the as-synthesized PAAm hydrogels. FTIR and Raman characterizations indicate the formation of strong interactions between PAAm chains and HAp particles, which are thought to be the main reason for the enhanced mechanical properties. The hydrogel-HAp composite also shows excellent osteoblast cell adhesion properties. These composite materials may find more applications in biomedical areas, e.g. as a matrix for tissue repair especially for orthopedic applications and bone tissue engineering.

Anisotropic tough poly(2-hydroxyethyl methacrylate) hydrogels fabricated by directional freezing redox polymerization.

This work reports a novel method for fabricating anisotropic hydrogels starting from monomers by combining directional freezing and redox polymerization (DFRP), and poly(2-hydroxyethyl methacrylate) (PHEMA) hydrogels with anisotropic porous structures and mechanical properties are obtained. Scanning electron microscopy (SEM) investigations show that the hydrogels have long and wide (up to several tens of micrometers) aligned channels in the direction parallel to the freezing direction, and pores in the perpendicular direction. The sizes of the channels and pores decrease with increasing freezing rate. Tensile, compressive and tearing tests show that the hydrogels (70 wt% water content) show very good mechanical properties, with tensile strength up to 0.44 MPa, compressive strength more than 20 MPa, and fracture energy up to 1000 J m-2. More importantly, the hydrogels exhibit significant anisotropy in their mechanical properties, which are better in the parallel direction. The hydrogels also show different swelling behaviour in comparison with conventional synthetic hydrogels. The anisotropic tough PHEMA hydrogels may find further application.

Synthesis of graphene peroxide and its application in fabricating super extensible and highly resilient nanocomposite hydrogels.

Functionalized graphene has been considered as one of the most important materials for preparing polymer nanocomposites due to its unique physical structure and properties. To increase the interfacial interaction between polymer component and graphene oxide (GO) sheets, in situ grafting polymerization initiated by a free radical initiator immobilized on GO sheets is a better choice. We report a facile and effective strategy for preparing graphene peroxide (GPO) via the radiation-induced peroxidation of GO. The formation of peroxides on GO is proven by iodometric measurement and other characterizations. Using GPO as a polyfunctional initiating and cross-linking center, we obtained GO composite hydrogels exhibiting excellent mechanical properties, namely, very high tensile strength (0.2-1.2 MPa), extremely high elongations (2000-5300%), and excellent resilience. This work provides new insight into the fabrication of GO/polymer nanocomposites to fulfill the excellent mechanical properties of graphene.

Mechanical properties, anisotropic swelling behaviours and structures of jellyfish mesogloea.

Learning from nature is a promising way for designing and fabricating new materials with special properties. As the first step, we need to understand the structures and properties of the natural materials. In this work, we paid attention to the mesogloea of an edible jellyfish (Rhopilema esculenta Kishinouye) and mainly focused on its structure, mechanical and swelling properties. Scanning electron microscope (SEM) investigations show that jellyfish mesogloea has a well-developed anisotropic microstructure, which consists of nano-sized membranes connected with many fibres. The tensile and compressive properties of swollen and dried jellyfish mesogloea samples are measured. The jellyfish mesogloea displays very high tensile strength (0.17 MPa) and compressive strength (1.43 MPa) even with 99 wt % water. The mechanical properties of jellyfish mesogloea exceed most synthetic hydrogels with similar or even lower water contents. Swelling in acidic and basic buffer solutions weakens the mechanical properties of jellyfish mesogloea. The dried jellyfish mesogloea has very high tensile strength and modulus, which are very similar to those of synthetic plastics. The swelling properties of jellyfish mesogloea in solutions with different pH values were studied. The jellyfish mesogloea exhibits pH-sensitive and anisotropic swelling properties. The jellyfish mesogloea swells (expands) in height but deswells (shrinks) in length and width, without significant change in the volume. This phenomenon has never been reported for synthetic hydrogels. This study may provide gel scientists new ideas in designing and fabricating hydrogels with well-defined microstructures and unique mechanical and swelling properties.

Responsive micellar films of amphiphilic block copolymer micelles: control on micelle opening and closing.

We reported the deliberate control on the micelle opening and closing of amphiphilic polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) micellar films by exposing them to selective solvents. We first treated the micellar films with polar solvents including ethanol and water (pH = 4, 8, and 12) that have different affinities to P2VP. We observed opening of the micelles in all the cases. Both the size of opened pores and the opening rate are dependent on the solvency of different solvents for P2VP. We then explored the closing behavior of the opened micelles using solvents having different affinities to PS. We found that the opened micelles were recovered to their initial closed micelle forms. The recovery was accompanied by a slow micelle disassociation process which gradually reduced the micelle size. The rates of the micelle closing and disassociation are also dependent on the solvency of different solvents for PS.