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barriers, which would lead to a too slow reaction, when the electrochemical gradient across the membrane is present, the chemistry must occur in a non-electrogenic manner. This explains why there is no energy conservation in cNOR.Radical vicinal carbohalofunctionalization of C-C multiple bonds via atom transfer processes constitutes an efficient method for the construction of halogenated building blocks with complete atom economy via radical cleavage of a pre-existing carbon-halogen σ-bond of an atom transfer reagent and their transposition over the π-bond of alkenes and alkynes. This review summarizes the recent advances in the photo-induced version of this class of transformations. A variety of transition-metal complexes, organic dyes, phosphines, amines, phenols and aldehydes were utilized as catalysts for the cleavage of the existing carbon-halogen bond of the corresponding atom transfer reagent in the presence of a light source. Alongside a variety of 1,2-haloalkylation and haloperfluoroalkylation reactions, atom transfer radical addition (ATRA) or cyclization (ATRC) reactions via the cleavage of the carbon-halogen bonds of aryl halides are also discussed.A rational approach to phosphaquinomethane metal(0) complexes, based on dearomatization of the phenylene unit in [W(CO)5](R)P(Cl)-C6H5-CPh2, is described, including theoretical studies on mechanisms and structures. Furthermore, the first phosphaquinone tungsten complex with reversible redox properties is reported thus illustrating the beneficial stabilization of ligation.In this study, the effect of CurDAc, a water-soluble curcumin derivative, on the formation and stability of amyloid fibers is revealed. CurDAc interaction with amyloid is structurally selective, which is reflected in a strong interference with hIAPP aggregation while showing weaker interactions with human-calcitonin and amyloid-β1-40 in comparison. Remarkably, CurDAc also exhibited potent fiber disaggregation for hIAPP generating a toxic oligomeric species.The reaction of N,N-di(2,6-bis(isopropyl)phenylimino-pyrrolyl-α-methyl)-N-methylamine H2L1 with copper(i) sources such as CuX (X = Cl (1), Br (2), and I (3)) afforded bis(chelated) ionic copper(ii) complexes of the type [CuL1H]X. A similar type of mononuclear structure was obtained with Cu(NO3)2·(H2O)3. Conversely, binuclear copper(ii) complexes [Cu2(μ-L1)(μ-OOCCH3)(μ-OH)](4) and [Cu2(μ-L1H)(μ-OOCPh)(μ-O)] (5) were obtained from the reaction of Cu(O2CR)2·H2O with H2L1. Notably, these reactions in the presence of a base yielded the neutral copper(ii) complex [CuL1] (6). This product was also obtained from the reaction of complex 2 or 4 with NaOH in methanol. All structures feature a dianionic imino-pyrrole motif and a protonated central amine function except 4. The reaction of H2L1 with NiCl2·DME gave the mononuclear complex [NiCl2(L1H2)], 7. In contrast to this, the reaction of the newly synthesized sterically less encumbered ligand N,N-di(phenylimino-pyrrolyl-α-methyl)-N-methylamine H2L2 with NiCl2·DME gave the binuclear complex [NiCl(L2H2)(HOMe)]2[Cl]2 (8). Both 7 and 8 show the amine-azafulvene ligand form and coordination of the central amine. The reaction of complex 7 with NaHBEt3 yielded a neutral complex [NiL1] (8) containing the imino-pyrrole form. In the molecular structures, interesting secondary coordination spheres incorporating guest molecules such as CHCl3 and MeOH in the crystal lattices and the presence of helical enantiomers were observed and analysed. In one case, CHCl3 was found inside an unusual cage-like structure supported by halogen bonds. Preliminary DFT calculations on the geometry of the nickel complex with H2L1 showed that the pentacoordinated tbp geometry is more stable than the square planar geometry.M. Basile, et al., Chem. Commun., 2015, 51, 5306-5309, showed that a sodium ion is sandwiched by uranyl(vi) oxygen atoms of two 3  3 uranyl(vi)-citrate complex molecules in single-crystals. By means of NMR spectroscopy supported by DFT calculations we provide unambiguous evidence for this complex to persist in aqueous solution above a critical concentration of 3 mM uranyl citrate. Unprecedented Ca2+ and La3+ coordination by a bis-(η3-uranyl(vi)-oxo) motif advances the understanding of uranium's aqueous chemistry. As determined from 17O NMR, Ca2+ and more distinctly La3+ cause strong O[double bond, length as m-dash]U[double bond, length as m-dash]O polarization, which opens up new ways for uranyl(vi)-oxygen activation and functionalization.A series of pentaatomic species has been investigated theoretically with relativistic DFT using the M06-L functional with both ZORA scalar relativistic correction, and including spin-orbit coupling effects. The distorted quasi-octahedral local minima for PtNO3+, PtN2O2 and PtN3O- corresponding to decavalent Pt were found to be unstable with respect to the elimination of O2, NO or N2. [https://www.selleckchem.com/products/z-vad(oh)-fmk.html selleck compound] However, barriers surrounding these minima suggest that these species could be achieved under low-temperature conditions, similar to what was predicted for PtO42+ dications. Decavalent platinum sets the upper limit for high oxidation states of the chemical elements.Hazardous remote places exist in the world. Why should health or life be risked sending a scientist to the investigation site, as the remote analytical instrumentation exists? Different scientific fields require instruments that could be used on-site (in situ), therefore the purpose of this work was to design a fully automated chemical analysis system small enough to be mountable on a drone. Here we show an autonomous analytical system with sampling capability on a drone. The system is suited for the remote and autonomous analysis of volatile and non-volatile chemicals in the air. The designed system weighs less than 800 g. Data are transmitted wirelessly. Collected substances are separated automatically without the intervention of the operator using the method of capillary zone electrophoresis. The analytes are detected using a miniaturized contactless conductivity detector quantifying them down to less than 1 μM. In this work, we demonstrated sampling and separation of volatile amines (triethylamine and diethylamine) and organic acids (acetic and formic acids), non-volatile inorganic cations (K+, Ca2+, Na+), and protein (bovine serum albumin) in the aerosol state.