Perryyork1936

The products formed following the photodissociation of UV (200 nm) excited CS2 are monitored in a time resolved photoelectron spectroscopy experiment using femtosecond XUV (21.5 eV) photons. By spectrally resolving the electrons, we identify separate photoelectron bands related to the CS2 + hν → S(1D) + CS and CS2 + hν → S(3P) + CS dissociation channels, which show different appearance and rise times. The measurements show that there is no delay in the appearance of the S(1D) product contrary to the results of Horio et al. [J. Chem. Phys. 147, 013932 (2017)]. Analysis of the photoelectron yield associated with the atomic products allows us to obtain a S(3P)/S(1D) branching ratio and the rate constants associated with dissociation and intersystem crossing rather than the effective lifetime observed through the measurement of excited state populations alone.We study the relaxation process through a conical intersection of a photo-excited retinal chromophore model. The analysis is based on a two-electronic-state two-dimensional Hamiltonian developed by Hahn and Stock [J. OSI906 Phys. Chem. B 104 1146 (2000)] to reproduce, with a minimal model, the main features of the 11-cis to all-trans isomerization of the retinal of rhodopsin. In particular, we focus on the performance of various trajectory-based schemes to nonadiabatic dynamics, and we compare quantum-classical results to the numerically exact quantum vibronic wavepacket dynamics. The purpose of this work is to investigate, by analyzing electronic and nuclear observables, how the sampling of initial conditions for the trajectories affects the subsequent dynamics.A realistic double many-body expansion potential energy surface (PES) is developed for the 2A″ state of the carbon-nitrogen-oxygen (CNO) system based on MRCI-F12/cc-pVQZ-F12 ab initio energies. The new PES reproduces the fitted points with chemical accuracy (root mean square deviation up to 0.043 eV) and explicitly incorporates long range energy terms that can accurately describe the electrostatic and dispersion interactions. Thermal rate coefficients were computed for the C(3P) + NO(2Π) reaction for temperatures ranging from 15 K to 10 000 K, and the values are compared to previously reported results. The differences are rationalized, and the major importance of long range forces in predicting the rate coefficients for barrierless reactions is emphasized.In this work, molecular dynamics simulations are used to examine the self-assembly of anisotropically coated "patchy" nanoparticles. Specifically, we use a coarse-grained model to examine silica nanoparticles coated with alkane chains, where the poles of the grafted nanoparticle are bare, resulting in strongly attractive patches. Through a systematic screening process, the patchy nanoparticles are found to form dispersed, string-like, and aggregated phases, dependent on the combination of alkane chain length, coating chain density, and the fractional coated surface area. Correlation analysis is used to identify the ability of various particle descriptors to predict bulk phase behavior from more computationally efficient single grafted nanoparticle simulations and demonstrates that the solvent-accessible surface area of the nanoparticle core is a key predictor of bulk phase behavior. The results of this work enhance our knowledge of the phase space of patchy nanoparticles and provide a powerful approach for future screening of these materials.We designed functionalized hexagonal boron nitride (FhBN) nanoflakes with high proton conductivity in both in- and through-plane directions as next generation polymer electrolyte membranes (PEMs) for energy storage and conversion systems. The synthesis and functionalization of hBN nanoflakes with sulfonic acid (SA) groups are obtained by one-step and in situ liquid-phase exfoliation with excellent dispersibility and stability over a period of three months. The physico/chemical properties of FhBN nanoflakes were investigated by different spectroscopic and microscopic characterization, confirming chemical interactions between hBN lattice and SA groups. High concentrations (65 and 75 wt %) of FhBN nanoflakes composed with Nafion solution formed stable FhBN-Nafion nanocomposite PEMs, offering extra proton conduction sites, doubling ion-exchange capacity, and reducing the swelling ratio compared to those of Nafion. Our results demonstrate that both the in-plane and through-plane proton conductivities of FhBN-Nafion PEMs significantly improve under various conditions comparative to that of Nafion. The maximum values of both in- and through-plane conductivities for FhBN75%-Nafion PEM at 80% of humidity and 80 °C are 0.41 and 0.1 S·cm-1, respectively, which are 7 and 14 times higher than those of Nafion. The bidirectional superionic transport in highly concentrated FhBN PEMs is responsible for outstanding properties, useful for electrochemical energy devices.2'-Fucosyllactose (2'-FL), one of the most valuable oligosaccharides in human milk, is used as an emerging food ingredient in the nutraceutical and food industries due to its numerous health benefits. Herein, the de novo and salvage pathways for GDP-fucose synthesis were engineered and optimized in Escherichia coli BL21 (DE3) to improve the production of 2'-FL. The de novo pathway genes encoding phosphomannomutase (ManB), mannose-1-phosphate guanyltransferase (ManC), GDP-d-mannose-4,6-dehydratase (Gmd), and GDP-l-fucose synthase (WcaG) combined with the gene from the salvage pathway encoding fucose kinase/fucose-1-phosphate guanylyltransferase (Fkp) were reconstructed in two vectors to evaluate the GDP-fucose biosynthesis. Then, the fucT2 gene, encoding α1,2-fucosyltransferase, was introduced into the GDP-fucose-overproducing strains to realize 2'-FL biosynthesis. Furthermore, the genes in bypass pathways, including lacZ, fucI, fucK, and wcaJ, were inactivated to improve 2'-FL production. In addition, the two GDP-fucose synthesis pathways, along with fucT2, were transcriptionally fine-tuned to efficiently increase 2'-FL production. The final metabolically engineered E. coli produced 2.62 and 14.1 g/L in shake-flask and fed-batch cultivations, respectively.