Simplicity Beneath Complexity: Counting Molecular Electrons Reveals Transients and Kinetics of Photodissociation Reactions

Time‐resolved pump–probe gas‐phase X‐ray scattering signals, extrapolated to zero momentum transfer, provide a measure of the number of electrons in a system, an effect that arises from the coherent addition of elastic scattering from the electrons. This allows to identify reactive transients and determine the chemical reaction kinetics without the need for extensive scattering simulations or complicated inversion of scattering data. We examine the photodissociation reaction of trimethylamine and identify two reaction paths upon excitation to the 3p state at 200 nm: a fast dissociation path out of the 3p state to the dimethyl amine radical (16.6±1.2 %) and a slower dissociation via internal conversion to the 3s state (83.4±1.2 %). The time constants for the two reactions are 640±130 fs and 74±6 ps, respectively. Additionally, it is found that the transient dimethyl amine radical has a N?C bond length of 1.45±0.02 Å and a C?N?C bond angle of 118°±4°.     

Transition Metal‐Free Reduction of Activated Alkenes Using a Living Microorganism

Microorganisms can be programmed to perform chemical synthesis via metabolic engineering. However, despite an increasing interest in the use of de novo metabolic pathways and designer whole‐cells for small molecule synthesis, the inherent synthetic capabilities of native microorganisms remain underexplored. Herein, we report the use of unmodified E. coli BL21(DE3) cells for the reduction of keto‐acrylic compounds and apply this whole‐cell biotransformation to the synthesis of aminolevulinic acid from a lignin‐derived feedstock. The reduction reaction is rapid, chemo‐, and enantioselective, occurs under mild conditions (37 °C, aqueous media), and requires no toxic transition metals or external reductants. This study demonstrates the remarkable promiscuity of central metabolism in bacterial cells and how these processes can be leveraged for synthetic chemistry without the need for genetic manipulation.     

Catalytic comparison of various polar Zn(II)-Schiff base complexes and VO(II)-Schiff base complexes in (ep)oxidation processes of 1,2-cyclohexene and cyclohexane

Research on Chemical Intermediates - The reactivity of Zn2+ and VO2+ ions towards pyridinyl Schiff bases, in the absence or presence of a p-sodium sulfonate group (HPSNa and HPS, respectively),...     

Evaluation of solvents’ effect on solubility,intermolecular interaction energies and habit of ascorbic acid crystals

Solubility of active pharmaceutical ingredient (API) in solvents is very important for drug development and manufacturing. Solubility data may provide further information such as thermochemical properties and intermolecular interactions that may lead to a better understanding of the formation of API crystals. In this study, solubility of ascorbic acid was determined by gravimetric method in four different commonly used polar protic solvents: water, methanol, ethanol and 2-propanol. The solubility of ascorbic acid crystal was also predicted using Conductor-like Screening Model – Realistic Solvent (COSMO-RS) approach. In this computational analysis, the generated ΔG values are based on the solubilities that were experimentally obtained to simulate the intermolecular forces. The intermolecular interaction data from COSMO-RS provide an insight into the relationship between the intermolecular interactions and its crystal habit across four different polar protic solvents. The habit of the crystals was then determined using light microscopy and scanning electron microscopy techniques, while the polymorphic form of the crystals was identified by X-ray powder diffraction and single X-ray diffraction techniques. The solubility and characterization data showed that the solvents with high polarity increased the solubility of ascorbic acid. The data also showed that different solvent polarity influenced the crystal habit, but did not change the crystal structure to form a new polymorph.     

Statistical Thermodynamics Unveils How Ions Influence an Aqueous Diels-Alder Reaction

The kinetics of Diels-Alder (DA) reactions in water has been known to be altered by salts for a long time. Yet the question how salts influence the reaction rate, either as rate-enhancing or rate-reducing additives, has so far remained unresolved. Conflicting hypotheses involve (i) indirect salt contributions through the modulation of internal pressure and (ii) making (or breaking) of the so-called “water-structure” by salts that strengthen (or weaken) the hydrophobic effect. In contrast to the qualitative nature of these hypotheses, here we answer this question quantitatively through a combination of transition state theory and fluctuation adsorption-solvation theory (FAST) using the DA reaction between anthracene-9-carbinol and N-ethylmaleimide as an example. We show that rate enhancement is driven by the salting out of the hydrophobic reactant, while rate-enhancing salts exhibit stronger affinity to the transition state.     

Triphenylphosphine and sodium iodide: a new catalyst combination to rival precious metal complexes in visible light photoredox catalysis

<正>Photoredox catalysis has changed the landscape of modern synthetic organic chemistry by prompting a dramatic increase in research activity into reactions that proceed through free radical intermediates~([1]). Instrumental in this shift in interest from two-electron to single-electron processes was the widespread appreciation of the synthetic utility of pho-     

Fast-ion energy-flux enhancement from ultrathin foils irradiated by intense and high-contrast short laser pulses

Recent significant improvements of the contrast ratio of chirped pulse amplified pulses allows us to extend the applicability domain of laser accelerated protons to very thin targets. In this framework, we propose an analytical model particularly suitable to reproducing ion laser acceleration experiments using high intensity and ultrahigh contrast pulses. The model is based on a self-consistent solution of the Poisson equation using an adiabatic approximation for laser generated fast electrons which allows one to find the target thickness maximizing the maximum proton (and ion) energies and population as a function of the laser parameters. Model furnished values show a good agreement with experimental data and 2D particle-in-cell simulation results.     

Jet substructure as a new Higgs-search channel at the Large Hadron Collider

It is widely considered that, for Higgs boson searches at the CERN Large Hadron Colider, WH and ZH production where the Higgs boson decays to bb are poor search channels due to large backgrounds. We show that at high transverse momenta, employing state-of-the-art jet reconstruction and decomposition techniques, these processes can be recovered as promising search channels for the standard model Higgs boson around 120 GeV in mass.     

Self-assembled chiral superstructures composed of rigid achiral molecules and molecular scale chiral induction by dopants

We explore the phase behavior of a rigid achiral bent-core model system. Nematic and smectic phases form at higher densities, whereas micelles and columns composed of chiral clusters of these molecules self-assemble at lower densities. No nucleation mechanism requiring transient chirality is possible in the formation of these chiral superstructures due to the rigid achiral nature of the substituents. We show the chiral micelles are minima of the potential energy surface using energy minimization and parallel tempering simulations. Chiral dopants were found to induce the system to adopt a consistent chiral twist direction, the first molecular scale computer simulation of this effect.     

Quantum Stochastic Convolution Cocycles II

Schürmann’s theory of quantum Lévy processes, and more generally the theory of quantum stochastic convolution cocycles, is extended to the topological context of compact quantum groups and operator space coalgebras. Quantum stochastic convolution cocycles on a C*-hyperbialgebra, which are Markov-regular, completely positive and contractive, are shown to satisfy coalgebraic quantum stochastic differential equations with completely bounded coefficients, and the structure of their stochastic generators is obtained. Automatic complete boundedness of a class of derivations is established, leading to a characterisation of the stochastic generators of *-homomorphic convolution cocycles on a C*-bialgebra. Two tentative definitions of quantum Lévy process on a compact quantum group are given and, with respect to both of these, it is shown that an equivalent process on Fock space may be reconstructed from the generator of the quantum Lévy process. In the examples presented, connection to the algebraic theory is emphasised by a focus on full compact quantum groups.