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The thermally driven progression and mechanism of enantiomeric transitions between the left and right enantiomers will be our main focus, and the strategy is to dissect the time development of the CVs collected from different sets of independent simulation runs. From simulation data, we found that an understanding of the dynamics of enantiomeric transitions needs first to seek out the left and right enantiomers through a molecular modeling and visualizing program, then to ferret out and identify between the left and right enantiomers a symmetrical structure, and finally to define from the latter a reaction coordinate. We showed in this work that this single reaction coordinate is predictive in unraveling the left ⇌ right enantiomeric transition events, providing a specific inkling of the transition time span and its associated distribution which can be checked further for its reasonableness by the autocorrelation function and a vibrational analysis, all of which shed light on the mechanisms of transition.Nucleophilic aromatic substitution (SNAr) is a classical reaction with well-known reactivity toward electron-poor fluoroarenes. However, electron-neutral and electron-rich fluoro(hetero)arenes are considerably underrepresented. Herein, we present a method for the nucleophilic defluorination of unactivated fluoroarenes enabled by cation radical-accelerated nucleophilic aromatic substitution. The use of organic photoredox catalysis renders this method operationally simple under mild conditions and is amenable to various nucleophile classes, including azoles, amines, and carboxylic acids. Select fluorinated heterocycles can be functionalized using this method. In addition, the late-stage functionalization of pharmaceuticals is also presented. Computational studies demonstrate that the site selectivity of the reaction is dictated by arene electronics.We investigated the Sr2-xPb x GeSe4 series from 0 ≤ x ≤ 2 to study the impact of Pb on structure and properties. While the noncentrosymmetric (NCS) compounds γ-Sr2GeSe4 and α-Pb2GeSe4 have already been reported previously, the substitution variants Sr1.31Pb0.69GeSe4 (space group Ama2, a = 10.31220(1) Å, b = 10.39320(1) Å, c = 7.42140(1) Å) and Sr0.19Pb1.81GeSe4 (I4̅3d, a = 14.6177(3) Å) are introduced here for the first time. The experimentally determined optical band gaps decrease as predicted with increasing Pb content from γ-Sr2GeSe4 to Sr1.31Pb0.69GeSe4, Sr0.25Pb1.75GeSe4, and α-Pb2GeSe4 from 2.00, to 1.65, 1.45 and 1.42 eV, respectively. The nonlinear optical (NLO) properties of the orthorhombic compounds γ-Sr2GeSe4 and Sr1.3Pb0.7GeSe4 (approximated with the supercell “Sr3PbGe2Se8”) were studied both theoretically, using first-principle calculations, and experimentally. The calculations found the effective nonlinear susceptibility, deff, of γ-Sr2GeSe4 and “Sr3PbGe2Se8” at the static limit to be 10.8 and 8.8 pm V-1, respectively. The experimental deff values of γ-Sr2GeSe4, Sr1.31Pb0.69GeSe4, Sr0.25Pb1.75GeSe4, and α-Pb2GeSe4 were 2.6, 2.3, 0.68, and 0.79 pm V-1, respectively.The development of adhesives with superior optical and mechanical performance, solvent resistance, and reworkability is gaining increasing attention in recent years. However, traditional materials do not possess reprocessability and healing characteristics for sustainable development. Here, a superior dynamic polythiourethane (PTU) adhesive with high reprocessability was developed by introducing covalent adaptable networks (CANs). Specifically, dynamic thiocarbamate bonds (TCB) were used to prepare PTU CANs, which showed dramatically enhanced malleability and recyclability. The Young’s modulus of the material was 2.0 GPa and the tensile strength was 62.7 MPa. The reprocessing temperature of CANs was reduced to 80 °C while more than 90% of their mechanical properties were retained, even after being reprocessed several times. Moreover, the highly transparent and water-resistant PTU CANs featured an excellent bonding property and reworkability for various materials including glass, with a lap shear strength of 2.9 MPa, metal (5.1 MPa), and wood (6.3 MPa), compared with commercially available adhesives. learn more Additionally, carbon fiber-reinforced composites constructed with PTU CANs were capable of being fully recycled and reused. Importantly, laminated glass with a toughened PTU-PU elastomer interface exhibited an outstanding impact fatigue-resistance behavior, sustaining thousands of impacts. These features demonstrate that PTU CANs show great potential as sustainable materials.Highly selective and water permeable dual-layer ultrafiltration (UF) membranes comprising a disordered poly(methyl methacrylate-stat-styrene)-block-poly(lactide) selective layer and a polysulfone (PSF) support layer were fabricated using a co-casting technique. A dilute solution of diblock polymer was spin coated onto a solvent-swollen PSF layer, rapidly heated to dry and disorder the block polymer layer, and subsequently immersed into an ice water coagulation bath to kinetically trap the disordered state in the block polymer selective layer and precipitate the support layer by nonsolvent-induced phase separation. Subsequent removal of the polylactide block generated porous membranes suitable for UF. The permeability of these dual-layer membranes was modulated by tuning the concentration of the PSF casting solution, while the size-selectivity was maintained because of the narrow pore size distribution of the self-assembled block polymer selective layer. Elimination of the thermal annealing step resulted in a dramatic increase in the water permeability without adversely impacting the size-selectivity, as the disordered nanostructure present in the concentrated casting solution was kinetically trapped upon rapid drying. The co-casting strategy outlined in this work may enable the scalable fabrication of block polymer membranes with both high permeability and high selectivity.The interface between ground rubber particles (GRPs) and virgin rubber is the focus of this investigation that aims to mitigate the detriments caused by recycled GRPs blended in virgin rubber. By studying laminates of cured and uncured rubber strips as models for the interface, modulus contrast across the interface has been identified as another cause for the poor mechanical properties of vulcanizates containing GRPs, in additional to poor interfacial bonding. A surface-devulcanization method was established to improve molecular contact between the GRPs and virgin rubber and consequently raised the adhesion energy to the level of cohesion energy. The interfacial modulus contrast that causes stress concentration at the interface was likely a result of diffusion of curatives from the virgin rubber to the GRPs. The modulus contrast was erased by diffusion of piperidine from the GRPs into the virgin rubber. Piperidine acted as a vulcanization accelerator, making sulfur cross-linking within the virgin rubber outcompete sulfur diffusion into the GRPs.