Tribological properties of self-assembled monolayers of catecholic imidazolium and the spin-coated films of ionic liquids

A novel compound of an imidazolium type of ionic liquid (IL) containing a biomimetic catecholic functional group normally seen in mussel adhesive proteins was synthesized. The IL can be immobilized on a silicon surface and a variety of other engineering material surfaces via the catecholic anchor, allowing the tribological protection of these substrates for engineering applications. The surface wetting and adhesive properties and the tribological property of the synthesized self-assembled monolayers (SAMs) are successfully modulated by altering the counteranions. The chemical composition and wettability of the IL SAMs were characterized by means of X-ray photoelectron spectroscopy (XPS) and contact angle (CA) measurements. The adhesive and friction forces were measured with an atomic force microscope (AFM) on the nanometer scale. IL composite films were prepared by spin coating thin IL films on top of the SAMs. The macrotribological properties of these IL composite films were investigated with a pin-on-disk tribometer. The results indicate that the presence of IL SAMs on a surface can improve the wettability of spin-coated ionic liquids and thus the film quality and the tribological properties. These films registered a reduced friction coefficient and a significantly enhanced durability and load-carrying capacity. The tribological properties of the composite films are better than those of pure IL films because the presence of the monolayers improves the adhesion and compatibility of spin-coated IL films with substrates.     

Highly sensitive detection of S-nitrosylated proteins by capillary gel electrophoresis with laser induced fluorescence

S-nitrosylated proteins are biomarkers of oxidative damage in aging and Alzheimer's disease (AD). Here, we report a new method for detecting and quantifying nitrosylated proteins by capillary gel electrophoresis with laser induced fluorescence detection (CGE-LIF). Dylight 488 maleimide was used to specifically label thiol group (SH) after switching the S-nitrosothiol (S-NO) to SH in cysteine using the "fluorescence switch" assay. In vitro nitrosylation model-BSA subjected to S-nitrosoglutathione (GSNO) optimized the labeling reactions and characterized the response of the LIF detector. The method proves to be highly sensitive, detecting 1.3 picomolar (pM) concentration of nitrosothiols in nanograms of proteins, which is the lowest limit of detection of nitrosothiols reported to date. We further demonstrated the direct application of this method in monitoring protein nitrosylation damage in MQ mediated human colon adenocarcinoma cells. The nitrosothiol amounts in MQ treated and untreated cells are 14.8±0.2 and 10.4±0.5 pmol/mg of proteins, respectively. We also depicted nitrosylated protein electrophoretic profiles of brain cerebrum of 5-month-old AD transgenic (Tg) mice model. In Tg mice brain, 15.5±0.4 pmol of nitrosothiols/mg of proteins was quantified while wild type contained 11.7±0.3 pmol/mg proteins. The methodology is validated to quantify low levels of S-nitrosylated protein in complex protein mixtures from both physiological and pathological conditions.     

Molybdenum nitride based hybrid cathode for rechargeable lithium-O2 batteries

Molybdenum nitride/nitrogen-doped graphene nanosheets (MoN/NGS) are synthesized and used as an alternative O(2) electrode for Li-O(2) batteries. In comparison with electrocatalysts proposed previously, this hybrid cathode exhibits a high discharge potential (around 3.1 V) and a considerable specific capacity (1490 mA h g(-1), based on carbon + electrocatalyst).     

Low-temperature tunneling and rotational dynamics of the ammonium cations in (NH4)2B12H12

Low-temperature neutron scattering spectra of diammonium dodecahydro-closo-dodecaborate [(NH(4))(2)B(12)H(12)] reveal two NH(4)(+) rotational tunneling peaks (e.g., 18.5 μeV and 37 μeV at 4 K), consistent with the tetrahedral symmetry and environment of the cations. The tunneling peaks persist between 4 K and 40 K. An estimate was made for the tunnel splitting of the first NH(4)(+) librational state from a fit of the observed ground-state tunnel splitting as a function of temperature. At temperatures of 50 K-70 K, classical neutron quasi-elastic scattering appears to dominate the spectra and is attributed to NH(4)(+) cation jump reorientation about the four C(3) axes defined by the N-H bonds. A reorientational activation energy of 8.1 ± 0.6 meV (0.79 ± 0.06 kJ/mol) is determined from the behavior of the quasi-elastic linewidths in this temperature regime. This activation energy is in accord with a change in NH(4)(+) dynamical behavior above 70 K. A low-temperature inelastic neutron scattering feature at 7.8 meV is assigned to a NH(4)(+) librational mode. At increased temperatures, this feature drops in intensity, having shifted entirely to higher energies by 200 K, suggesting the onset of quasi-free NH(4)(+) rotation. This is consistent with neutron-diffraction-based model refinements, which derive very large thermal ellipsoids for the ammonium-ion hydrogen atoms at room temperature in the direction of reorientation.     

一种基于光谱分析的二元不完全重叠色谱峰的分离解析方法

基于二极管阵列检测器获得的色谱-光谱数据,建立了一种二元不完全重叠液相色谱峰的解析方法: 色谱数据经过去噪、归一化处理后,计算各时间点的光谱差异并进行系统聚类分析,提取特征光谱后,利用非负最小二乘法对色谱-光谱矩阵进行解析,得到基于特征光谱的流出曲线,进而得到分离后的色谱峰。将解析结果和纯标样的色谱峰进行比较,解析后的光谱图和纯标样的光谱图无显著差异,保留时间相差小于0.01 min。实验结果表明,该方法在二元不完全重叠液相色谱峰的解析方面能取得良好的效果。     

Simultaneous large enhancements in thermopower and electrical conductivity of bulk nanostructured half-Heusler alloys

Large reductions in the thermal conductivity of thermoelectrics using nanostructures have been widely demonstrated. Some enhancements in the thermopower through nanostructuring have also been reported. However, these improvements are generally offset by large drops in the electrical conductivity due to a drastic reduction in the mobility. Here, we show that large enhancements in the thermopower and electrical conductivity of half-Heusler (HH) phases can be achieved simultaneously at high temperatures through coherent insertion of nanometer scale full-Heusler (FH) inclusions within the matrix. The enhancements in the thermopower of the HH/FH nanocomposites arise from drastic reductions in the "effective" carrier concentration around 300 K. Surprisingly, the mobility increases drastically, which compensates for the decrease in the carrier concentration and minimizes the drop in the electrical conductivity. Interestingly, the carrier concentration in HH/FH nanocomposites increases rapidly with temperature, matching that of the HH matrix at high temperatures, whereas the temperature dependence of the mobility significantly deviates from the typical T(-α) law and slowly decreases (linearly) with rising temperature. This remarkable interplay between the temperature dependence of the carrier concentration and mobility in the nanocomposites results in large increases in the power factor at 775 K. In addition, the embedded FH nanostructures also induce moderate reductions in the thermal conductivity leading to drastic increases in the ZT of HH(1 - x)/FH(x) nanocomposites at 775 K. By combining transmission electron microscopy and charge transport data, we propose a possible charge carrier scattering mechanism at the HH/FH interfaces leading to the observed anomalous electronic transport in the synthesized HH(1 - x)/FH(x) nanocomposites.     

Two new triterpene glycosides with monomethyl malonate groups from the rhizome of Cimifuga foetida L

Two new 9,19-cycloartane triterpene glycosides 1-2, together with four known compounds--26-deoxyactein (3), actein (4), 7,8-didehydro-26-deoxyactein (5) and cimiaceroside B (6)--were isolated from the rhizome of Cimicifuga foetida. The new triterpene glycosides were identified as 23-O-methyl-24-deoxy-2'-O-(3'-methylmalonyl)-cimiaceroside B (1) and 2'-O-(3'-methylmalonyl)actein (2) based on analysis of their spectral data and chemical reactions.     

Antioxidant activity of papaya seed extracts

The antioxidant activities of the ethanol, petroleum ether, ethyl acetate, n-butanol and water extract fractions from the seeds of papaya were evaluated in this study. The ethyl acetate fraction showed the strongest DPPH and hydroxyl free radical-scavenging activities, and its activities were stronger than those of ascorbic acid and sodium benzoate, respectively. The n-butanol fraction demonstrated the greatest ABTS? radicals scavenging activity. The ethyl acetate fraction and the n-butanol fraction not only showed higher antioxidant activities than the petroleum ether fraction, water fraction and ethanol fraction, but also showed higher superoxide anion and hydrogen peroxide radicals scavenging activities than those of the other extract fractions. The high amount of total phenolics and total flavonoids in the ethyl acetate and n-butanol fractions contributed to their antioxidant activities. The ethyl acetate fraction was subjected to column chromatography, to yield two phenolic compounds, p-hydroxybenzoic acid and vanillic acid, which possessed significant antioxidant activities. Therefore, the seeds of papaya and these compounds might be used as natural antioxidants.     

Protection of Li metal anode by surface-coating of PVDF thin film to enhance the cycling performance of Li batteries

The PVDF thin film on the surface of the lithium metal can highly suppress the lithium dendrites.     

Mn(III)-promoted synthesis of spiroannular tricyclic scaffolds via sulfonylation/dearomatization of biaryl ynones

A Mn(III)-promoted radical oxidative ipso-annulation reaction of biaryl ynones with sodium sulfinates to construct various substituted spiro[5.5]trienones has been explored in this study. This protocol is characterized by mild reaction conditions, good substrates functional group compatibility, cheap and easily prepared Mn(OAc)₃·2H₂O, and it demonstrates a simple operation.