Design and development of self-repairable and recyclable crosslinked poly(thiourethane-urethane) via enhanced aliphatic disulfide chemistry

Thermoset polymer elastomers that are capable of autonomous repairability upon physical damage at ambient temperature are highly desirable because of their thermal and environmental resistance, outstanding mechanical toughness and stability. To aim at this goal, we demonstrated that tris(diethylamino)phosphine was initially proven as an efficient catalyst for the aliphatic disulfide exchange at mild condition. By making use of the aliphatic disulfide bond reshuffling and elasticity of polyurethane elastomers, the inherently cross-linked polysulfide-based poly(thiourethane-urethane) elastomers were prepared and exhibited the ability to mend without extrinsic stimuli in the presence of phosphorus catalyst at room temperature after artificially damaged. The self-healing efficiency via the mechanical recovery approach was investigated to be mainly dependent upon the cross-linking density of polysulfide and hard segments chemistry, which in turns determined the molecular chain diffusion and reshuffling that was corroborated by the stress-relaxation study. The thermoset elastomer based on asymmetric diisocynate showed a maximum self-healing efficiency of 85.6% compared to 71.6% for the elastomer with symmetric monomer building blocks. The self-healable polymer was confirmed to be recyclable and reprocessable through a cut-compression processing cycle under a quite mild pressure and temperature thanks to the disulfide bond reshuffling. Meanwhile, the recycled thermoset elastomer well maintained the mechanical properties to its original material.     

Co-hydrolysis and Seed-Induced Synthesis of Basic Mesoporous ZSM-5 Zeolites with Enhanced Catalytic Performance

For zeolite catalysts, the regulation of active site and pore structure plays an important role in the enhancement of their catalytic performance. In this work, a one-pot and organic template-free co-regulation route is proposed to straightforwardly synthesize basic mesoporous ZSM-5 zeolites with adjustable alkaline-earth metal species. The synthesis pathway combines two decisive strategies: 1) the seed-induced interface assembly growth method and 2) the acidic co-hydrolysis/condensation of aluminosilicate species and alkaline-earth metal (e.g., Mg, Ca, Sr, or Ba) sources. It is interesting that the mesoporous structure was self-evolved through particle-attached seed-interfacial crystallization without the assistance of any template. Meanwhile, the incorporation of alkaline-earth metals species is homogeneous and highly dispersed in the solid products during the whole crystallization process, and finally generate the superior basicity. Catalysis tests of the as-synthesized samples displayed their novel performance in the typical base reaction of Knoevenagel condensation, even for bulky substrates owing to the enhanced diffusion arising from the meso/microporous network. This finding opens new possibilities for facile, cost-effective, and environmentally friendly synthesis of mesoporous high-silica zeolites with tunable acid/base properties, and deepens our understanding of the particle-attached crystallization.     

Multilayered 2D Cesium-Based Hybrid Perovskite with Strong Polarization Sensitivity: Dimensional Reduction of CsPbBr3

3D perovskite CsPbBr₃ has recently taken a blooming position for optoelectronic applications. However, due to the lack of natural anisotropy of optical attributes, it is a great challenge to fulfil polarization-sensitive photodetection. Here, for the first time, we exploited dimensionality reduction of CsPbBr₃ to tailor a 2D-multilayered hybrid perovskite, (TRA)₂CsPb₂Br₇ ( 1 , in which TRA is (carboxy)cyclohexylmethylammonium), serving as a potential polarized-light detecting candidate. Its unique quantum-confined 2D structure results in intrinsic anisotropy of electrical conductivity, optical absorbance, and polarization-dependent responses. Particularly, it exhibits remarkable dichroism with the photocurrent ratio (I_pc/I_pa) of ≈2.1, being much higher than that of the isotropic CsPbBr₃ crystal and reported CH₃NH₃PbI₃ nanowire (≈1.3), which reveals its great potentials for polarization-sensitive photodetection. Further, crystal-based detectors of 1 show fascinating responses to the polarized light, including high detectivity (>10¹⁰ Jones), fast responding time (≈300 μs), and sizeable on/off current ratios (>10⁴). To our best knowledge, this is the first study on 2D Cs-based hybrid perovskite exhibiting strong polarization-sensitivity. The work highlights an effective pathway to explore new polarization sensitive candidates for hybrid perovskites and promotes their future electronic applications.     

Visible-Light-Mediated Click Chemistry for Highly Regioselective Azide–Alkyne Cycloaddition by a Photoredox Electron-Transfer Strategy

Click chemistry focuses on the development of highly selective reactions using simple precursors for the exquisite synthesis of molecules. Undisputedly, the Cu^I-catalyzed azide–alkyne cycloaddition (CuAAC) is one of the most valuable examples of click chemistry, but it suffers from some limitations as it requires additional reducing agents and ligands as well as cytotoxic copper. Here, we demonstrate a novel strategy for the azide–alkyne cycloaddition reaction that involves a photoredox electron-transfer radical mechanism instead of the traditional metal-catalyzed coordination process. This newly developed photocatalyzed azide–alkyne cycloaddition reaction can be performed under mild conditions at room temperature in the presence of air and visible light and shows good functional group tolerance, excellent atom economy, high yields of up to 99 %, and absolute regioselectivity, affording a variety of 1,4-disubstituted 1,2,3-triazole derivatives, including bioactive molecules and pharmaceuticals. The use of a recyclable photocatalyst, solar energy, and water as solvent makes this photocatalytic system sustainable and environmentally friendly. Moreover, the azide–alkyne cycloaddition reaction could be photocatalyzed in the presence of a metal-free catalyst with excellent regioselectivity, which represents an important development for click chemistry and should find versatile applications in organic synthesis, chemical biology, and materials science.     

Sustained and Controlled Release of Volatile Precursors for Chemical Vapor Deposition of Graphene at Atmospheric Pressure

Precursors and catalysts play vital roles in chemical reactions. Considerable efforts have been devoted to the investigation of catalysts for graphene growth by chemical vapor deposition in recent years. However, there has been little research on precursors because of a lack of innovation in term of creating a controllable feeding method. Herein, we present a novel sustained and controlled release approach, and develop a convenient, safe, and potentially scalable feeding system with the assistance of matrix materials and a simple portable feeder. As a result, a highly volatile liquid precursor can be fed accurately to grow large-area, uniform graphene films with optimal properties. This feeding approach will further benefit the synthesis of other two-dimensional materials from various precursors.     

Recent Advances in Iodine-Promoted C−S/N−S Bonds Formation

Sulfur-containing scaffold, as a ubiquitous structural motif, has been frequently used in natural products, bioactive chemicals and pharmaceuticals, particularly C−S/N−S bonds are indispensable in many biological important compounds and pharmaceuticals. Development of mild and general methods for C−S/N−S bonds formation has great significance in modern research. Iodine and its derivatives have been recognized as inexpensive, environmentally benign and easy-handled catalysts or reagents to promote the construction of C−S/N−S bonds under mild reaction conditions, with good regioselectivities and broad substrate scope. Especially based on this, several new strategies, such as oxidation relay strategy, have been greatly developed and accelerated the advancement of this field. This review focuses on recent advances in iodine and its derivatives promoted hybridized C−S/N−S bonds formation. The features and mechanisms of corresponding reactions are summarized and the results of some cases are compared with those of previous reports. In addition, the future of this domain is discussed.     

Supramolecular Assembly of TPE-Based Glycoclusters with Dicyanomethylene-4H-pyran (DM) Fluorescent Probes Improve Their Properties for Peroxynitrite Sensing and Cell Imaging

Two red-emitting dicyanomethylene-4H-pyran (DM) based fluorescent probes were designed and used for peroxynitrite (ONOO⁻) detection. Nevertheless, the aggregation-caused quenching effect diminished the fluorescence and restricted their further applications. To overcome this problem, tetraphenylethylene (TPE) based glycoclusters were used to self-assemble with these DM probes to obtain supramolecular water-soluble glyco-dots. This self-assembly strategy enhanced the fluorescence intensity, leading to an enhanced selectivity and activity of the resulting glyco-dot comparing to DM probes alone in PBS buffer. The glyco-dots also exhibited better results during fluorescence sensing of intracellular ONOO⁻ than the probes alone, thereby offering scope for the development of other similar supramolecular glyco-systems for chemical biological studies.     

Enzymatic Insertion of Lipids Increases Membrane Tension for Inhibiting Drug Resistant Cancer Cells

Although lipids contribute to cancer drug resistance, it is challenging to target diverse range of lipids. Here, we show enzymatically inserting exceedingly simple synthetic lipids into membranes for increasing membrane tension and selectively inhibiting drug resistant cancer cells. The lipid, formed by conjugating dodecylamine to d -phosphotyrosine, self-assembles to form micelles. Enzymatic dephosphorylation of the micelles inserts the lipids into membranes and increases membrane tension. The micelles effectively inhibit a drug resistant glioblastoma cell (T98G) or a triple-negative breast cancer cell (HCC1937), without inducing acquired drug resistance. Moreover, the enzymatic reaction of the micelles promotes the accumulation of the lipids in the membranes of subcellular organelles (e.g., endoplasmic reticulum (ER), Golgi, and mitochondria), thus activating multiple regulated cell death pathways. This work, in which for the first time membrane tension is increased to inhibit cancer cells, illustrates a new and powerful supramolecular approach for antagonizing difficult drug targets.