α‑Alkylation of Ketones with Primary Alcohols Catalyzed by a Cp*Ir Complex Bearing a Functional Bipyridonate Ligand

A Cp*Ir complex bearing a functional bipyridonate ligand was found to be a highly effective and versatile catalyst for the α-alkylation of ketones with primary alcohols under extremely environmentally benign and mild conditions (0.1 equiv of Cs₂CO₃ per substrate, reflux in <i>tert</i>-amyl alcohol under an air atmosphere for 6 h). Furthermore, this complex also exhibited a high level of catalytic activity for the α-methylation of ketones with methanol. The mechanistic investigation revealed that the carbonyl group on the ligand is of critical importance for catalytic hydrogen transfer. Notably, the results of this study revealed the unique potential of Cp*Ir complexes bearing a functional bipyridonate ligand for the development of C–C bond-forming reactions with the activation of primary alcohols as electrophiles

Catalytic Acceptorless Dehydrogenative Coupling of Arylhydrazines and Alcohols for the Synthesis of Arylhydrazones

The direct synthesis of arylhydrazones via catalytic acceptorless dehydrogenative coupling of arylhydrazines and alcohols has been accomplished. More importantly, complete selectivity for arylhydrazones and none of the <i>N</i>-alkylated byproducts were generated in this process, which exhibit new potential and provide a new horizon for the development of catalytic acceptorless dehydrogenative coupling reactions

Regioselective Hydration of Terminal Alkynes Catalyzed by a Neutral Gold(I) Complex [(IPr)AuCl] and One-Pot Synthesis of Optically Active Secondary Alcohols from Terminal Alkynes by the Combination of [(IPr)AuCl] and Cp*RhCl[(<i>R</i>,<i>R</i>)‑TsDPEN]

A neutral gold­(I) complex [(IPr)­AuCl] (IPr = 1,3-bis­(diisopropylphenyl)­imidazol-2-ylidene) was found to be a highly effective catalyst for the hydration of terminal alkynes, including aromatic alkynes and aliphatic alkynes. The desired methyl ketones were obtained in high yields with complete regioselectivities. Furthermore, a series of optically active secondary alcohols could be obtained in high yield with good to excellent enatioselectivities via one-pot sequential hydration/asymmetric transfer hydrogenation (ATH) from terminal alkynes by the combination of of [(IPr)­AuCl] and Cp*RhCl­[(<i>R</i>,<i>R</i>)-TsDPEN] (Cp* = pentamethylcyclopentadienyl, TsDPEN = <i>N</i>-(<i>p</i>-toluenesulfonyl)-1,2-diphenylethylenediamine). Notably, this research exhibited the potential of the direct use of neutral gold­(I) complexes instead of cationic ones as catalysts for the activation of multiple bonds for organic synthesis

Additional file 1 of Cellular nanomechanics derived from pattern-dependent focal adhesion and cytoskeleton to balance gene transfection of malignant osteosarcoma

Additional file 1: Table S1. Characters of prepared micropatterns. The data are calculated from 3 independent micropatterns. Table S2. Diameters and spreading areas of micropatterned and non-patterned MG63 cells. The data are calculated from five cells for each type micropatterns

Enhanced Selective Adsorption of Pb(II) from Aqueous Solutions by One-Pot Synthesis of Xanthate-Modified Chitosan Sponge: Behaviors and Mechanisms

Sponge-like xanthate-modified chitosan with a three-dimensional network macroporous structure was prepared using a facile one-pot approach. The as-prepared adsorbent possessed remarkable adsorption capacity and excellent mechanical property as well as rapid and intact separation performance. Adsorption properties of Pb­(II), Cd­(II), Ni­(II), and Zn­(II) on xanthate-modified chitosan sponge (XCTS) were systematically investigated in single and multiple systems. The experimental data for each heavy metal adsorption well fitted to the pseudo-second-order kinetic model and Langmuir isotherm model. The maximum adsorption capacities of Pb­(II), Cd­(II), Ni­(II), and Zn­(II) were 216.45, 92.85, 45.46, and 41.88 mg/g, respectively. The mutual interference effects of heavy metals in multiple systems were investigated using the inhibitory effect and equilibrium adsorption capacity ratios. The results indicated that the coexisting metal ions had a synergistic promoting effect on Pb­(II) adsorption. The competitive adsorption behaviors of Pb­(II) in multiple systems were successfully described by the Langmuir and Langmuir competitive models. The adsorption capacity of Pb­(II) in multiple systems was higher than that in single system while those of Cd­(II), Ni­(II), and Zn­(II) had a significant decrease in multiple systems, especially for Ni­(II) and Zn­(II). It turned out that Pb­(II) could be effectively removed from an aqueous solution in the presence of Cd­(II), Ni­(II), and Zn­(II), whereas the removal of Cd­(II), Ni­(II), and Zn­(II) would be restrained by the presence of Pb­(II). The high selective factor and physicochemical properties of these studied heavy metals revealed the selective adsorption sequence: Pb­(II) > Cd­(II) > Ni­(II) > Zn­(II). The characteristic analyses showed sulfur and nitrogen atoms participated in the heavy metal adsorption. The interaction mechanism between Pb­(II) and coexisting metal ions could be attributed mainly to the direct displacement effect

Hydrogenated TiO₂ Branches Coated Mn₃O₄ Nanorods as an Advanced Anode Material for Lithium Ion Batteries

Rational design and delicate control on the component, structure, and surface of electrodes in lithium ion batteries are highly important to their performances in practical applications. Compared with various components and structures for electrodes, the choices for their surface are quite limited. The most widespread surface for numerous electrodes, a carbon shell, has its own issues, which stimulates the desire to find another alternative surface. Here, hydrogenated TiO₂ is exemplified as an appealing surface for advanced anodes by the growth of ultrathin hydrogenated TiO₂ branches on Mn₃O₄ nanorods. High theoretical capacity of Mn₃O₄ is well matched with low volume variation (∼4%), enhanced electrical conductivity, good cycling stability, and rate capability of hydrogenated TiO₂, as demonstrated in their electrochemical performances. The proof-of-concept reveals the promising potential of hydrogenated TiO₂ as a next-generation material for the surface in high-performance hybrid electrodes

Significant Enhancement in the Electrochemical Performances of a Nanostructured Sodium Titanate Anode by Molybdenum Doping for Applications as Sodium-Ion Batteries

Sodium titanate is considered as one of the most promising anode materials for sodium-ion batteries without any serious safety concerns due to its high theoretical capacity at sufficiently low voltage. However, its low electrical conductivity severely restricts the electrochemical performances as an anode for sodium-ion batteries. Because suitable doping is always found to be a trump card strategy to especially enhance the conductivity, a molybdenum-doped sodium titanate nanostructured anode was successfully synthesized for the first time using the solvothermal method. Molybdenum-doped sodium titanate electrode materials showed superior electrochemical performances than the pristine sample. On more precise consideration, the sodium titanate electrode doped with 15 wt % molybdenum not only delivers ∼24% high reversible capacity at a high current density of 1 A g–1 in comparison to the pure sodium titanate electrode but also maintains it until 2500 cycles. It is believed that the improved electrochemical performances are mainly contributed by the combination of enhanced electrical conductivity and oxygen vacancy generated in the sodium titanate framework as a result of molybdenum doping. Molybdenum doping may also allow Na+ ion diffusion through multiple pathways within the sodium titanate crystal lattice and increase the transport rate of Na+ ions

Defect Sites-Rich Porous Carbon with Pseudocapacitive Behaviors as an Ultrafast and Long-Term Cycling Anode for Sodium-Ion Batteries

Room-temperature sodium-ion batteries have been regarded as promising candidates for grid-scale energy storage due to their low cost and the wide distribution of sodium sources. The main scientific challenge for their practical application is to develop suitable anodes with long-term cycling stability and high rate capacity. Here, novel hierarchical three-dimensional porous carbon materials are synthesized through an in situ template carbonization process. Electrochemical examination demonstrates that carbonization temperature is a key factor that affects Na⁺-ion-storage performance, owing to the consequent differences in surface area, pore volume, and degree of crystallinity. The sample obtained at 600 °C delivers the best sodium-storage performance, including long-term cycling stability (15 000 cycles) and high rate capacity (126 mAh g^–1 at 20 A g^–1). Pseudocapacitive behavior in the Na⁺-ion-storage process has been confirmed and studied via cyclic voltammetry. Full cells based on the porous carbon anode and Na₃V₂(PO₄)₃-C cathode also deliver good cycling stability (400 cycles). Porous carbon, combining the merits of high energy density and extraordinary pseudocapacitive behavior after cycling stability, can be a promising replacement for battery/supercapacitors hybrid and suggest a design strategy for new energy-storage materials

DataSheet_1_Identification of the shared genetic architecture underlying seven autoimmune diseases with GWAS summary statistics.docx

BackgroundThe common clinical symptoms and immunopathological mechanisms have been observed among multiple autoimmune diseases (ADs), but the shared genetic etiology remains unclear.MethodsGWAS summary statistics of seven ADs were downloaded from Open Targets Genetics and Dryad. Linkage disequilibrium score regression (LDSC) was applied to estimate overall genetic correlations, bivariate causal mixture model (MiXeR) was used to qualify the polygenic overlap, and stratified-LDSC partitioned heritability to reveal tissue and cell type specific enrichments. Ultimately, we conducted a novel adaptive association test called MTaSPUsSet for identifying pleiotropic genes.ResultsThe high heritability of seven ADs ranged from 0.1228 to 0.5972, and strong genetic correlations among certain phenotypes varied between 0.185 and 0.721. There was substantial polygenic overlap, with the number of shared SNPs approximately 0.03K to 0.21K. The specificity of SNP heritability was enriched in the immune/hematopoietic related tissue and cells. Furthermore, we identified 32 pleiotropic genes associated with seven ADs, 23 genes were considered as novel genes. These genes were involved in several cell regulation pathways and immunologic signatures.ConclusionWe comprehensively explored the shared genetic architecture across seven ADs. The findings progress the exploration of common molecular mechanisms and biological processes involved, and facilitate understanding of disease etiology.</p

Synergistically Enhanced Interfacial Interaction to Polysulfide via N,O Dual-Doped Highly Porous Carbon Microrods for Advanced Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries have received tremendous attention because of their extremely high theoretical capacity (1672 mA h g^–1) and energy density (2600 W h kg^–1). Nevertheless, the commercialization of Li–S batteries has been blocked by the shuttle effect of lithium polysulfide intermediates, the insulating nature of sulfur, and the volume expansion during cycling. Here, hierarchical porous N,O dual-doped carbon microrods (NOCMs) were developed as sulfur host materials with a large pore volume (1.5 cm³ g^–1) and a high surface area (1147 m² g^–1). The highly porous structure of the NOCMs can act as a physical barrier to lithium polysulfides, while N and O functional groups enhance the interfacial interaction to trap lithium polysulfides, permitting a high loading amount of sulfur (79–90 wt % in the composite). Benefiting from the physical and chemical anchoring effect to prevent shuttling of polysulfides, S@NOCMs composites successfully solve the problems of low sulfur utilization and fast capacity fade and exhibit a stable reversible capacity of 1071 mA h g^–1 after 160 cycles with nearly 100% Coulombic efficiency at 0.2 C. The N,O dual doping treatment to porous carbon microrods paves a way toward rational design of high-performance Li–S cathodes with high energy density