Supporting_information_PDF – Supplemental material for Atom-efficient chlorination of benzoic acids with PCl₃ generating acyl chlorides

Supplemental material, Supporting_information_PDF for Atom-efficient chlorination of benzoic acids with PCl3 generating acyl chlorides by Jing Xiao and Li-Biao Han in Journal of Chemical Research</p

Nickel-Catalyzed Direct C–H/C–O Cross Couplings Generating Fluorobenzenes and Heteroarenes

The Ni-catalyzed direct C–H/C–O cross couplings of benzylic alcohol derivatives with fluorobenzenes and heteroarenes are disclosed. This transformation provides a straightforward and efficient method for the synthesis of these valuable heteroatom-containing compounds

CO₂ Adsorption Thermodynamics over N‑Substituted/Grafted Graphanes: A DFT Study

This work examines CO₂ adsorption over various N-substituted/grafted graphanes to identify the promotional effects of various N-functionalities have on the adsorption characteristics using DFT. CO₂ adsorbs weakly on a graphane surface functionalized with a single, isolated substituted N- or grafted NH₂-sites. The presence of coadsorbed H₂O on the surface promotes CO₂ adsorption on both N- and NH₂-sites, with highly exothermic adsorption energies (∼−50 kJ mol^–1). Directly grafted −NH₂ or −OH functional groups on C atoms adjacent to C atoms which have a −NH₂ group grafted suffer from geometrical restrictions preventing dual stabilization of formed carbamate upon adsorption of CO₂. CO₂ adsorption can be greatly enhanced with the presence of a −OH group or second −NH₂ group in the proximity of a −NH₂ site on graphane, and only if a <i>n</i>(−CH₂−) (<i>n</i> ≥ 1) linker is introduced between the −NH₂ or −OH and graphane surface (adsorption energies of −58.8 or −43.1 kJ mol^–1 at <i>n</i> = 2). The adsorption mechanistics provided by DFT can be used to guide the atomic-level rational design of N-based graphane and carbon adsorbents for CO₂ capture

Unraveling Structure Sensitivity in CO₂ Electroreduction to Near-Unity CO on Silver Nanocubes

The renewable-energy-powered electrochemical CO2 reduction reaction (CO2RR) provides an attractive strategy to simultaneously address the energy storage and environmental issues through the synthesis of carbon-neutral fuels. This study unravels structure sensitivity of ultrasmall Ag nanocubes with lengths below 25 and 70 nm (L25- and L70-Ag-NCs) enclosed completely by the (100) facet toward an efficient CO2RR to CO. The ultrasmall L25-Ag-NCs deliver a remarkably larger current density, a significantly higher Faraday efficiency (FE) of near-unity, and a comparably higher energy efficiency of 64.0% as well as a better stability of ∼18 h as compared to L70-Ag-NCs, Ag nanoparticles, and bulk Ag. More importantly, CO generation initiates at an ultralow overpotential of 146 mV, accompanied with a remarkably high onset CO FE of 59.6%, further demonstrating the excellence of L25-Ag-NCs for highly active and selective CO2RR. Density functional theory calculations, the percentages of various catalytically active sites, and how the architecture of NCs affecting the active sites as well as the partial density of states were analyzed; the results reveal that the essential origins credited for the enhanced catalytic activity and near-unity CO selectivity over L25-Ag-NCs at lowered η originate from the particular nanostructure, where energetically favorable active sites toward CO2RR are maximally introduced through accurately synthesizing the specific nanostructure enclosed by a certain facet

Presentation1_An Efficient Score Test Integrated with Empirical Bayes for Genome-Wide Association Studies.pdf

Many methods used in multi-locus genome-wide association studies (GWAS) have been developed to improve statistical power. However, most existing multi-locus methods are not quicker than single-locus methods. To address this concern, we proposed a fast score test integrated with Empirical Bayes (ScoreEB) for multi-locus GWAS. Firstly, a score test was conducted for each single nucleotide polymorphism (SNP) under a linear mixed model (LMM) framework, taking into account the genetic relatedness and population structure. Then, all of the potentially associated SNPs were selected with a less stringent criterion. Finally, Empirical Bayes in a multi-locus model was performed for all of the selected SNPs to identify the true quantitative trait nucleotide (QTN). Our new method ScoreEB adopts the similar strategy of multi-locus random-SNP-effect mixed linear model (mrMLM) and fast multi-locus random-SNP-effect EMMA (FASTmrEMMA), and the only difference is that we use the score test to select all the potentially associated markers. Monte Carlo simulation studies demonstrate that ScoreEB significantly improved the computational efficiency compared with the popular methods mrMLM, FASTmrEMMA, iterative modified-sure independence screening EM-Bayesian lasso (ISIS EM-BLASSO), hybrid of restricted and penalized maximum likelihood (HRePML) and genome-wide efficient mixed model association (GEMMA). In addition, ScoreEB remained accurate in QTN effect estimation and effectively controlled false positive rate. Subsequently, ScoreEB was applied to re-analyze quantitative traits in plants and animals. The results show that ScoreEB not only can detect previously reported genes, but also can mine new genes.</p

Ultra-Deep Adsorptive Desulfurization of Light-Irradiated Diesel Fuel over Supported TiO₂–CeO₂ Adsorbents

This study investigates ultra-deep adsorptive desulfurization (ADS) from light-irradiated diesel fuel over supported TiO2–CeO2 adsorbents. A 30-fold higher desulfurization capacity of 95 mL of fuel per gram of adsorbent (mL-F/g-sorb) or 1.143 mg of sulfur per gram of adsorbent (mg-S/g-sorb) was achieved from light-irradiated fuel over the original low-sulfur fuel containing about 15 ppm by weight (ppmw) of sulfur. The sulfur species on spent TiO2–CeO2/MCM-48 adsorbent was identified by sulfur K-edge XANES as sulfones and the adsorption selectivity to different compounds tested in a model fuel decreases in the order of indole > dibenzothiophenesulfone ≫ dibenzothiophene > 4-methyldibenzothiophene > benzothiophene > 4,6-dimethyldibenzothiophene > phenanthrene > 2-methylnaphthalene ∼ fluorene > naphthalene. The results suggest that during ADS of light-irradiated fuel, the original sulfur species were chemically transformed to sulfones, resulting in the significant increase in desulfurization capacity. For different supports for TiO2–CeO2 oxides, the ADS capacity increases with a decrease in the point of zero charge (PZC) value; for silica-supported TiO2–CeO2 oxides (the lowest PZC value of 2–4) with different surface areas, the ADS capacity increases monotonically with increasing surface area. The supported TiO2–CeO2/MCM-48 adsorbent can be regenerated using oxidative air treatment. The present study provides an attractive new path to achieve ultraclean fuel more effectively

DataSheet1_An Efficient Score Test Integrated with Empirical Bayes for Genome-Wide Association Studies.docx

Many methods used in multi-locus genome-wide association studies (GWAS) have been developed to improve statistical power. However, most existing multi-locus methods are not quicker than single-locus methods. To address this concern, we proposed a fast score test integrated with Empirical Bayes (ScoreEB) for multi-locus GWAS. Firstly, a score test was conducted for each single nucleotide polymorphism (SNP) under a linear mixed model (LMM) framework, taking into account the genetic relatedness and population structure. Then, all of the potentially associated SNPs were selected with a less stringent criterion. Finally, Empirical Bayes in a multi-locus model was performed for all of the selected SNPs to identify the true quantitative trait nucleotide (QTN). Our new method ScoreEB adopts the similar strategy of multi-locus random-SNP-effect mixed linear model (mrMLM) and fast multi-locus random-SNP-effect EMMA (FASTmrEMMA), and the only difference is that we use the score test to select all the potentially associated markers. Monte Carlo simulation studies demonstrate that ScoreEB significantly improved the computational efficiency compared with the popular methods mrMLM, FASTmrEMMA, iterative modified-sure independence screening EM-Bayesian lasso (ISIS EM-BLASSO), hybrid of restricted and penalized maximum likelihood (HRePML) and genome-wide efficient mixed model association (GEMMA). In addition, ScoreEB remained accurate in QTN effect estimation and effectively controlled false positive rate. Subsequently, ScoreEB was applied to re-analyze quantitative traits in plants and animals. The results show that ScoreEB not only can detect previously reported genes, but also can mine new genes.</p

Quasi-classical Trajectory Study of the Ne + H₂⁺ → NeH⁺ + H Reaction Based on Global Potential Energy Surface

Using the multireference configuration interaction method with a Davidson correction and a large orbital basis set (aug-cc-pVQZ), we obtain an energy grid that includes 32 038 points for the construction of a new analytical potential energy surface (APES) for the Ne + H2+ → NeH+ + H reaction. The APES is represented as a many-body expansion containing 142 parameters, which are fitted from 31 000 ab initio energies using an adaptive nonlinear least-squares algorithm. The geometric characteristics of the reported APES and the one presented here are also compared. On the basis of the APES we obtained, reaction cross sections are computed by means of quasi-classical trajectory (QCT) calculations and compared with the experimental and theoretical data in the literature

Active Sites on Ti–Ce Mixed Metal Oxides for Reactive Adsorption of Thiophene and Its Derivatives: A DFT Study

Density functional theory was used to investigate the mechanistic aspects of the adsorption of sulfur-containing compounds over Ti–Ce mixed metal oxides. We elucidate the promotional effect of the Ce dopant on TiO₂ and report the importance of oxygen vacancy-bound molecular oxygen as an active site on Ti–Ce mixed metal oxides for adsorption of thiophenic sulfur. The presence of surface-activated molecular oxygen leads to the oxidation of the sulfur, thus providing strongly bound sulfoxide and sulfone species. Ce doping of TiO₂ makes the oxidation process feasible both thermodynamically and kinetically. Surface oxygen vacancy sites act as catalytic sites in an adsorption cycle. DRIFTS results corroborate the presence of vacancy bound molecular oxygen. Our DFT calculations also examine thiophene and methyl-, dimethyl-, benzo-, and dibenzothiophenes adsorbed on TiO₂ and Ce-doped TiO₂ (001), (101), and (100) surfaces

Nickel-Catalyzed Phosphorylation of Phenol Derivatives via C–O/P–H Cross-Coupling

An efficient nickel-catalyzed phosphorylation of phenol derivatives with P­(O)–H compounds via C–O/P–H cross-coupling is described. Under the reaction conditions, various phenyl pivalates coupled readily with hydrogen phosphoryl compounds to afford the corresponding coupling products aryl phosphonates and aryl phosphine oxides in good to high yields