Isoindigo-Based Dual-Acceptor Conjugated Polymers Incorporated Conjugation Length and Intramolecular Charge Transfer for High-Efficient Photothermal Conversion.

Photothermal tumor therapy (PTT) and photoacoustic imaging (PA) have emerged as promising noninvasive diagnostic and therapeutic approaches for cancer treatment. However, the development of efficient PTT agents with high photostability and strong near-infrared (NIR) absorption remains challenging. This study synthesizes three isoindigo-based dual-acceptor conjugated polymers (CPs) (P-IIG-TPD, P-IIG-DPP, and P-IIG-EDOT-BT) via a green and nontoxic direct arylation polymerization (DArP) method and characterizes their optical, electrochemical, and NIR photothermal conversion properties. By incorporating two acceptors into the backbone, the resulting polymers exhibit enhanced photothermal conversion efficiency (PCE) due to improved synergy among conjugation length, planarity, and intramolecular charge transfer (ICT). The nanoparticles (NPs) of P-IIG-EDOT-BT and P-IIG-DPP have a uniform size distribution around 140 nm and exhibit remarkable NIR absorption at 808 nm. In addition, P-IIG-EDOT-BT and P-IIG-DPP NPs exhibit high PCEs of 62% and 78%, respectively. This study promotes the molecular design of CPs as NIR photothermal conversion materials and provides guidance for the development of novel dual-acceptor CPs for tumor diagnosis and treatment.

A self-oscillating gel system with complex dynamic behavior based on a time delay between the oscillations.

The time delay existing between the chemical oscillation and mechanical oscillation (C-M delay) in a self-oscillating gel (SOG) system is observable in previous experimental studies. However, how the C-M delay affects the dynamic behavior of a large anisotropic SOG has not been quantified or reported systematically. In this study, we observed that the oscillation period increases with a decrease in the cross-linking density of the anisotropic SOG, and this determined whether regular mechanical oscillation occurs. Unlike before, the disrupted mechanical oscillations interestingly tend to be regular and periodic under visible light, which is an inhibitor for the B-Z reaction incorporating the Ru complex as a catalyst (Ru-BZ reaction). Moreover, the study of the C-M delay at different scales has far-reaching implications for intelligent soft actuators.

A rapidly recoverable shape memory polymer with a topologically well-controlled poly(ethyl methacrylate) structure.

Many of the unique properties of a conventionally crosslinked shape memory network are not found at the same time, and this is a large challenge for the development of advanced shape memory functional materials. In this work, a topologically well-controlled network shape memory poly(ethyl methacrylate) (CN-SMPEMA) is designed and fabricated by introducing two tetra-armed functional structures simultaneously as well-defined structure units to promote switch segment and net-point uniform distribution via the combined technology of the unique controllable atom transfer radical polymerization (ATRP) and copper(i)-catalyzed azide-alkyne cycloaddition (CuAAC). Compared with conventionally crosslinked networks, the as-prepared CN-SMPEMA not only exhibits a combination of excellent mechanical properties, shape fixity, shape recovery ratios and outstanding cycling stability, but also displays rapid recoverability. Additionally, a feasible molecular mechanism for the shape memory effect of the CN-SMPEMA system is analyzed and proposed. We anticipate that such a topologically well-defined network shape memory material with multiple excellent properties will broaden the practical application range of acrylate-based shape memory polymer materials.

Organic solvents-free and ambient-pressure drying melamine formaldehyde resin aerogels with homogeneous structures, outstanding mechanical strength and flame retardancy.

Atmospheric drying method for fabricating aerogels is considered the most promising way for casting aerogels on a large scale. However, the organic solvent exchange, remaining environmental pollution risk, is a crucial step in mitigating the impact of surface tension during the atmospheric drying process, especially for wet gel formed through the alkoxy-derived sol-gel process, such as melamine-formaldehyde resin (MF) aerogel. Herein, a tough polymer-assisted in situ polymerization was proposed to fabricate MF resin aerogel with a combination of mechanical toughness and strength, enabling it to withstand the capillary force during water evaporation. The monolithic MF resin aerogel through the sol-gel method can be directly prepared without additional network strengthening or organic solvent exchange. The resulting MF resin aerogel exhibits a homogeneous as well as hierarchical structure with macropores and mesopores (~6 µm and ~5 nm), high compressive modulus of 31.8 MPa, self-extinguishing property, and high-temperature thermal insulation with 97 % heat decrease for butane flame combustion. This work presents a straightforward and environmentally friendly method for fabricating MF resin aerogels with nanostructures and excellent performance in open conditions, exhibiting various applications.

Catalytic polymer self-cleavage for CO2 generation before combustion empowers materials with fire safety.

Polymeric materials, rich in carbon, hydrogen, and oxygen elements, present substantial fire hazards to both human life and property due to their intrinsic flammability. Overcoming this challenge in the absence of any flame-retardant elements is a daunting task. Herein, we introduce an innovative strategy employing catalytic polymer auto-pyrolysis before combustion to proactively release CO2, akin to possessing responsive CO2 fire extinguishing mechanisms. We demonstrate that potassium salts with strong nucleophilicity (such as potassium formate/malate) can transform conventional polyurethane foam into materials with fire safety through rearrangement. This transformation results in the rapid generation of a substantial volume of CO2, occurring before the onset of intense decomposition, effectively extinguishing fires. The inclusion of just 1.05 wt% potassium formate can significantly raise the limiting oxygen index of polyurethane foam to 26.5%, increase the time to ignition by 927%, and tremendously reduce smoke toxicity by 95%. The successful application of various potassium salts, combined with a comprehensive examination of the underlying mechanisms, underscores the viability of this strategy. This pioneering catalytic approach paves the way for the efficient and eco-friendly development of polymeric materials with fire safety.

Polyelectrolyte Complex with Controllable Viscosity by Doping Cu2+ Protects Nylon-Cotton Fabric against Fire.

Nylon-cotton (NC) blend fabrics are widely used in military and industrial applications, but their high flammability still remains a serious problem. In an effort to effectively and quickly impart flame retardancy to the NC fabric, it was treated by simply blade coating with a Cu2+-doped polyelectrolyte complex (CPEC) that consists of ammonium polyphosphate (APP), polyethylenimine (PEI), and copper sulfate. The viscosity of the CPEC can be adjusted by altering the content of CuSO4, which controls the amount of extrinsic and intrinsic ion pairs. By adjusting the proportion and content of PEI, APP, and CuSO4, CPEC suitable for treating the NC fabric was obtained. Only 0.067 wt % Cu2+ was needed to adjust the viscosity and impart self-extinguishing behavior in a vertical burning test. This simple two-step treatment provides a promising technology to protect flammable polymeric substrates with ultralow metal-doped polyelectrolyte complexes.

A self-deformable gel system with asymmetric shape change based on a gradient structure.

A self-deformable gel system is constructed by coupling a gradient structured gel with a chemical oscillating reaction. The system exhibits periodic and asymmetric shape change. The asymmetric shape change of the gel is based on the gradient structure.

Real-time rheology of shear-induced organoclay dispersion in isotactic polypropylene.

In this paper, rheological properties evolution of the simple mixed isotactic polypropylene/organoclay composites, impacted by intermediate- or large-amplitude oscillatory shear fields, was followed by dynamic melt rheometry. The physical meanings of such rheological evolution upon oscillatory shearing, which related closely to the dispersion and intercalation of organoclay in polymer, were discussed deeply. Especially, a structural recovery test was adopted to assess microstructure development induced by large-amplitude oscillatory shear and to better understand the intercalation mechanism. Based on the experimental results, a novel intercalation mechanism that was taken to account for the disentanglement of polymer chains was suggested to describe shear-induced dispersion behaviors of organoclay in polymer matrix.