Density functional theory studies on the mechanism of the reduction of CO2 to CO catalyzed by copper(I) boryl complexes

The detailed reaction mechanism for the reduction of CO2 to CO catalyzed by (NHC)Cu(boryl) complexes (NHC = N-heterocyclic carbene) was studied with the aid of DFT by calculating the relevant intermediates and transition state structures. Our DFT calculations show that the reaction occurs through CO2 insertion into the Cu-B bond to give a Cu-OC(=O)-boryl species (i.e., containing Cu-O and C-B bonds), and subsequent boryl migration from C to O, followed by alpha-bond metathesis between pinB-Bpin (B2pin2, pin = pinacolate = OCMe2CMe2O) and (NHC)Cu(OBpin). The overall reaction is exergonic by 38.0 kcal/mol. It is the nucleophilicity of the Cu-B bond, a function of the very strong alpha-donor properties of the boryl ligand, rather than the oxophilicity of boron, which determines the direction of the CO2 insertion process. The boryl migration from C to O, which releases the product CO, is the rate-determining step and involves the "vacant" orbital orbital on boron. The (NHC)Cu(boryl) complexes show unique activity in the catalytic process. For the analogous (NHC)Cu(alkyl) complexes, the CO2 insertion into the Cu-C bond giving a copper acetate intermediate occurs with a readily achievable barrier. However, the elimination of CO from the acetate intermediate through a methyl migration from C to O is energetically inaccessible.     

Cubic phases of block copolymers under shear and electric fields by cell dynamics simulation. I. Spherical phase

Cell dynamics simulation is used to investigate pathways of sphere-to-cylinder transition in block copolymer melt under applied simple shear flow and electric field. Both fields can induce the transition when their strength is above some critical value. At weak fields the spherical phase is preserved, with spheres being deformed into ellipsoids. Weak shear flow is found to improve order in the spherical phase. Observed sliding of layers of spheres under shear is very similar to the experimental finding by Hamley et al. [J. Chem. Phys. 108, 6929 (1998)]. The kinetic pathways are sensitive to the degree of microphase separation in the system and hence affected by temperature. The details of the pathways are described by means of Minkowski functionals.     

Solubility of budesonide in {ethanol + water} mixtures from T = (293.2 to 313.2) K: Experimental measurement and mathematical modelling

The solubility of budesonide (BDS) in binary mixtures of ethanol and water at T = (293.2–313.2) K is determined and mathematically represented using two cosolvency models, i.e. Jouyban–Acree model and Jouyban–Acree–van’t Hoff model. The mean relative deviations for fitting the solubility data of BDS in binary mixtures of ethanol + water are 6.6% and 6.5%, respectively. Furthermore, the apparent thermodynamic properties, dissolution enthalpy, dissolution entropy, and Gibbs free energy change of dissolution process of BDS in all the mixed solvents were calculated according to van’t Hoff and Gibbs equations. Dissolution of BDS in these mixed solvents is an endothermic process.     

10 Gb/s Reconfigurable Optical Logic Gate Using a Single Hybrid-Integrated SOA-MZI

Abstract

A novel reconfigurable Boolean device based on a single Mach-Zehnder interferometer with semiconductor optical amplifiers is demonstrated at 10 Gb/s using intensity return-to-zero modulated signals. The experimental results show that the device can be dynamically reconfigured to operate as a logic XOR, AND, OR, and NOT gate using optical switches. By properly adjusting the input powers, an extinction ratio higher than 10 dB may be obtained. The potential of integration of this architecture makes it an interesting approach in photonic computing and optical signal processing.     

High-speed 1H MAS NMR investigations of the weathered surface of a phosphate glass

Solid-state high-speed 1H MAS NMR spectroscopy was used to investigate the weathered surface of a potassium aluminum phosphate (KAP) glass exposed to a humid environment (30K2O10Al2O360P2O5, mol%). Through the combination of spin-spin relaxation and double quantum (DQ) filtering it was possible to resolve seven or eight different proton environments within the weathered surface of the KAP glass. Two-dimensional (2D) DQ and 2D NOESY NMR correlation experiments were performed to probe the spatial proximity of these different proton species. These 1H-1H correlation experiments helped confirm the spectral assignments. The analysis of these different 1H environments provides additional information about the chemical processes that occur at the weathered glass surface.     

Simulations of Closed Timelike Curves

Proposed models of closed timelike curves (CTCs) have been shown to enable powerful information-processing protocols. We examine the simulation of models of CTCs both by other models of CTCs and by physical systems without access to CTCs. We prove that the recently proposed transition probability CTCs (T-CTCs) are physically equivalent to postselection CTCs (P-CTCs), in the sense that one model can simulate the other with reasonable overhead. As a consequence, their information-processing capabilities are equivalent. We also describe a method for quantum computers to simulate Deutschian CTCs (but with a reasonable overhead only in some cases). In cases for which the overhead is reasonable, it might be possible to perform the simulation in a table-top experiment. This approach has the benefit of resolving some ambiguities associated with the equivalent circuit model of Ralph et al. Furthermore, we provide an explicit form for the state of the CTC system such that it is a maximum-entropy state, as prescribed by Deutsch.     

On choosing state variables for piecewise-smooth dynamical system simulations

Nonlinear Dynamics - Choosing state variables in a state-space representation of a nonlinear dynamical system is a nonunique procedure for a given input–output relationship and therefore a...     

Computational study of the hydrogen peroxide scavenging mechanism of allyl methyl disulfide,an antioxidant compound from garlic

Molecular Diversity - Although many sulfur containing garlic compounds present antioxidant activity, little is known about molecular mechanisms through which these compounds react with reactive...     

Optimization of Aqueous Stability versus π-Conjugation in Tetracationic Bis(triarylborane) Chromophores: Applications in Live-Cell Fluorescence Imaging

The stability of tetracationic triarylboranes in dilute aqueous solution was investigated by tuning the steric demand of the linker in a (para-(N,N,N-trimethylammonio)xylyl)₂B–(linker)–B(para-(N,N,N-trimethylammonio)xylyl)₂ structure. With increasing steric bulk of the linker, namely 1,4-phenylene, 2,2′′′-(3,3′′′-dimethyl)-5,2′:5′,2′′:5′′,5′′′-quaterthiophene, 9,10-anthracenylene, and 4,4′′′-(5′-(3,5-dimethylphenyl))(5′′-(3′′′,5′′′-dimethylphenyl))-2′,2′′-bithiophene, the stability of the compounds increased. The anthracene-based chromophore, compound 3M is water-stable for at least 48 h, is nontoxic to cells and exhibits an exceedingly high fluorescence quantum yield of 0.86 in water making it an ideal candidate for confocal live-cell imaging of lysosomes.