Surface of room temperature ionic liquid [bmim][PF6] studied by polarization- and experimental configuration-dependent sum frequency generation vibrational spectroscopy

Understanding and control of the surface properties such as molecular orientations are of great importance in numerous applications of ionic liquids. However, there remain discrepancies among the previous experimental and theoretical studies on the surface orientation and structures of room temperature ionic liquids(RTIL) systems. In this article, the orientation of 1-butyl-3-methylimidazolium([bmin]) cation at the air/liquid interface of a characteristic RTIL, 1-butyl-3-methylimidazolium hexafluorophosphate([bmim][PF6]), was investigated by the sum frequency generation vibrational spectroscopy(SFG-VS). Detailed polarization and experimental configuration analyses of the SFG-VS spectra showed the possibility of a small spectral splitting in the CH3 symmetric stretching region, which can be further attributed to the probable existence of multiple orientations for the interfacial [bmim] cations. In addition, the(N)–CH3 vibrations were absent, ruling out the prediction by several recent molecular dynamics simulations which state that portions of the [bmim] cations orient with a standing-up(N)–CH3 group at the ionic liquid surface. Hence, new realistic theoretical models have to be developed to reflect the complex nature of the ionic liquid surface.     

Chemical equilibrium controlled synthesis of polyoxymethylene dimethyl ethers over sulfated titania

The chemical equilibrium and reaction kinetic behavior in the synthesis of polyoxymethylene dimethyl ethers(DMMn) were investigated over sulfated titania in order to reveal the decisive factor controlling the reaction. The results showed that the molar ratio of adjacent DMMn products in equilibrium solution had the same value, which depended absolutely on the reaction temperature. Meanwhile, the reactions had the same DMMn products distributions under varied reaction conditions. The equilibrium constants of the related step-wise reactions for DMMn formation were equal, which were calculated based on the bulk compositions of the reaction solution. And thus, the selectivity to DMMn was mainly controlled by the chemical equilibrium, i.e., thermodynamic control. In brief, the present results provide some guidance for future synthesis of DMMn.     

Surface modification of polyolefin separators for lithium ion batteries to reduce thermal shrinkage without thickness increase

Surface chemical modification of polyolefin separators for lithium ion batteries is attempted to reduce the thermal shrinkage, which is important for the battery energy density. In this study, we grafted organic/inorganic hybrid crosslinked networks on the separators, simply by grafting polymerization and condensation reaction. The considerable silicon-oxygen crosslinked heat-resistance networks are responsible for the reduced thermal shrinkage. The strong chemical bonds between networks and separators promise enough mechanical support even at high temperature. The shrinkage at 150 C for 30 min in the mechanical direction was 38.6% and 4.6% for the pristine and present graft-modified separators, respectively. Meanwhile, the grafting organic-inorganic hybrid crosslink networks mainly occupied part of void in the internal pores of the separators, so the thicknesses of the graft-modified separators were similar with the pristine one. The half cells prepared with the modified separators exhibited almost identical electrochemical properties to those with the commercial separators, thus proving that, in order to enhance the thermal stability of lithium ion battery, this kind of grafting-modified separators may be a better alternative to conventional silica nanoparticle layers-coated polyolefin separators.     

Ratiometric mode with dyads: a breakthrough in dynamic trapping and quantification for redox regulation in living cells

Redox-based post-translational modification of protein thiols has become an attractive strategy in cellular homeostasis and cell signaling.Due to the reductive end of the redox buffer network,the vicinal dithiol-containing proteins(VDPs)maintains an appropriate oxidation-reduction state of proteins through the reversible transformation from vicinal dithiols to disulfide,which is responsible for a variety of     

Characteristics of black carbon aerosol in Jiaxing,China during autumn 2013

We conducted measurements of black carbon（BC） aerosol in Jiaxing,China during autumn from September 26 to November 30,2013.We investigated temporal and diurnal variations of BC,and its correlations with meteorological parameters and other major pollutants.Results showed that hourly mass concentrations of BC ranged from 0.2 to 22.0 μg/m³,with an average of 5.1 μg/m³.The diurnai variation of BC exhibited a bimodal distribution,with peaks at 07:00 and 18:00.The morning peak was larger than the evening peak.The mass percentages of BC in PM_2.5 and PM₁₀ were 7.1%and 4.8%,respectively.The absorption coefficient of BC was calculated to be 44.4 Mm^-1,which accounted for 11.1%of the total aerosol extinction.BC was mainly emitted from local sources in southwestern Jiaxing where BC concentrations were generally greater than 11 μg/m³ during the measurement period.Correlation analysis indicated that the main sources of BC were motor vehicle exhaust,and domestic and industrial combustion.     

Understanding the Origin of Highly Selective CO2 Electroreduction to CO on Ni,N-doped Carbon Catalysts

Ni,N-doped carbon catalysts have shown promising catalytic performance for CO₂ electroreduction (CO₂R) to CO; this activity has often been attributed to the presence of nitrogen-coordinated, single Ni atom active sites. However, experimentally confirming Ni−N bonding and correlating CO₂ reduction (CO₂R) activity to these species has remained a fundamental challenge. We synthesized polyacrylonitrile-derived Ni,N-doped carbon electrocatalysts (Ni-PACN) with a range of pyrolysis temperatures and Ni loadings and correlated their electrochemical activity with extensive physiochemical characterization to rigorously address the origin of activity in these materials. We found that the CO₂R to CO partial current density increased with increased Ni content before plateauing at 2 wt % which suggests a dispersed Ni active site. These dispersed active sites were investigated by hard and soft X-ray spectroscopy, which revealed that pyrrolic nitrogen ligands selectively bind Ni atoms in a distorted square-planar geometry that strongly resembles the active sites of molecular metal–porphyrin catalysts.     

Direct synthesis of propylene carbonate from propylene and carbon dioxide catalyzed by quaternary ammonium heteropolyphosphatotungstate–TBAB system

In this paper,we have developed a highly efficient method for the direct preparation of propylene carbonate from propylene and carbon dioxide(CO2) using quaternary ammonium heteropolyphosphatotungstate–quaternary ammonium halide catalytic system with anhydrous hydrogen peroxide as an oxidant through one-pot two-step process.The effects of the amount of tetrabutylammonium bromide(TBAB),the concentration of hydrogen peroxide and other reaction conditions were investigated.The catalyst system gave an optimum propylene oxide yield(91%) at75°C in oxidation step and the highest propylene carbonate yield(99%) at 140°C and 3.0 MPa in cycloaddition step.Based on the results,a reaction mechanism has been proposed.     

The enhanced expression of IL-17-secreting T cells during the early progression of atherosclerosis in ApoE-deficient mice fed on a western-type diet

Atherosclerosis is a chronic progressive inflammatory disorder and the leading cause of cardiovascular mortality. Here we assessed the dynamic changes of T-cell-derived cytokines, such as inteferon (IFN)-γ, interleukin (IL)-17 and IL-4, during the progression of atherosclerosis in apolipoprotein E-null (ApoE^−/−) mice, to understand the role of immune responses in different stages of atherosclerosis. Male ApoE^−/− mice were fed a high-fat, western-type diet (WD: 21% lipid, 1.5% cholesterol) after 5 weeks of age and were compared with C57BL/6 wild-type control mice fed a standard chow diet. Atherosclerotic lesions appeared in the aortic sinus of ApoE^−/− mice 4 weeks after WD and the lesions progressed and occupied >50% of the total sinus area 16 weeks after WD. Aortic IL-17 mRNA and protein expression started to increase in ApoE^−/− mice after 4 weeks on the WD and peaked at around 8–12 weeks on the WD. In terms of systemic expression of T-cell-derived cytokines, IL-17 production from splenocytes after anti-CD3/CD28 stimuli increased from 4 weeks on the WD, peaked at 12 weeks and returned to control levels at 16 weeks. The production of IFN-γ and IL-4 (Th1 and Th2 cytokines, respectively) from splenocytes was delayed compared with IL-17. Taken together, the present data indicate that Th17 cell response may be involved at an early stage in the development of atherosclerosis.     

Three New Lignan Derivatives from Lindera glauca (Siebold et Zucc.) Blume

Two new aryl‐tetralin lignan glycosides, linderanosides A and B ( 1 and 2 , resp.), and a new dihydrobenzofuran neolignan glycoside, linderanoside C ( 3 ), together with five known lignan derivatives ( 4 – 8 ) were isolated from the trunk of Lindera glauca. The structures of these new compounds were determined through spectroscopic analyses, including extensive 2D‐NMR data and acid hydrolysis. The absolute configurations of the compounds were clarified by circular dichroism (CD) spectroscopic studies. Compounds 1 – 8 were evaluated for their cytotoxicity against A549 (non‐small cell lung adenocarcinoma), SK‐OV‐3 (ovarian cancer cells), A498 (human kidney epithelial cells), and HCT‐15 (colon cancer cells) human tumor cell lines using sulforhodamine B assays in vitro.