Synthesis and characterization of VO–vanillin complex immobilized on MCM-41 and its facile catalytic application in the sulfoxidation reaction,and synthesis of 2,3-dihydroquinazolin-4(1H)-ones and disulfides in green media

In this work, a vanillin complex is immobilized onto MCM-41 and characterized by FT-IR, X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetric analysis, and BET techniques. This supported Schiff base complex was found to be an efficient and recoverable catalyst for the chemoselective oxidation of sulfides into sulfoxides and thiols into their corresponding disulfides (using hydrogen peroxide as a green oxidant) and also a suitable catalyst for the preparation of 2,3-dihydroquinazolin-4(1H)-one derivatives in water at 90°C. Using this protocol, we show that a variety of disulfides, sulfoxides, and 2,3-dihydroquinazolin-4(1H)-one derivatives can be synthesized in green conditions. The catalyst can be recovered and recycled for further reactions without appreciable loss of catalytic performance.     

微波瑞利散射法测定空气电火花激波等离子体射流的时变电子密度

大气压空气电火花激波等离子体射流的电子密度在亚微秒时间尺度上瞬变,其电子密度的测定很难.基于微波瑞利散射原理,本文测量了空气电火花冲击波流注放电等离子体射流的时变电子密度.实验结果表明:测量系统的标定参数A为1.04 × 105 V·Ω·m–2;空气流注放电等离子体射流的电子密度与等离子体射流的半径和长度有关,结合高速放电影像展示的等离子体射流的等效半径和等效长度,测定的电子密度在1020 m–3的量级,且随时间先快速增长至峰值再成指数衰减.此外,本文还探讨了等离子体射流的不同等效尺度对测定结果的影响;分析结果表明,采用时变等效半径和时变等效长度的计算结果最有效,且第1个快速波峰是由光电离的电离波导致的.     

基于自由曲面反射镜的低投射比超短焦投影物镜的光学设计

为了设计低投射比的超短焦投影物镜,本文采用自由曲面和折反式的光路结构设计了一种具有低投射比的超短焦投影物镜系统。该物镜由一个旋转对称的折射透镜组和一个自由曲面反射镜组成。采用11.938 mm的数字微镜器件(DMD)作为空间光调制器产生图像源。采用法线加权迭代优化的方法计算自由曲面。最后,分析了系统的性能。仿真结果表明:超短焦投影物镜可在580 mm的投影距离处实现3048 mm尺寸的大屏幕投影,系统的投射比低至0.19,系统的最大畸变小于0.72%。能够满足低投射比超短焦投影物镜的设计要求。该投影系统具有低投射比、低畸变、投影效果好等优点,可为超短焦投影系统的进一步发展提供有益参考。     

3d过渡金属掺杂M_2@Si_(20)(M=Sc-Zn)团簇的密度泛函理论研究

利用密度泛函理论(DFT)研究3d过渡金属掺杂硅团簇的几何结构和稳定性,计算了绝热电子亲和能和垂直电离能,内嵌双金属间距,自旋磁矩等.结果表明内嵌的Sc、Ti、V、Mn金属二聚体和十二面体硅笼构成了稳定的富勒烯结构,随着d电子数目的增加其内嵌的富勒烯构型有部分畸变,总体而言Si_(20)团簇掺杂双金属后稳定性得到了提高.     

Sliding mode control for a diffuse interface tumor growth model coupling a Cahn–Hilliard equation with a reaction–diffusion equation

We consider the sliding mode control (SMC) problem for a diffuse interface tumor growth model coupling a Cahn–Hilliard equation with a reaction–diffusion equation perturbed by a maximal monotone nonlinearity. We prove existence and regularity of strong solutions and, under further assumptions, a uniqueness result. Then, we show that the chosen SMC law forces the system to reach within finite time a sliding manifold that we chose in order that the tumor phase remains constant in time.     

Sextic centrifugal distortion constants: interplay of density functional and basis set for accurate yet feasible computations

Quantum-chemical calculations assist the analysis of laboratory spectra, and often provide the only means to determine spectroscopic data that cannot be accessed experimentally. Accurate predictions of vibrational and rotational spectroscopic parameters are required for applications in the field of high-resolution molecular spectroscopy. While the accuracy issue of the quantum-chemical calculation of vibrational properties and of equilibrium structures has been addressed in the literature, the same is not true for centrifugal distortion constants that however play an essential role for the interpretation of remote sensing data. In this work, the performance of several model chemistries, rooted mainly in density functional theory, in computing sextic centrifugal distortion constants is assessed employing a benchmark set of molecules of both atmospheric and astrochemical relevance. The Jensen’s (aug-)pcs-n basis sets, different flavours of Dunning’s triple-ζ basis sets and the SNSD basis set, are employed in conjunction with different functionals, and their predictions are benchmarked against experimental and theoretical data at the coupled cluster level of theory. This study also demonstrates the reliability of the calculation of sextic centrifugal distortion constants within the Gaussian16 rev. B.01 program package. Reliable predictions of the sextic centrifugal distortion constants for the gauche- and trans-conformers of ethyl-mercaptan are also presented.     

基于三维荧光光谱法和PARAFAC对多环芳烃定性定量分析

三维荧光光谱法在研究多环芳烃(PAHs)类物质的荧光信息时起到了重要作用。多环芳烃类物质具有致癌性,难降解性,多由尾气排放,垃圾焚烧产生,危害着人类健康及环境,因此人们不断探索对多环芳烃检测的方法。实验选取多环芳烃中的苊和萘作为检测物质,利用FLS920荧光光谱仪,为避免荧光光谱仪本身产生的瑞利散射影响,设置起始的发射波长滞后激发波长40 nm,设置扫描的激发波长(λex)范围为:200~370 nm,发射波长(λem)范围为:240~390 nm,对多环芳烃进行荧光扫描获取荧光数据,采用三维荧光光谱技术结合平行因子算法对混合溶液中的苊和萘进行定性定量分析。实验选用的苊和萘均购于阿拉丁试剂官网,配制浓度为10 mg·L-1的一级储备液,再将一级储备液稀释,得到苊和萘浓度为0.5,1,1.5,2,2.5,3,3.5,4和4.5 mg·L-1的二级储备液,并将苊和萘进行混合。在进行光谱分析前需要对苊和萘的光谱进行预处理,采用空白扣除法扣除拉曼散射的影响,并采用集合经验模态分解(EEMD)消除干扰噪声。实验测得苊存在两个波峰,位于λex=298 nm,λem=324/338 nm处,萘存在一个波峰,位于λex=280 nm,λem=322 nm处。选用的PARAFAC算法对组分数的的选择很敏感,因此采用核一致诊断法预估组分数,估计值2和3的核一致值都在60%以上,分别对混合样品进行了2因子和3因子的PARAFAC分解,将分解后得到的激发发射光谱数据和各组分浓度数据进行归一化处理,并绘制光谱图,与归一化处理后的真实的激发发射光谱图和各组分浓度图进行对比。同时将PARAFAC得到的混合样本的预测浓度,通过计算回收率(R)和均方根误差(RMSEP)来判定定量分析的准确度。选择2因子时,各混合样品中苊和萘拟合度为95.7%和96.7%,平均回收率分别为101.8%和98.9%,均方根误差分别为0.0187和0.0316;选择3因子时,各混合样品中苊和萘拟合度为95.3%和95.8%,平均回收率分别为97%和102.5%,均方根误差分别为0.033和0.116,由三项指标可得选用2因子进行定性定量分析的效果明显好于选用3因子。分析实验结果表明,基于三维荧光光谱法和PARAFAC算法对混合样品进行定性定量分析,能够有效的判定混合样品的类别,同时能够成功的预测出混合样品的浓度。     

Cascaded electron transition in CuWO_4/CdS/CDs heterostructure accelerating charge separation towards enhanced photocatalytic activity

CuWO_4,as an n-type oxide semiconductor with a bandgap of 2.2 eV,has stimulated enormous interest as a potential broad-spectrum-active photocatalyst for environmental pollution remediations.However,rapid charge recombination greatly hinders its practical applications.Herein,we present a cascaded electron transition pathway in a ternary heterostructure consisting of CdS quantum dots,carbon dots(CDs) and CuWO_4 hollow spheres,which proves to greatly facilitate the photogenerated electron-hole separation,and eventually boosts the degradation efficiency of phenol and congo red by 100% and 46%compared to bare CuWO_4.The enhanced performance of the CuWO_4/CdS/CDs heterostructure mainly originates from the unidirectional electron migration from CdS to CuWO_4 and then to the organics through CDs.This work elucidates the electron transfer kinetics in multi-phase system and provides a new design paradigm for optimizing the properties of CuWO_4 based photocatalysts.