喷丸镍基合金材料微区残余应力的切槽法测量研究

本文结合聚焦离子束-电子束(Focused ion beam-electron beam,简称FIB-EB)双束系统和真空镀膜工艺,进行微区散斑的制备工艺研究,并将所发展的微散斑制备工艺应用于喷丸镍基合金材料表面制斑,进而结合切槽法进行残余应力高温释放规律的测量研究。在FIB-EB双束系统下记录切槽前后制斑微区的图像,利用数字图像相关法计算切槽后的位移,结合InglisMuskhelishvili理论公式可计算得到残余应力。文中研究了不同温度及保温时间对残余应力释放的影响规律。结果表明,残余应力随保温时间的增长释放速度逐渐减小,最后残余应力趋于稳定值。同时,温度越高,残余应力释放越彻底,800℃下近乎完全释放。该工艺具有适用性好,效率高等优点,可望在材料微区变形测量中得到进一步应用。     

表面活性剂存在下铽-镥(钆、钇)-乙酰水杨酸共发荧光体系的研究

本文研究了镥等三种稀土离子与铽-乙酰水杨酸配合物产生的共发荧光效应。在最佳条件下,Lu³⁺、Gd³⁺、Y³⁺的存在可使铽-乙酰水杨酸配合物的荧光分别增强108,58和73倍。讨论了共发光体系的形成条件和荧光特性。利用Tb-Lu-乙酰水杨酸体系和Tb-Lu-乙酰水杨酸-乙二胺四乙酸-十六烷基三甲基溴化铵体系分析了合成稀土样品和包头稀土标准氧化物中的铽,结果满意,加标回收率为90.5～105.6%,并对共发光的机理和表面活性剂的作用进行了初步探讨。     

漆酶在纳米金溶胶/多重壁碳纳米管复合载体上固定方法的比较及粒子尺寸效应

以纳米金溶胶（NGS）和多重壁碳纳米管（MWCNTs）的共混物(NGS/MWCNTs)作为固定漆酶的载体,研究了3种固定漆酶方法在酶固定量、比活力上的差异。 研究了不同的固定方法对固定酶热稳定性和重复使用性及纳米金溶胶颗粒粒径对酶固定量和固定酶动力学参数的影响。 实验结果表明,NGS/MWCNTs具有良好的固定漆酶能力和高固酶比活力,NGS/MWCNTs（NGS粒径37 nm）通过简单物理吸附法固定漆酶的量和固酶的比活力最高,分别可达33.80 mg/g和9.433 U/mg。 在NGS-MWCNTs上采用化学键合方法固定的漆酶在70 ℃放置2 h后仍然保持初始活力的75％,重复使用20次后仍保持初始活力的70％。 纳米金溶胶粒子越小（24 nm）,底物和固定漆酶间亲和力越好（KM=0.027 mmol/L）,表观速率常数越大。     

AMP-Cu2+-脱氧胆酸-凝胶体系的时空图案及其结构的研究

核苷酸是一类重要的生命物质,在体外模拟胆结石形成的实验中,选取了腺嘌呤核苷酸(AMP)为研究对象,研究了它对Cu2 脱氧胆酸体系形成时空图案的影响,用FTIR表征各种形态沉淀物的结构。结果表明:在AMP存在下的脱氧胆酸 铜离子 凝胶体系中,可形成周期沉淀及分形结构共存的复杂时空图案,红外光谱结果显示其结构中除了脱氧胆酸根(DC- )与铜离子配位外,AMP也参与了配位,可能形成DC- 1 Cu AMP的混配型非化学计量的化合物;AMP 脱氧胆酸 葡萄糖 铜凝胶体系的周期沉淀及分形结构中,AMP、葡萄糖、DC与Cu2 多核配位作用形成和组成结构更复杂的沉淀。     

A simple colorimetric sensor for biologically important anions based on intramolecular charge transfer (ICT)

A sensitive colorimetric sensor (1) based on 4,5-dinitrobenzene-1,2-diamine was designed and synthesized. Binding of anions such as AcO⁻, F⁻ and results in a notable change in the visible region of spectrum (an approximately 90 nm red shift), which can be detected by the ‘naked-eye’. Furthermore, the binding ability was evaluated by UV–vis titration experiments as following: AcO⁻ > F⁻ >   Cl⁻, Br⁻, I⁻. The nature of the color change of 1 induced by AcO⁻ was due to the intramolecular charge transfer (ICT) which was confirmed by X-ray crystal structure and ¹H NMR titration spectra.     

The preparation and structural characterization of ambient-dried porous methylsilicone matrix doped with SiO2 powder

Porous methylsilicone monoliths doped with SiO₂ powder were prepared by dispersion of SiO₂ nanoparticles in methylsilicone oligomer solution followed by ammonia-catalyzed gelation and ambient drying. The microstructure of the porous composite monoliths was investigated by FTIR, SEM, and N₂ adsorption. The results indicated that SiO₂ evenly dispersed in methylsilicone matrix. The thermal stability of SiO₂-doped methylsilicone monoliths had been enhanced. The structure stability and hydrophobic property of the composite monoliths were maintained until 400 °C.     

Enantioselective total synthesis of (+)- and (-)-nigellamine A2

The nigellamine alkaloids are dolabellane diterpenes displaying potent lipid metabolism-promoting activity. Total synthesis of (+)- and (-)-nigellamine A2 has been accomplished. Absolute stereochemistry of synthetic nigellamine A2 was established through an intramolecular asymmetric allylic alkylation using a Pd(phosphinooxazoline) catalyst. Other notable transformations include a radical alkynylation, a diastereoselective Nozaki-Hiyama-Kishi cyclization, and a regio- and stereoselective catalytic epoxidation. On the basis of X-ray crystallographic analysis of an optically active intermediate, we have confirmed the assigned absolute stereochemistry of the natural product. Minor modifications of the synthetic sequence outlined here should provide access to the other nigellamine alkaloids.     

Molecularly imprinted photonic polymer as an optical sensor to detect chloramphenicol

An inverse opal photonic crystal sensor that could specifically detect chloramphenicol (CAP) in a label-free way was introduced in the current research. A colloidal crystal template was first prepared from monodisperse SiO(2) nanospheres. Precursors with different compositions were infused into the void spaces of the respective templates and aggregated. The template and the imprinted CAP were removed, and a molecularly imprinted photonic polymer (MIPP) with numerous nanocavities derived from the SiO(2) template was prepared. The MIPP could specifically recognize the target CAP. The results showed that the embedding and transporting of CAP could change the reflection peak intensity of the MIPP. The MIPP exhibited good responsiveness, with a detection range from 1 ng mL(-1) to 1 μg mL(-1) of CAP. The MIPP response time was 8 min upon its addition to CAP at a concentration of 10 ng mL(-1), which is shorter than that of other methods. After repeated use, the MIPP maintained a good performance and detection capacity. Thus, the results prove that the novel sensor could specifically detect CAP in a simple, time-saving, and low-cost manner.     

Communication: Effect of the orbital-overlap dependence in the meta generalized gradient approximation

We study for the first time the effect of the dependence of meta generalized gradient approximation (MGGA) for the exchange-correlation energy on its input, the kinetic energy density, through the dimensionless inhomogeneity parameter, α, that characterizes the extent of orbital overlap. This leads to a simple MGGA exchange functional, which interpolates between the single-orbital regime, where α = 0, and the slowly varying density regime, where α ≈ 1, and then extrapolates to α → ∞. When combined with a variant of the Perdew-Burke-Ernzerhof GGA correlation, the resulting MGGA performs equally well for atoms, molecules, surfaces, and solids.