The 1,3-Dipolar Cycloadditions of Nitrile Oxides and Nitrile Imines to Alkyl Dicyanoacetates

The readily available alkyl dicyanoacetates 1 reacted with the 1,3-dipolar reagents arenecarbonitrile oxides 2 ′ and arenecarbonitrile imines 5 ′ to afford 1,2,4-oxadiazol and 1,2,4-triazol derivatives. The arenecarbonitrile oxides 2 ′ with electron-donating groups on the arene ring gave products 3a – d resulting from addition on both CN groups of 1 , and those with electron-withdrawing groups provided mono-adducts 4a – e (Scheme 1). Arylnitrile imines 5 ′ reacted with 1 to offer both bis- and mono-addition products (Scheme 2); the bis-adducts 8a , b possess an ester structure, whereas the mono-adducts 6a – d present a ketene-hemiacetal structure.     

Micro-electrospray with stainless steel emitters

The physical processes underlying micro-electrospray (micro-ES) performance were investigated using a stainless steel (SS) emitter with a blunt tip. Sheathless micro-ES could be generated at a blunt SS tip without any tapering or sanding if ESI conditions were optimized. The Taylor cone was found to shrink around the inner diameter of the SS tubing, which permitted a low flow rate of 150 nL/min for sheathless microspray on the blunt tip (100 microm i.d. x 400 microm o.d.). It is believed that the wettability and/or hydrophobicity of SS tips are responsible for their micro-ES performance. The outlet orifice was further nipped to reduce the size of the spray cone and limit the flow rate to 50-150 nL/min, resulting in peptide detection down to attomole quantities consumed per spectrum. The SS emitter was also integrated into a polymethylmethacrylate microchip and demonstrated satisfactory performance in the analysis and identification of a myoglobin digest.     

Rapid chiral analysis based on liquid-phase cyclic chemiluminescence

Rapid chiral analysis has become one of the important aspects of academic and industrial research. Here we describe a new strategy based on liquid-phase cyclic chemiluminescence (CCL) for rapid resolution of enantiomers and determination of enantiomeric excess (ee). A single CCL measurement can acquire multistage signals that provide a unique way to examine the intermolecular interactions between chiral hosts and chiral guests, because the lifetime (τ) of the multistage signals is a concentration-independent and distinguishable constant for a given chiral host–guest system. According to the τ values, CCL allows discrimination between a wide range of enantiomeric pairs including chiral alcohols, amines and acids by using only one chiral host. Even the chiral systems hardly distinguished by nuclear magnetic resonance and fluorescence methods can be distinguished easily by CCL. Additionally, the τ value of a mixture of two enantiomers is equal to the weighted average of each enantiomer, which can be used for the direct determination of ee without the need to separate the chiral mixture and create calibration curves. This is extremely crucial for the cases without readily available enantiomerically pure samples. This strategy was successfully applied to monitoring of the Walden inversion reaction and analysis of chiral drugs. The results were in good agreement with those obtained by high-performance liquid chromatography, indicating the utility of CCL for routine quick ee analysis. Mechanism study revealed that the τ value is possibly related to the activity of the chiral substance to catalyze a luminol–H₂O₂ reaction. Our research provides an unprecedented and general protocol for chirality differentiation and ee determination, which is anticipated to be a useful technology that will find wide application in chirality-related fields, particularly in asymmetric synthesis and the pharmaceutical industry.

Rapid chiral analysis has become one of the important aspects of academic and industrial research.     

CuAl2O4 powder synthesis by sol-gel method and its photodegradation property under visible light irradiation

Nanocrystalline spinel CuAl₂O₄ powders were prepared by sol-gel method from nitrate Cu(NO₃)₂·3H₂O, Al(NO₃)₃·9H₂O and complex C₆H₈O₇·H₂O. Sintering was carried out at 400, 500, 600, 700, 800°C respectively for 2 h in air. The XRD patterns started to appear CuAl₂O₄ peaks after sintering of 500°C and consist of only CuAl₂O₄ peaks as spinel crystal after sintering of 700°C. The powders were analyzed by TEM and UV-vis diffuse reflectance spectrum to be round, about 10–30 nm in size and Eg=1.77 eV. Photodegradation property of nanocrystalline CuAl₂O₄ powders was investigated by using methyl orange as model pollutant and mercury lamp (λ>400 nm) as energy source. The results indicated that CuAl₂O₄ powders sintered at 700°C had the excellent visible photocatalytic property. Under the irradiation of visible light, methyl orange could be degraded 97% in 120 min.     

Partial P-Type Metal Ions Doping Induced Variation of Both Crystal Structure and Oxygen Vacancy Within Cu/SnO2 Metastable Solid Solution Nanofibers for Highly Sensitive C2H2 Sensor

Partial P-type metal ions doping(PPMID) is an alternative method to further enhance the gas sensing performance of N-type metal oxides(NMOs) in contrast to that of P-N metal oxides heterojunctions, but the influences of the introduction of PPMID on the grain size and oxygen vacancies of NMOs have been rarely investigated. Herein, a simple and effective route has been demonstrated to address this problem with Cu²⁺-doped SnO₂ metastable solid solution nanofibers(CSMSSNs) as model and C₂H₂ as target molecule by combining electrospinning and calcination technique. It seems that the introduction of PPMID can also affect crystal structure and oxygen vacancies of NMOs, proven by combining X-ray diffraction(XRD) and X-ray photoelectron spectra(XPS). Thus, PPD, crystal structure and oxygen vacancies have been combined to clarify the enhanced sensing performance of Cu-doped SnO₂ metastable solid solution nanofibers angainst C₂H₂.     

支持向量回归同时测定苯丙氨酸、酪氨酸和色氨酸的研究

在波长200~400 nm范围内,测定酪氨酸、色氨酸和苯丙氨酸混合体系的吸光度,用连续小波变换(CWT)对光谱数据进行预处理,再用支持向量回归(SVR)方法进行建模,建立了支持向量回归紫外分光光度法同时测定酪氨酸、色氨酸和苯丙氨酸的方法,用所建方法对模拟样品进行了测定。结果表明,酪氨酸、色氨酸和苯丙氨酸预测结果的回收率在98%~102%之间,测定结果准确。     

离散小波变换-支持向量回归方法同时测定苯酚、苯胺和苯甲酸

在波长范围200～400nm测定苯酚、苯胺和苯甲酸混合液的吸收光谱,用离散小波变换（DWT）对光谱数据进行处理,再用支持向量回归SVR方法进行建模,建立了离散小波变换一支持向量回归方法（DWT—SVR）。方法用于模拟样品和污染水样中苯酚、苯胺和苯甲酸的同时测定,结果满意。     

Rapid Detection of Five Estrogens Added Illegally to Dietary Supplements by Combining TLC with Raman Imaging Microscope

Estrogens added illegally to dietary supplements are hazardous to human health. Traditional detection and analysis methods have many limitations, and we have developed an assay that combines thin-layer chromatography with Raman imaging microscopy (TLC-RIM). The five estrogens (estrone, estradiol, estriol, ethinyl estradiol, and diethylstilbestrol) were initially separated by TLC, then detected by area scanning Raman imaging with a 532 nm laser under a microscope. Raman spectra were obtained for each estrogen, which were used for detecting estrogen illegally added to botanical dietary supplements. The LOD of each estrogen was 0.4, 1.0, 0.8, 0.2, and 0.2 mg/mL, respectively. The matrix in the real sample did not interfere with the detection of estrogens. The method was fast, sensitive, stable, specific, and reliable.     

Electrical, dielectric and surface wetting properties of multi-walled carbon nanotubes/nylon-6 nanocomposites

This paper reports that the multi-walled carbon nanotubes(MWCNT)/nylon-6 (PA6) nanocomposites with different MWCNT loadingshave been prepared by a simple melt-compounding method. Theelectrical, dielectric, and surface wetting properties of theCNT/PA6 composites have been studied. The temperature dependence ofthe conductivity of the CNT/PA6 composite with 10.0 wt{\%} CNTloading ($\sigma _{\rm RT} \sim 10^{-4}$ S/cm) are measured, andafterwards a charge-energy-limited tunnelling model (ln $\sigma (T)\sim T^{-1/2})$ is found. With increasing CNT weight percentage from0.0 to 10.0 wt%, the dielectric constant of the CNT/PA6composites enhances and the dielectric loss tangent increases twoorders of magnitude. In addition, water contact angles of theCNT/PA6 composites increase and the composites with CNT loadinglarger than 2.0 wt%even become hydrophobic. The obtainedresults indicate that the electrical and surface properties of thecomposites have been significantly enhanced by the embedded carbonnanotubes.     

基于低相干光的阵列透镜束匀滑技术研究

基于激光加载的材料状态方程的实验研究对靶面光强分布的均匀性及稳定性提出了极高的要求,靶面光强的上述两大特性在很大程度上决定了实验结果的精度和可重复性.本文针对传统窄带高相干激光装置在激光加载材料状态方程实验中表现出的靶面光强均匀性和光强分布稳定性两方面可能存在的问题,提出了基于宽带低相干激光,利用消衍射阵列透镜联合诱导非相干技术的束匀滑方案,并重点分析了波前相位畸变对靶面不均匀性及稳定性的影响.模拟结果表明,该方法明显降低了靶面不均匀性,提高了对波前相位畸变的包容度,获得了均匀、稳定的光强分布.统计分析显示,焦斑强度分布极差和不均匀性与波前相位畸变均方根梯度相关性较强.因此,可以根据统计结果以及实验对焦斑强度分布的要求,给出波前相位畸变的容差范围,对状态方程实验中激光驱动器参数的设计与优化具有指导意义.