Franckclark6470

A PTSB was also discovered to be present in Ni and Pt allylic activation but with less bifurcation. These results offer a unique view into the mechanism of metal-catalyzed allylic substitution.Charge transfer between molecules and catalysts plays a critical role in determining the efficiency and yield of photochemical catalytic processes. In this paper, we study light-induced electron transfer between transition-metal-doped aluminum clusters and CO2 molecules using first-principles time-dependent density-functional theory. Specifically, we carry out calculations for a range of dopants (Zr, Mn, Fe, Ru, Co, Ni, and Cu) and find that the resulting systems fall into two categories Cu- and Fe-doped clusters exhibit no ground-state charge transfer, weak CO2 adsorption, and light-induced electron transfer into the CO2. In all other systems, we observe ground-state electron transfer into the CO2 resulting in strong adsorption and predominantly light-induced electron back-transfer from the CO2 into the cluster. These findings pave the way toward a rational design of atomically precise aluminum photocatalysts.The solid-state cultivation of Acaulium sp. H-JQSF isolated from Armadillidium vulgare produces acautalides A-C (1-3) as skeletally unprecedented Diels-Alder adducts of a 14-membered macrodiolide to an octadeca-9,11,13-trienoic acid. The acautalide structures, along with the intramolecular transesterifications of 1-acylglycerols, were elucidated by mass spectrometry, nuclear magnetic resonance, chemical transformation, and single-crystal X-ray diffraction. Compounds 1-3 were found to be neuroprotective with antiparkinsonic potential in the 1-methyl-4-phenylpyridinium-challenged nematode model, with the magnitude impacted by the glycerol esterification.Ruthenium(II) complexes, like [(tbbpy)2Ru(dppz)]2+ (Ru-dppz; tbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine, dppz = dipyrido-[3,2-a2',3'-c]phenazine), have emerged as suitable photosensitizers in photoredox catalysis. Since then, there has been ongoing interest in the design of π-extended Ru-dppz systems with red-shifted visible absorption maxima and sufficiently long-lived excited states independent of the solvent or pH value. Herein, we explore the photophysical properties of protonation isomers of the linearly π-extended [(tbbpy)2Ru(L)]2+-type complexes bearing a dppz ligand with directly fused imidazole (im) and methyl-imidazole units (mim) as L. Steady-state UV-vis absorption, resonance Raman, as well as time-resolved emission and transient absorption spectroscopy reveal that Ru-im and Ru-mim show desirable properties for the application in photocatalytic processes, i.e., strong visible absorbance and two long-lived excited states in the 3ILCT and 3MLCT manifold, at pH values between 3 and 12. However, protonation of the (methyl-)imidazole unit at pH ≤ 2 unit causes decreased excited-state lifetimes and an emission switch-off.Ni(COD)2-catalyzed cycloaddition reactions to access pyridines have been extensively studied. However, this catalyst typically requires drying procedures and inert-atmosphere techniques for the reactions. CTP-656 Herein, we report operationally simple nickel(0) catalysis to access substituted pyridines from various nitriles and 1,6-diynes without the aid of air-free techniques. The Ni-Xantphos-based catalytic manifold is tolerant to air, moisture, and heat while promoting the [2 + 2 + 2] cycloaddition reactions with high reaction yields and broad substrate scope. In addition, we disclose that not only the steric effect but also the frontier molecular orbital interactions can play a critical role in determining the regiochemical outcome of nickel-catalyzed [2 + 2 + 2] cycloaddition for the synthesis of substituted pyridines.Pickering emulsions (PEs) achieve interfacial stabilization by colloidal particle surfactants and are commonly used in food, cosmetics, and pharmaceuticals. Carbon nanotubes (CNTs) have recently been used as stabilizing materials to create dynamic single emulsions. In this study, we used the formation of Meisenheimer complexes on functionalized CNTs to fabricate complex biphasic emulsions containing hydrocarbons (HCs) and fluorocarbons (FCs). The reversible nature of Meisenheimer complex formation allows for further functionalization at the droplet-water interface. The strong affinity of fluorofluorescent perylene bisimide (F-PBI) to the CNTs was used to enhance the assembly of CNTs on the FC-water interface. The combination of different concentrations of the functionalized CNTs and the pelene additive enables predictable complex emulsion morphologies. Reversible morphology reconfiguration was explored with the addition of molecular surfactants. Our results show that the interfacial properties of functionalized CNTs have considerable utility in the fabrication of complex dynamic emulsions.Silicone elastomer-based fouling release coatings have been gaining increased attention in marine antibiofouling. However, the lack of fouling resistance limits their application. Introducing a zwitterionic polymer into silicone enhances its fouling resistance, but their incompatibility makes this challenging. In this work, a silicone elastomer with zwitterionic pendant chains has been prepared by grafting a telomer of tertiary carboxybetaine dodecafluoroheptyl ester ethyl acrylate (TCBF) and 3-mercaptopropyltriethoxysilane to the bis-silanol-terminated poly(dimethylsiloxane) (PDMS). The fluorocarbon groups drive the telomer onto the surface in the film formation process, while the TCBF groups hydrolyze and generate zwitterions on the surface, which is confirmed by attenuated total reflection infrared spectra analysis and water contact angle measurements. Bioassays using marine bacteria (Pseudomonas sp.) and diatoms (Navicula incerta) demonstrate that the antifouling efficacy is improved as the telomer content increases. The bacteria and diatom adhesion decreases by 95 and 81%, respectively, for the PDMS with 30 wt % telomer compared with the unmodified PDMS control. Meanwhile, the fouling release performance of PDMS is maintained with a pseudobarnacle removal strength of ∼0.1 MPa. This work provides a facile way to fabricate efficient silicone-based antifouling coatings.