Fluorochromic polymeric elastomer film containing copper nanoclusters in response to multistimuli.

Smart chromic elastomers exhibiting multistimuli responsiveness are of interest with regard to the development of sensors, optical data storage, and smart wearable devices. We report a new design of Cu nanoclusters (Cu NCs) containing polymeric elastomer film, showing reversible fluorescence ON/OFF when subjected to organic solvents (e.g. ethanol, methanol and tetrahydrofuran), and heating/cooling cycles at temperatures lower than 80 °C. Different from the solvato-responsiveness of Cu NCs in solution state, organic solvents increase nonradiative decay and quench fluorescence emission in the solid polymer matrix. It is deduced that lower temperatures (<80 °C) increase reversible nonradiative decay, while higher temperatures (>80 °C) trigger an irreversible change of the aggregation state of Cu NCs in the elastomer film. A strong oxidizer (e.g. H2O2) irreversibly quenches the fluorescence emission and changes its color (under sunlight) from light green to blue, by oxidizing Cu NCs to Cu2+ ions. This Cu NC-containing elastomer film illustrates a new pathway to the fabrication of multi-responsive smart optical materials, particularly for potential applications in optical data storage (e.g. thermo-printing), and multistimuli-responsive elastomeric sensors integrated into wearable devices.

Fluorochromic polymer films containing ultrasmall silver nanoclusters.

Fluorochromic materials that change their emission properties in response to their environment are of interest for the development of sensors, optical data storage and light-emitting materials. A thermally fluorochromic elastic polymer film that exhibits remarkable fluorochromism (from red to yellow) and enhancement of fluorescence intensity after thermal treatment (>120 °C) is designed by the incorporation of silver nanoclusters. The thermal treatment also leads to a significant increase of quantum yield and fluorescence lifetime. It is found that the thermo-induced etching on larger silver nanoclusters generates smaller silver nanoclusters. This simple and efficient size-tuning process in solid state is responsible for the thermo-fluorochromism and enhancement of fluorescence emission from silver nanoclusters. Such a thermo-fluorochromic polymer material is finally demonstrated to be useful for thermo-printing. This material illustrates a new way to make smart optical materials, particularly for potential applications in optical data storage and soft OLED display.

Adaptable Eu-containing polymeric films with dynamic control of mechanical properties in response to moisture.

Self-healing polymers often have a trade-off between healing efficiency and mechanical stiffness. Stiff polymers that sacrifice their chain mobility are slow to repair upon mechanical failure. We herein report adaptable polymer films with dynamically moisture-controlled mechanical and optical properties, therefore having tunable self-healing efficiency. The design of the polymer film is based on the coordination of europium (Eu) with dipicolylamine (DPA)-containing random copolymers of poly(n-butyl acrylate-co-2-hydroxy-3-dipicolylamino methacrylate) (P(nBA-co-GMADPA)). The Eu-DPA complexation results in the formation of mechanically robust polymer films. The coordination of Eu-DPA has proven to be moisture-switchable given the preferential coordination of lanthanide metals to O over N, using nuclear magnetic resonance and fluorescence spectroscopy. Water competing with DPA to bind Eu3+ ions can weaken the cross-linking networks formed by Eu-DPA coordination, leading to the increase of chain mobility. The in situ dynamic mechanical analysis and ex situ rheological studies confirm that the viscofluid and the elastic solid states of Eu-polymers are switchable by moisture. Water speeds up the self-healing of the polymer film by roughly 100 times; while it can be removed after healing to recover the original mechanical stiffness of polymers.

Dynamic Coordination of Eu-Iminodiacetate to Control Fluorochromic Response of Polymer Hydrogels to Multistimuli.

New fluorochromic materials that reversibly change their emission properties in response to their environment are of interest for the development of sensors and light-emitting materials. A new design of Eu-containing polymer hydrogels showing fast self-healing and tunable fluorochromic properties in response to five different stimuli, including pH, temperature, metal ions, sonication, and force, is reported. The polymer hydrogels are fabricated using Eu-iminodiacetate (IDA) coordination in a hydrophilic poly(N,N-dimethylacrylamide) matrix. Dynamic metal-ligand coordination allows reversible formation and disruption of hydrogel networks under various stimuli which makes hydrogels self-healable and injectable. Such hydrogels show interesting switchable ON/OFF luminescence along with the sol-gel transition through the reversible formation and dissociation of Eu-IDA complexes upon various stimuli. It is demonstrated that Eu-containing hydrogels display fast and reversible mechanochromic response as well in hydrogels having interpenetrating polymer network. Those multistimuli responsive fluorochromic hydrogels illustrate a new pathway to make smart optical materials, particularly for biological sensors where multistimuli response is required.

Cross-linking of COOH-containing polymers using Ag(i)-catalyzed oxidative decarboxylation in aqueous solution.

Cross-linking that defines the three-dimensional networks in hydrogels has a significant impact on their physiochemical properties. The cross-linking of hydrophilic polymers via post-polymerization reactions is an ideal way to manufacture hydrogels with high reproducibility and without monomer residuals. We herein report the use of Ag(i)-catalyzed oxidative decarboxylation to cross-link poly(acrylic acid) (PAA) and a family of COOH-containing hydrophilic polymers. Our method is based on the radical-mediated elimination reaction to remove COOH group(s) and generate alkyl radical(s) simultaneously, in the presence of AgNO3 and persulfates. The further intermolecular radical coupling is demonstrated to be very effective in inducing cross-linking and gelation of COOH-containing hydrophilic polymers. The cross-linking reaction can be readily achieved by simply mixing a small amount of AgNO3 (as low as 0.03 wt%) and persulfates with polymers at room temperature in air. Rheological measurements show that the gelation occurs in 20-30 min. The applications of oxidative decarboxylation in the preparation of hydrogels of COOH-containing hydrophilic copolymers and their interpenetrating polymer network (IPN) hydrogels are further validated. Finally, the residual Ag(i) ions in hydrogels are discussed in terms of how Ag(i) ions further change the mechanical and optical properties of hydrogels by photoreduction of Ag(i) to Ag nanoparticles. We expect that this Ag(i)-catalyzed oxidative decarboxylation chemistry can not only serve as a facile and general strategy to produce hydrogels through post-polymerization, but also enrich the toolbox of cross-linking chemistries of COOH-containing polymers in all forms (e.g. films, colloids and dispersions).

Large-scale orientation in a vulcanized stretched natural rubber network: proved by in situ synchrotron X-ray diffraction characterization.

In situ studies of strain-induced crystallization in unfilled and multiwalled carbon nanotube (MWCNT)-filled natural rubber (NR) were carried out by using synchrotron wide-angle X-ray diffraction (WAXD). Synchrotron WAXD results indicate that more nuclei appear in the MWCNT-filled NR sample, leading to higher crystallinity, lower onset strain of crystallization, and remarkable enhancement in tensile strength. During deformation, despite the amorphous chains remaining in isotropic orientation, the domains of larger scale (10-100 nm) with high network chain density in the NR matrix are oriented. The MWCNTs induce significant variation of this orientational process, and it is monitored by the stearic acid (SA) crystallites, which are effective nanoprobes of the amorphous phase. The results indicate that a small amount of MWCNTs and SA crystallites can be used as new tools to analyze the microstructural orientation of NR during deformation. The results also yield new insight into the strain-induced crystallization mechanism.