Bruhnknowles1682

lncRNAs actively regulate gene expression. They contribute to chromosomal interactions at close or distant genomic regions, which, in turn, regulate transcription [1]. Ariel et al [2] reveal in a recent study a new molecular mechanism of the Arabidopsis lncRNA APOLO. The authors extend previously reported functions of APOLO in cis-regulation of chromosomal looping and transcription of its neighbor gene to a set of distant genes involved in auxin-induced molecular pathways controlling lateral root development. Noteworthy, APOLO recognition of multiple trans-modulated targets occurs through a novel mechanism involving R-loop formation. © 2020 The Authors.Scientic evidence has shown oxygenates help to reduce dangerous pollutants arising from burning fossil fuel in the automotive sector. For this reason, they have spread widely as additives. The aim of this work consists in providing a comprehensive identification of the main primary oxidation products of diisopropyl ether (DIPE), one of the most promising among etheric oxygenates. The Cl-initiated oxidation of DIPE is examinated by using a vacuum ultraviolet (VUV) synchrotron radiation at the Advanced Light Source (ALS) of the Lawrence Berkeley National Laboratory (LBNL). Products are identified on the basis of their mass-to-charge ratio, shape of photoionization spectra, adiabatic ionization energies, and chemical kinetic profiles, at three different temperatures (298, 550, and 650 K). Acetone, propanal, propene, and isopropyl acetate have been identified as major reaction products. Acetone is the main primary product. Theoretical calculations using the composite CBS-QB3 method provided useful tools to validate the postulated reaction mechanisms leading to experimentally observed species. The formation of other species is also discussed. © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.Haloalkynylation reactions represent an efficient method for the simultaneous introduction of a halogen atom and an acetylenic unit. For the first time, we are reporting a gold(I)-catalyzed haloalkynylation of aryl alkynes which delivers exclusively the cis addition product. This protocol enables the simple synthesis of conjugated and halogenated enynes in yields up to 90%. Notably, quantum chemical calculations reveal exceptional interplay between the regioselective attack at the chloroacetylene No matter which C-C bond is formed, always the same enyne product is formed. This is only possible via rearrangement of the corresponding skeleton. Hereby, one reaction pathway proceeds via a chloronium ion with a subsequent aryl shift; in the second case the corresponding vinyl cation is stabilized by a 1,3-chlorine shift. 13C-labeling experiments confirmed that the reaction proceeds via both reaction pathways. © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.A palladium-catalyzed cross-coupling between in situ generated allenyl/propargyl-lithium species and aryl bromides to yield highly functionalized allenes is reported. The direct and selective formation of allenic products preventing the corresponding isomeric propargylic product is accomplished by the choice of SPhos or XPhos based Pd catalysts. The methodology avoids the prior transmetalation to other transition metals or reverse approaches that required prefunctionalization of substrates with leaving groups, resulting in a fast and efficient approach for the synthesis of tri- and tetrasubstituted allenes. Experimental and theoretical studies on the mechanism show catalyst control of selectivity in this allene formation. © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.Chiral 1,2-bimetallic reagents are useful motifs in synthetic chemistry. Although  syn -1,2-bimetallic compounds can be prepared by alkene dimetallation,  anti -1,2-bimetallics are still rare. The stereospecific 1,2-metallate shift that occurs during conjunctive cross-coupling is shown to enable a practical and modular approach to the catalytic synthesis of enantioenriched  anti -1,2-borosilanes.  In addition to reaction development, the synthetic utility of  anti -1,2-borosilanes was investigated, including applications to the synthesis of  anti -1,2-diols and  anti -1,2-amino alcohols. © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.We report the first examples of catalytic enantioselective benzilic ester rearrangement reaction. In the presence of a catalytic amount of Cu(OTf)2 and a chiral box ligand under mild conditions, reaction of 2,3-diketoesters with alcohols afforded structurally diverse α-aryl(alkyl) substituted-α-hydroxy malonates (tartronic esters) in good to excellent yields with high enantioselectivities. Preliminary mechanistic studies indicated that hemiketalization, rather than the dynamic kinetic resolution of hemiketal, was the enantiodetermining step under our reaction conditions. © 2020 Wiley-VCH Verlag GmbH & Co. MEK inhibitor review KGaA, Weinheim.The nematic twist-bend (NTB ) liquid crystal phase possesses a local helical structure with a pitch length of a few nanometres and is the first example of spontaneous symmetry breaking in a fluid system. All known examples of the NTB phase occur in materials whose constituent mesogenic units are aromatic hydrocarbons. It is not clear if this is due to synthetic convenience or a bona fide structural requirement for a material to exhibit this phase of matter. In this work we demonstrate that materials consisting largely of saturated hydrocarbons can also give rise to this mesophase. © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.Nickel iron oxyhydroxide is the benchmark catalyst for the oxygen evolution reaction (OER) in alkaline medium. Whereas the presence of Fe ions is essential to the high activity, the functions of Fe are currently under debate. Using oxygen isotope labeling and operando Raman spectroscopic experiments, we obtain turnover frequencies (TOFs) of both Ni and Fe sites for a series of Ni and NiFe layered double hydroxides (LDHs), which are structurally defined samples of the corresponding oxyhydroxides. The Fe sites have TOFs 20-200 times higher than the Ni sites such that at an Fe content of 4.7 % and above the Fe sites dominate the catalysis. Higher Fe contents lead to larger structural disorder of the NiOOH host. A volcano-type correlation was found between the TOFs of Fe sites and the structural disorder of NiOOH. Our work elucidates the origin of the Fe-dependent activity of NiFe LDH, and suggests structural ordering as a strategy to improve OER catalysts. © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.