The fundamental kinetics of the electrocatalytic sulfur reduction reaction (SRR), a complex 16-electron conversion process in lithium-sulfur batteries, is insufficiently explored to date. Herein, by directly profiling the activation energies in the multi-step SRR, we reveal that the initial reduction of sulfur to the soluble polysulfides is relatively easy with low activation energy, while the subsequent conversion of the polysulfides into the insoluble Li 2 S 2 /Li 2 S is more difficult with much higher activation energy, which contribute to the accumulation of polysulfides and exacerbate the polysulfide shuttling effect. We use heteroatom-doped graphene as a model system to explore electrocatalytic SRR. We show nitrogen and sulfur dual-doped graphene considerably reduces the activation energy to improve SRR kinetics. Density functional calculations confirm that the doping tunes the p-band center of the active carbons for an optimal adsorption strength of intermediates and electroactivity. This study establishes electrocatalysis as a promising pathway to high performance lithium-sulfur batteries. The sulfur reduction reaction (SRR) in lithium-sulfur (Li-S) chemistry undergoes a complex 16-electron conversion process, transforming S 8 ring molecules into a series of soluble lithium polysulfides (LiPSs) with variable chain lengths before fully converting them into 2 insoluble Li 2 S 2 /Li 2 S products. This 16-electron SRR process is of considerable interest for high-density energy storage with theoretical capacity of 1672 mAh g-1 , but the chemistry is plagued by sluggish sulfur reduction kinetics and polysulfide (PS) shuttling effect. In practical Li-S cells, these effects limit the rate capability and cycle life 1,2. These limitations are fundamentally associated with the slow and complex reduction reaction involving S 8 ring molecules. In general, the insulating nature of elemental sulfur and its reduced products, and the sluggish charge transfer kinetics lead to incomplete conversion of S 8 molecules to soluble LiPSs. These polysulfides may shuttle across the separator to react with and deposit on the lithium anode, resulting in rapid capacity fading 3. Considerable efforts have been devoted to combating the PS shuttling effect, typically by employing a passive strategy by using various sulfur host materials to physically or electrostatically trap the LiPSs in the cathode structure 4-13. These passive confinement/entrapping strategies have partly mitigated the PS shuttling
The modification of viruses using chemical conjugation techniques has brought the distant worlds of virology right into the center of nanotechnology. Viruses are naturally resilient biomolecules and this makes them exceptional templates for the creation of higher order polymers and as scaffolds for biological imaging and targeted drug delivery. In this review, we highlight progress in utilizing chemical strategies to interface viruses with synthetic polymers, to create bright bionanoparticles using synthetic fluorescent dyes, and how orthogonal chemical transformations allow for targeted drug delivery. WIREs Nanomed Nanobiotechnol 2016, 8:512-534. doi: 10.1002/wnan.1379 For further resources related to this article, please visit the WIREs website.
This article is available online at http://www.jlr.org on lipid parameters and dyslipidemia in a Chinese population. J. Lipid Res. 2011. 52: 354-360. Supplementary key words genetic polymorphisms • lipid levels • strokeDyslipidemia is a common health problem in developing countries, including China ( 1 ). A vast line of evidence has demonstrated that plasma lipids and lipoprotein concentrations are important risk factors for atherosclerosis and related vascular diseases, which are the leading causes of death in China and the rest of the world ( 2, 3 ). Although plasma lipid concentrations are strongly infl uenced by smoking, diet, level of physical activity, and other lifestyles choices, twin and family studies suggest that about 50% of the variation in HDL cholesterol (HDL-C), LDL-C, and total cholesterol (TC) levels is genetically determined ( 4 ).Since 2008, genome-wide association (GWA) studies of plasma lipid levels have further identifi ed several common variants associated with plasma lipid levels, exerting a modest fraction of variance (2% or less) ( 5-15 ). Some newly identifi ed genes are potential new drug targets, so these recent genetic advances have broadened our understanding of basic metabolic pathways and can improve patient classifi cation, disease diagnosis, and treatment strategies ( 14 ). However, because of the known differences in genome-wide linkage disequilibrium patterns among Abstract A number of recent genome-wide association (GWA) studies have identifi ed several novel genetic determinants of plasma lipid and lipoprotein concentrations in European populations. However, it is still unclear whether these loci identifi ed in Caucasian GWA studies also exert the same effect on lipid and lipoprotein concentrations in a Chinese population. We genotyped 10 single-nucleotide polymorphisms (SNPs) in nine loci in a Chinese Han population sample (n = 4,192) and assessed the associations of these SNPs with metabolic traits, using linear regression adjusted for age, gender, diabetes status, and body mass index. Three variants (rs12654264, P ~ 1.7 × 10 ؊ 6 ; rs3764261, P ~ 7.1 × 10 ؊ 7 ; and rs4420638, P ~ 1.1 × 10 ؊ 3 ) showed strong evidence for association with total cholesterol; four variants (rs780094, P ~ 1.8 × 10 ؊ 11 ; rs17145738, P ~ 5.0 × 10 ؊ 7 ; rs326, P ~ 2.3 × 10 ; and rs4420638, P ~ 3.6 × 10 ؊ 4 ) showed strong evidence for association with LDL-C, and four variants (rs326, P ~ 2.8 × 10 ؊ 3 ; rs1800588, P ~ 6.1 × 10 ؊ 4 ; rs3764261, P ~ 2.0 × 10 ؊ 3 ; and rs4420638, P ~ 9.4 × 10 ؊ 5 ) showed strong evidence for association with total cholesterol-HDL-C-related ratio. These SNPs generated strong combined effects on lipid traits and dyslipidemia. Our fi ndings indicate that the variants that associated with metabolic traits in Europeans may also play a role in a Chinese Han
Given the important agricultural and medicinal application of optically pure heterocycles bearing a trifluoromethyl group at the stereogenic carbon center in the heterocyclic framework, the exploration of efficient and practical synthetic strategies to such types of molecules remains highly desirable. Catalytic enantioselective synthesis has one clear advantage that it is more cost-effective than other synthetic methods, but remains limited by challenges in achieving excellent yield and stereoselectivities with a low catalyst loading. Thus far, numerous models of organo- and organometal-catalyzed asymmetric reactions have been exploited to achieve this elusive goal over the past decade. This review article describes recent progress on this research topic, and focuses on an understanding of the catalytic asymmetric protocols exemplified in the catalytic enantioselective synthesis of a wide range of complex enantioenriched trifluoromethylated heterocycles.
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