Activation of Hydrogen Peroxide by Ionic Liquids: Mechanistic Studies and Application in the Epoxidation of Olefins

Imidazolium‐based ionic liquids that contain perrhenate anions are very efficient reaction media for the epoxidation of olefins with H₂O₂ as an oxidant, thus affording cyclooctene in almost quantitative yields. The mechanism of this reaction does not follow the usual pathway through peroxo complexes, as is the case with long‐known molecular transition‐metal catalysts. By using in situ Raman, FTIR, and NMR spectroscopy and DFT calculations, we have shown that the formation of hydrogen bonds between the oxidant and perrhenate activates the oxidant, thereby leading to the transfer of an oxygen atom onto the olefin demonstrating the special features of an ionic liquid as a reaction environment. The influence of the imidazolium cation and the oxidant (aqueous H₂O₂, urea hydrogen peroxide, and tert‐butyl hydrogen peroxide) on the efficiency of the epoxidation of cis‐cyclooctene were examined. Other olefinic substrates were also used in this study and they exhibited good yields of the corresponding epoxides. This report shows the potential of using simple complexes or salts for the activation of hydrogen peroxide, owing to the interactions between the solvent medium and the active complex.     

贫燃条件 In-Ag/TiO2-γ-Al2O3催化 CO选择性还原NO

汽车尾气中主要污染成分 CO和 NOx可导致酸雨、光化学烟雾和臭氧空洞效应,对生物、环境及生态系统造成重大危害。污染源中 CO是性能优良的还原剂,如能不添加还原剂实现 CO催化还原 NOx,将成为最具经济技术优势的 NOx脱除技术。在富氧、低温条件下,利用 CO选择性催化还原 NOx为 N2,是目前选择性催化还原研究中的热点和难点。催化 CO还原 NOx常用的贵金属 Ir, Rh, Pt和Pd矿藏稀少,价格昂贵,有氧条件下活性急降,而分子筛催化剂和一些金属氧化物催化剂普遍存在反应温度高,尤其对 N2选择性差等问题。为解决上述问题,需寻找新的适合我国矿产资源的催化体系。研究发现,稀散金属基催化剂对氮氧化物的净化具有一定效果,因而可将我国的稀散金属资源优势转化为技术优势和经济优势。因此,本文以 TiO2-γ-Al2O3(TA)为载体, In/Ag为活性组分,采用等体积浸渍法制备了 InAg/TA以及 In/TA, Ag/TA和InAg/Al (γ-Al2O3为载体)催化剂,考察了贫燃条件下 CO选择性还原NO的催化活性。研究表明,双金属催化剂InAg/Al和 InAg/TA的活性比单金属催化剂In/TA和 Ag/TA高, In/TA催化剂中引入 Ag物种能降低起燃温度;另外,相比于InAg/Al催化剂, InAg/TA催化剂具有较高的催化活性,550?600°C时 N2产率超过60%,说明载体中引入TiO2可以提高催化剂活性。为了深入研究 InAg/TA催化剂中 Ag物种和TiO2对 In物种的作用,通过比表面测定、X射线衍射(XRD)、透射电子显微镜(TEM)、X射线光电子能谱、紫外-可见光吸收光谱、氢气程序升温还原、傅立叶变换红外线光谱等方法分析了催化剂结构和表面形态。结果表明, Ag物种可以提高 In物种的分散性, In和 Ag物种在 TA载体表面可以很好地分散,从而有利于提高催化活性。 In和 Ag物种在 TA载体表面以氧化态形式存在,并且 Ag物种可以提高 In物种表面含量,表面 In和 Ag物种含量越高,吸附活性位越多,催化活性越高;同时, TiO2也可以促进 NO吸附,从而提高 InAg/TA催化剂活性。 InAg/TA催化剂在450°C连续反应72 h进行稳定性测试,测试前后分别在50?600°C进行活性测试,并用 XRD和 TEM对反应后的催化剂进行表征测试。结果表明, InAg/TA催化剂具有较好的稳定性,连续反应前后催化剂活性基本保持不变,推测可能由于在有 CO和O2存在的体系中, Ag物种利用自身 Ag+与 Ag0之间的氧化还原反应抑制了活性组分 In2O3的还原和聚集,稳定了 In物种乃至催化剂活性。 InAg/TA催化剂用于贫燃条件下CO还原NO具有较好的催化效果,主要归因于催化剂活性组分分散性好,稳定性高,对NO吸附能力强。 Ag物种可以稳定In物种并提高其分散性, TiO2可以改善In物种和Ag物种的分散性并促进NO吸附。     

Ultrasound-assisted extraction of phillyrin from Forsythia suspensa

Forsythia suspensa (Thunb.) Vahl is one of the most widely used traditional Chinese medicines, and possesses important biological activities, such as antibacterial, antiviral, anti-inflammatory and antioxidant activities. Phillyrin is the main bioactive component of Forsythia suspensa. In this paper, ultrasound-assisted extraction of phillyrin from Forsythia suspensa was studied with HPLC-photodiode array detection. Effects of several experimental parameters, such as type and concentration of extracting solvent, ratio of liquid to material, extraction temperature, and time of sonication on extraction efficiencies of phillyrin from Forsythia suspensa were evaluated. The optimal extraction conditions were 1g plant sample with 10 ml of 20% methanol and the extraction for 60 min at 60°C under ultrasonic irradiation. Under the optimum conditions, the yield of phillyrin was 0.713±0.009 mg/g. The results indicated that the ultrasound-assisted extraction is a very useful method for the extraction of important phytochemicals from plant materials.     

高速高饱和单行载流子光探测器的设计与分析

设计了一种In P基的背入射台面结构的单行载流子光探测器.通过在吸收层中采取高斯型掺杂界面及引入合适厚度和掺杂浓度的崖层,使得光探测器同时具备了高速和高饱和电流特性.理论分析表明,在光敏面为14μm2、反向偏压为2 V条件下,该器件的3 d B带宽可达58 GHz,直流饱和电流高达158 m A.在大功率光注入条件下,详细分析了光探测器带宽降低和电流饱和现象,得出能带偏移和电场坍塌是其根本原因的结论.     

Solid‐phase extraction based on a molecularly imprinted polymer for the selective determination of four benzophenones in tap and river water

This work reports the preparation of molecularly imprinted polymer particles for the selective extraction and determination of four benzophenones from aqueous media. The polymer was prepared by using 4‐vinylpridine as functional monomer, ethylene glycol dimethacrylate as cross‐linker, acetonitrile as porogenic solvent and 2,2’,4,4’‐tetrehydroxybenzophenone as template. Good specific adsorption capacity (Q_max = 27.90 μmol/g) for 2,2’,4,4’‐tetrehydroxybenzophenone was obtained in the sorption experiment and good class selectivity for 2,2’,4,4’‐tetrehydroxybenzophenone, 2,4‐dihydroxybenzophenone, 2,2’‐dihydroxy‐4‐methoxybenzophenone, 2,2’‐dehydroxy‐4,4’‐dimethoxybenzophenone was demonstrated by the chromatographic evaluation experiment. Factors affecting the extraction efficiency of the molecularly imprinted solid‐phase extraction procedure were investigated systematically. An accurate and sensitive analytical method based on the molecularly imprinted solid‐phase extraction coupled with high‐performance liquid chromatography and diode array detection has been successfully developed for the simultaneous determination of four benzophenones from tap water and river water with method detection limits of 0.25–0.72 ng/mL. The recoveries of benzophenones for water samples at two spiking levels (500 and 5000 ng/mL for each benzophenone) were in the range of 86.9–103.3% with relative standard deviations (n = 3) below 9.2%.     

大非线性相移下光学非线性Z扫描特性的研究

采用高斯分解法(GD)对大非线性相移下的Z扫描特性进行了分析，通过对数值算法的优化，将GD推广到对脉冲入射激光下大非线性相移下的Z扫描理论分析.对不同条件下大非线性相移Z扫描曲线峰谷结构的比较，发现在大非线性相移的情况下，Z扫描曲线的峰和谷随透过光阑或入射光强变化表现出某些新的特性.随着透过光阑孔径的增加，Z扫描曲线峰的变化要明显快于谷的变化，而且在谷明显存在的情况下，峰很快消失.采用皮秒脉冲激光下的纯二硫化碳实验对理论结果加以验证，实验结果和理论分析相一致.我们的分析结果对大非线性相移下Z扫描测量有一定的指导性意义，避免在大非线性相移下对Z扫描结果产生错误的分析. 关键词： 大非线性相移 高斯分解法 Z扫描     

厚非线性介质瞬态热光非线性效应的研究

瞬态热光非线性效应是指由脉冲宽度可以和非线性效应的建立时间相比拟的纳秒脉冲激光入射产生的热光非线性效应.用Zscan法测量了不同厚度、不同束腰半径碘的酒精溶液的瞬态热光非线性效应曲线.从声波的传播方程和光波的非线性传播方程出发,用数值计算方法模拟了这一非线性过程.并对实验结果和数值模拟结果进行了比较 关键词： 瞬态热光非线性效应 非线性光学 数值计算     

All-silicon chiral metasurfaces and wavefront shaping assisted by interference

The usage of full-color imaging in digital pathology produces significant results. Compared with a grayscale image or a pseudocolor image containing contrast information, a full-color image can identify and detect the target object better with color texture information. Fourier ptychographic microscopy(FPM) is a high-throughput computational imaging technique that breaks the tradeoff between high resolution(HR) and a large field of view. It also eliminates the artifacts of scanning and stitching in digital pathology and improves its imaging efficiency. However, the conventional full-color digital pathology based on FPM is still time-consuming because of the repeated experiments with tri-wavelengths. A color transfer FPM approach termed "CFPM" was reported. The color texture information of a low-resolution full-color pathologic image is directly transferred to the HR grayscale FPM image captured by only a single wavelength. Both of the color space of FPM based on the standard CIE-XYZ color model and the display based on the standard RGB color space were established. Different FPM colorization schemes were analyzed and compared with 30 biological samples. Three types of evaluation approaches were provided, including the root-mean-square error(RMSE), the difference maps, and the image histogram cosine similarity. The average RMSE values of the conventional method and CFPM compared with the ground truth were 5.3% and 5.7%, respectively. Therefore, the reconstruction time is significantly reduced by 2/3 with the sacrifice of precision of only 0.4%. The CFPM method is also compatible with advanced fast FPM approaches to further reduce computation time.     

Impact of sugar stereochemistry on natural killer T cell stimulation by bacterial glycolipids

Natural killer T (NKT) cells recognize glycolipids produced by Sphingomonas bacteria, and these glycolipids contain C6-oxidized sugars, either glucuronic acid or galacturonic acid, linked to ceramides. Glycolipids with gluco stereochemistry are the most prevalent. Multiple studies have demonstrated that galactosylceramides are more potent stimulators of NKT cells than their glucose isomers. To determine if this stereoselectivity is retained in the context of the C6-oxidized sugars found in bacterial glycolipids, we prepared two sets of gluco and galacto-glycolipids oxidized at their C6 positions and compared their NKT stimulatory properties. In the context of carboxylic acid groups at C6, gluco stereochemistry gave the more potent responses. We also prepared bacterial glycolipids containing more complex ceramide groups to determine if these chains impact NKT cell responses.     

Infrared Photodissociation Spectroscopic and Theoretical Study of the HC2nO+ (n=3-6) Cations

The carbon chain cations, HC_2nO⁺ (n=3-6) are produced via a pulsed laser vaporization supersonic expansion ion source in the gas phase. Their infrared spectra are measured via mass-selected infrared photodissociation spectroscopy of the CO “tagged” [HC_2nO·CO]⁺ cation complexes in 1600-3500 cm^-1 frequency range. The geometric and electronic structures of the [HC_2nO·CO]⁺ complexes and the core HC_2nO⁺ (n=3-6) cations are determined with the aid of density functional theory calculations. These HC_2nO⁺(n=3-6) ions are identified to be linear carbon chain derivatives terminally capped by hydrogen and oxygen. The triplet ground states are 10-15 kcal/mol lower in energy than the singlet states, indicating cumulene-like carbon chain structures.