Chiral corannulenes abound, but suffer generally from configurational lability associated with bowl‐to‐bowl inversion, 1 thus obviating questions of stereogenicity and stereoelement construction. 2 In contrast, peri‐annulated corannulenes show greatly increased barriers for bowl‐to‐bowl inversion; specifically indenocorannulenes invert on a time scale too slow to observe by normal NMR methods and raise the possibility of creating chiral atropisomeric bowl‐shaped aromatics. 3 Two methods for preparing indenocorannulene from simple 2‐haloarylcorannulenes—silyl cation C–F activation, 4 and Pd‐mediated C–Cl activation[5]—enable the synthesis of an array of such chiral atropisomeric indenocorannulenes. 6 Resolution of the enantiomers by high‐performance liquid chromatography over chiral support phases motivates the study of chiroptical properties, the assignment of absolute “Cartesian” configuration, and the assessment of configurational stability. 7 These studies bring into question any systematic assignment of nontrivial stereoelements (i.e. not the molecule in its entirety) and refute any assertion of congruence between “Cahn–Ingold–Prelog elements” and the physical or “Cartesian” basis of chirality. 相似文献
The cannabinoid CB1 receptor (CB1R) is an abundant metabotropic G‐protein‐coupled receptor that has been difficult to address therapeutically because of CNS side effects exerted by orthosteric drug candidates. Recent efforts have focused on developing allosteric modulators that target CB1R. Compounds from the recently discovered class of mixed agonistic and positive allosteric modulators (Ago‐PAMs) based on 2‐phenylindoles have shown promising functional and binding properties as CB1R ligands. Here, we identify binding modes of both the CP 55,940 agonist and GAT228, a 2‐phenylindole allosteric modulator, by using our metadynamics simulation protocol, and quantify their affinity and cooperativity by atomistic simulations. We demonstrate the involvement of multiple adjunct binding sites in the Ago‐PAM characteristics of the 2‐phenylindole modulators and explain their ability to compete with orthosteric agonists at higher concentrations. We validate these results experimentally by showing the contribution of multiple sites on the allosteric binding of ZCZ011, another homologous member of the class, together with the orthosteric agonist. 相似文献
Palladium on carbon catalyzes C?O bond cleavage of aryl ethers (diphenyl ether and cyclohexyl phenyl ether) by alcohols (R?OH) in H2. The aromatic C?O bond is cleaved by reductive solvolysis, which is initiated by Pd‐catalyzed partial hydrogenation of one phenyl ring to form an enol ether. The enol ether reacts rapidly with alcohols to form a ketal, which generates 1‐cyclohexenyl?O?R by eliminating phenol or an alkanol. Subsequent hydrogenation leads to cyclohexyl?O?R. 相似文献
Microbes use siderophores to access essential iron resources in the environment. Over 500 siderophores are known, but they utilize a small set of common moieties to bind iron. Azotobacter chroococcum expresses iron‐rich nitrogenases, with which it reduces N2. Though an important agricultural inoculant, the structures of its iron‐binding molecules remain unknown. Here, the “chelome” of A. chroococcum is examined using small molecule discovery and bioinformatics. The bacterium produces vibrioferrin and amphibactins as well as a novel family of siderophores, the crochelins. Detailed characterization shows that the most abundant member, crochelin A, binds iron in a hexadentate fashion using a new iron‐chelating γ‐amino acid. Insights into the biosynthesis of crochelins and the mechanism by which iron may be removed upon import of the holo‐siderophore are presented. This work expands the repertoire of iron‐chelating moieties in microbial siderophores. 相似文献
Electrodeposition is a common technique for coating metallic or semiconducting substrates. The growth of the layers occurs through faradaic processes in which charges are transferred across the substrate-electrolyte interface. Since more than one reaction can occur simultaneously, it is important to study the faradaic efficiency (ε) associated to the growth of the desired layers and relate it to other parameters in order to optimize the process. In this work, an indirect method to determine the faradaic efficiency of electrodeposits with porosity (p) is proposed. The method was satisfactorily applied to porous β-Ni(OH)2 films obtained by light-assisted anodic electrodeposition. These films were grown using different electrolyte concentrations (C) and temperatures (T). In this case, a direct dependence of p and ε with C and T was found.
In this article we report the results of an experiment performed in 1993 at PSI. The goal was to determine the absolute rate of nuclear muon capture by3He. In the experiment we used a new technique recently developed at Gatchina. As a preliminary result from this experiment we obtained
c=(1496±3(stat)-3(syst)) s–1. 相似文献