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Sulfamates and sulfamides are prevalent in biological molecules, but their universal synthetic methods are limited. We herein report a sulfamoylation agent with high solubility and shelf stability. Various sulfamates and sulfamides can be synthesized directly from alcohols or amines by employing this agent with high selectivity and high yields. This protocol was also successfully used for late-stage sulfamoylation of pharmaceuticals containing a hydroxyl or amino group.Although light is the fastest means to manipulate the interfacial spin injection and magnetic proximity related quantum properties of two-dimensional (2D) magnetic van der Waals (vdW) heterostructures, its potential remains mostly untapped. Here, inspired by the recent discovery of 2D ferromagnets Fe3GeTe2 (FGT), we applied the real-time density functional theory (rt-TDDFT) to study photoinduced interlayer spin transfer dynamics in 2D nonmagnetic-ferromagnetic (NM-FM) vdW heterostructures, including graphene-FGT, silicene-FGT, germanene-FGT, antimonene-FGT and h-BN-FGT interfaces. We observed that laser pulses induce significant large spin injection from FGT to nonmagnetic (NM) layers within a few femtoseconds. In addition, we identified an interfacial atom-mediated spin transfer pathway in heterostructures in which the photoexcited spin of Fe first transfers to intralayered Te atoms and then hops to interlayered NM layers. Interlayer hopping is approximately two times slower than intralayer spin transfer. Our results provide the microscopic understanding for optically control interlayer spin dynamics in 2D magnetic heterostructures.A method for the enantio- and chemoselective iridium-catalyzed O-allylation of oximes is described. Kinetic resolution in an intramolecular setting provides enantioenriched oxime ethers and aliphatic allylic alcohols. The synthetic potential of the products generated with this method is showcased by their elaboration into a series of heterocyclic compounds and the formal synthesis of glycoprotein GP IIb-IIIa receptor antagonist (-)-roxifiban. Preliminary mechanistic experiments and computational data shed light on the remarkable chemoselectivity of the reaction.Transient receptor potential ankyrin 1 (TRPA1) is a nonselective calcium-permeable ion channel highly expressed in the primary sensory neurons functioning as a polymodal sensor for exogenous and endogenous stimuli and has generated widespread interest as a target for inhibition due to its implication in neuropathic pain and respiratory disease. Herein, we describe the optimization of a series of potent, selective, and orally bioavailable TRPA1 small molecule antagonists, leading to the discovery of a novel tetrahydrofuran-based linker. https://www.selleckchem.com/products/Rapamycin.html Given the balance of physicochemical properties and strong in vivo target engagement in a rat AITC-induced pain assay, compound 20 was progressed into a guinea pig ovalbumin asthma model where it exhibited significant dose-dependent reduction of inflammatory response. Furthermore, the structure of the TRPA1 channel bound to compound 21 was determined via cryogenic electron microscopy to a resolution of 3 Å, revealing the binding site and mechanism of action for this class of antagonists.A formal synthesis of (±)-cochlearol A was accomplished. The synthesis features Suzuki coupling and Friedel-Crafts cyclization as a convergent strategy to the functionalized tetralone ring and an intramolecular construction of the C/D ring involving sequential epoxide formation/acetal formation.Regulating cell-cell interactions and cell behaviors via cell surface engineering is of significance for biological research such as cell fate control and cell therapy. While extensive efforts have been made to induce cell-cell assembly via various cell surface modifications triggered by macromolecules or organic metabolites, controllable cell-cell interactions that include both assembly and disassembly triggered by metal ions remain a challenge. Herein, we report a strategy based on DNAzymes to realize controllable cell-cell interactions, triggered by metal ions. The metal-dependent DNAzyme-based cleavage can effectively manipulate cell behaviors, including cell-cell conjunctions and disaggregation. Using a Zn2+-specific DNAzyme, a Mg2+-specific DNAzyme, and their respective substrate strands as the building blocks, the corresponding DNA double-chain switches enabling two-factor disassembly are demonstrated. Moreover, the method has been applied to control the assembly and disassembly between two cell spheroids. Since a wide variety of metal-specific DNAzymes are available, this method can be readily applied to construct cell dynamic systems controlled by other metal ions, providing a smart and versatile platform to regulate dynamic cell behavior.The influence of donor-acceptor (D-A) groups on the nonlinear optical (NLO) property of B12N12 functionalized nanocluster has been investigated by density functional theory. We study the effect of bonding of three electron acceptor ligands (CN, COOH, and NO2) and three donor ligands (NH2, N(CH3)2, and PhNH2) positioned at opposite ends of B12N12 nanocluster in the gas phase. The result reveals that the complexation of D-A groups on the B12N12 nanocluster is energetically favorable and significantly narrowed the HOMO-LUMO gaps. The functionalization of D-A groups lead to an extremely large first hyperpolarizability value. Our survey reports the strongest NLO responses found in PhNH2-B12N12-PhCN cluster (1882.47 × 10-30 esu), whereas centrosymmetric B12N12 cluster yields a zero hyperpolarizability value. Designed systems are analyzed through the HOMO-LUMO gap, frontier molecular orbital, hyperpolarizability, Δr index, transition dipole moment density, density of states (DOS), and molecular electrostatic potential. The obtained results are well correlated with the computed absorption spectra of the molecule. The results demonstrate that phenyl ring incorporated D-A groups amplify the NLO response to a larger extent. The significant first hyperpolarizability arises due to charge transfer from the donor to the acceptor moiety. As a whole, this theoretical work provides a direction to researchers that the right choice of substitution can considerably impact the nonlinear optical property of BN nanoclusters.
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