For more than three decades the catalytic synthesis of acrylates from the cheap and abundantly available C(1) building block carbon dioxide and alkenes has been an unsolved problem in catalysis research, both in academia and industry. Herein, we describe a homogeneous catalyst based on nickel that permits the catalytic synthesis of the industrially highly relevant acrylate sodium acrylate from CO(2), ethylene, and a base, as demonstrated, at this stage, by a turnover number of greater than 10 with respect to the metal.

Interatomic (or intermolecular) Coulombic decay is a general, very efficient mode of decay of inner valence vacancies in clusters. The physically appealing interpretation of such decays as a transfer of a virtual photon between two cluster units rests on the neglect of the orbital overlap between them. We show that even in loosely bound van der Waals clusters the orbital overlap is a crucial factor. At the equilibrium geometry of a cluster, the overlap effect can bring about an enhancement of the decay rate by 2-3 orders of magnitude, making the process dramatically more efficient than implied by the simple estimations.

Rivaling the best one: Thermal [2+2] cycloadditions of TCNE, TCNQ, and F(4)-TCNQ to N,N-dimethylanilino-substituted cyanoalkynes afforded a new class of organic super-acceptors featuring efficient intramolecular charge-transfer interactions. These acceptors rival the acceptor F(4)-TCNQ in the propensity for reversible electron uptake as well as in electron affinity (see figure), which makes them interesting as p-type dopants for potential application in optoelectronic devices.Thermal [2+2] cycloadditions of tetracyanoethene (TCNE), 7,7,8,8-tetracyanoquinodimethane (TCNQ), and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F(4)-TCNQ) to N,N-dimethylanilino-substituted (DMA-substituted) alkynes bearing either nitrile, dicyanovinyl (DCV; -CH==C(CN)(2)), or tricyanovinyl (TCV; -C(CN)==C(CN)(2)) functionalities, followed by retro-electrocyclization, afforded a new class of stable organic super-acceptors. Despite the nonplanarity of these acceptors, as revealed by X-ray crystallographic analysis and theoretical calculations, efficient intramolecular charge-transfer (CT) interactions between the DMA donors and the CN-containing acceptor moieties are established. The corresponding CT bands appear strongly bathochromically shifted with maxima up to 1120 nm (1.11 eV) accompanied by an end-absorption in the near infrared around 1600 nm (0.78 eV) for F(4)-TCNQ adducts. Electronic absorption spectra of selected acceptors were nicely reproduced by applying the spectroscopy oriented configuration interaction (SORCI) procedure. The electrochemical investigations of these acceptors by cyclic voltammetry (CV) and rotating disc voltammetry (RDV) in CH(2)Cl(2) identified their remarkable propensity for reversible electron uptake rivaling the benchmark compounds TCNQ (E(red,1)=-0.25 V in CH(2)Cl(2) vs. Fc(+)/Fc) and F(4)-TCNQ (E(red,1)=+0.16 V in CH(2)Cl(2) vs. Fc(+)/Fc). Furthermore, the electron-accepting power of these new compounds expressed as adiabatic electron affinity (EA) has been estimated by theoretical calculations and compared to the reference acceptor F(4)-TCNQ, which is used as a p-type dopant in the fabrication of organic light-emitting diodes (OLEDs) and solar cells. A good linear correlation exists between the calculated EAs and the first reduction potentials E(red,1). Despite the substitution with strong DMA donors, the predicted EAs reach the value calculated for F(4)-TCNQ (4.96 eV) in many cases, which makes the new acceptors interesting for potential applications as dopants in organic optoelectronic devices. The first example of a charge-transfer salt between the DMA-substituted TCNQ adduct (E(red,1)=-0.27 V vs. Fc(+)/Fc) and the strong electron donor decamethylferrocene ([FeCp*(2)]; Cp*=pentamethylcyclopentadienide; E(ox,1)=-0.59 V vs. Fc(+)/Fc) is described. Interestingly, the X-ray crystal structure showed that in the solid state the TCNQ moiety in the acceptor underwent reductive sigma-dimerization upon reaction with the donor.

The valence ionization and double ionization spectra of the water molecule, of the water dimer, and the cyclic water clusters (H2O)3 and (H2O)4 are calculated by ab initio Green's function methods and discussed in some detail. Particular attention is paid to the analysis of the development of the spectra with increasing cluster size. Electronic decay following inner valence ionization is addressed and a crude estimate for the kinetic energy spectrum of the secondary electrons is given for the clusters.

The relative proximity of Al atoms substituted in zeolite lattices is an important parameter that influences both hydrothermal stability and catalytic function, but the underlying chemistry that governs Al site proximity is not well understood. Here, we examine relationships between exchanged countercations and different Al–Al arrangements in a chabazite (SSZ-13) zeolite lattice. We report periodic supercell density functional theory (DFT) calculations for structures and energies of SSZ-13 lattices with systematically enumerated and varied Al–Al proximity, both charge-uncompensated and charge-compensated by either proton pairs (H+/H+) or divalent copper cations (Cu2+). Al–Al interactions are electrostatically repulsive without charge compensation, but the relative energies of certain Al–Al site arrangements change upon compensation by countercations. Al–Al interactions are uniformly attractive when compensated by H+/H+ pairs but are attractive at long and repulsive at short Al–Al distances when compensated by Cu2+, highlighting the role of the countercation in stabilizing different Al–Al arrangements. Through descriptor analysis, we find that the Cu2+ energy landscape can be described by models consisting of electrostatics and a binary term that specifies whether or not Cu2+ resides in the six-membered ring (6MR). The H+/H+ and Cu2+ energy landscapes together imply that Cu2+ prefers to reside at 6MR Al–Al pairs. These results shed light on how countercations influence Al distribution and rearrangement during synthesis and postsynthetic treatments of the SSZ-13 zeolite, which potentially influences its susceptibility to dealumination during hydrothermal aging. The systematic DFT computation workflow and descriptor analysis reported here are promising approaches that can be applied generally to examine other combinations of ions and zeotypes of interest.

The simulation of polymerization processes is of enormous industrial importance. A quantum chemical method based on density functional theory is developed and validated that provides almost chemical accuracy for radical polymerization propagation of industrially relevant monomers in aqueous solution. The necessary corrections are computed using the CC level of theory. Solvent effects are accounted for by the solvation model COSMO‐RS. The method is capable of reproducing and rationalizing, for example, monomer concentration effects on the propagation rate for NVP. A comparison is performed with recent PLP experimental data. The method does not rely on error compensation effects or empiric corrections and is suitable for industrially relevant systems.

In the search for a highly active and selective heterogenized metathesis catalyst, we systematically varied the pore geometry and size of various silica-based mesoporous (i.e., MCM-41, MCM-48, and SBA-15) and microporous (ZSM-5 and MWW) versus macroporous materials (D11-10 and Aerosil 200), besides other process parameters (temperature, dilution, and mean residence time). The activity and, especially, selectivity of such "linker-free" supports for ruthenium metathesis catalysts were evaluated in the cyclodimerization of cis-cyclooctene to form 1,9-cyclohexadecadiene, a valuable intermediate in the flavor and fragrance industry. The optimized material showed not only exceptionally high selectivity to the valuable product, but also turned out to be a truly heterogeneous catalyst with superior activity relative to the unsupported homogeneous complex.

In higher plants, the redox-active tripeptide glutathione (GSH) fulfills a plethora of functions. These include its pivotal role for maintaining the cellular redox poise and its involvement in detoxification of heavy metals and xenobiotics. Intimately linked to these functions, GSH also acts as a cellular signal, mediating control of enzyme and/or regulatory protein activities, either directly or via glutaredoxins. The redox potential of the GSH/GSSG couple is not only affected by the GSH/GSSG ratio but also by changes in GSH synthesis and/or degradation. As this couple operates as redox buffer in several cellular compartments, the regulation of GSH biosynthesis and transport (both intra- and intercellularly) are fundamental to the maintenance of cellular redox homeostasis during plant development and, even more so, when plants are exposed to biotic or abiotic stress. This review highlights novel aspects of GSH biosynthesis and transport with a focus on the regulation of the GSH1 (= gamma-glutamylcysteine synthetase) enzyme. Interestingly, GSH1 appears to be exclusively confined to the plastids, whereas the second biosynthetic enzyme, GSH2, is predominantly localized in the cytosol. GSH1 expression and enzyme activity are under multiple controls, extending from transcriptional regulation to post-translational redox control. Now that the plant GSH1 protein structure has been solved, the molecular basis of GSH1 function and redox regulation can be addressed. The review concludes with a discussion of the simultaneous changes observed for GSH synthesis, transport, and metabolism during Cd-induced phytochelatin accumulation.