Efficient glycosylation with glycosyl ortho-allylbenzoates as donors

Glycosylation reactions are significant as they provide access to model compounds that are useful for elucidating biochemical pathways. Herein, we describe the development of glycosyl ortho-alkynylbenzoates as novel, bench-top stable, and readily available glycosyl donors. Glycosylation is promoted by inexpensive trimethylsilyl triflate (TMSOTf) in combination with N-iodosuccinimide (NIS) under mild reaction conditions; hence, the novel glycosyl donors are promising reagents for the synthesis of glycosides.     

Vacuum Ultraviolet Free-Electron Laser Photoionization Mass Spectrometry of Alpha-pinene Ozonolysis

\begin{document}$\alpha$\end{document}-pinene is the most abundant monoterpene that represents an important family of volatile organic compounds. Molecular identification of key transient compounds during the \begin{document}$\alpha$\end{document}-pinene ozonolysis has been proven to be a challenging experimental target because of a large number of intermediates and products involved. Here we exploit the recently developed hybrid instruments that integrate aerosol mass spectrometry with a vacuum ultraviolet free-electron laser to study the \begin{document}$\alpha$\end{document}-pinene ozonolysis. The experiments of \begin{document}$\alpha$\end{document}-pinene ozonolysis are performed in an indoor smog chamber, with reactor having a volume of 2 m\begin{document}$^3$\end{document} which is made of fluorinated ethylene propylene film. Distinct mass spectral peaks provide direct experimental signatures of previously unseen compounds produced from the reaction of \begin{document}$\alpha$\end{document}-pinene with O\begin{document}$_3$\end{document}. With the aid of quantum chemical calculations, plausible mechanisms for the formation of these new compounds are proposed. These findings provide crucial information on fundamental understanding of the initial steps of \begin{document}$\alpha$\end{document}-pinene oxidation and the subsequent processes of new particle formation.     

Quick stabilization of capillary for rapid determination of potassium ions in the blood of epilepsy patients by capillary electrophoresis without sample pretreatment

Mutations in the potassium channel genes may be linked to the development of epilepsy and affect the blood potassium levels. Therefore, accurate determination of potassium in the blood will be critical to diagnose the cause of epilepsy. CE is a competent technique for the fast detection of multiple ions, but complicated matrices of a blood sample may cause significant variation of migration times and the peak shape. In this work, a procedure for rapid stabilization of the capillary inner surface through preflushing of a blood sample was employed. The process takes only 40 min for a capillary and then it can be used for more than 2 weeks. No pretreatment of the blood sample or other surface modification of the capillary is needed for the analysis. The RSDs of the migration time and peak area were reduced to 1.5 and 5.1% from 12.6 and 14.5%, respectively. The proposed method has been successfully applied to the determination of the potassium contents in the blood sample of patients with epilepsy at different stages. The recoveries of potassium ions in these blood samples are in a range from 86.5 to 104.5%.     

氮化铝薄膜的光学性能

分别使用X衍射仪和紫外（190 nm～800 nm）分光光度仪,测量了用分子束外延法生长在SiC（001）基底面上的AIN薄膜的X衍射、透射谱和不同温度下的吸收谱.X衍射表明:实验所用的AIN薄膜在c-轴存在应变和应力,该应变和应力主要是由于AIN的晶格常量与基底SiC的晶格常量不匹配所致.透射谱表明:AIN薄膜的禁带宽度大约为6.2eV;而其对应的吸收谱在6.2eV处存在一个明显的台阶,此台阶被认为是AIN薄膜中的带边自由激子吸收所产生,忽略激子的结合能(与禁带宽度相比),则该值就对应为AIN的禁带宽度.而其对应的不同温度下（10 k～293 k）的吸收谱的谱线的形状和位置无明显的变化表明:温度对AIN薄膜的禁带宽度亦无明显的影响,这主要是由于在AIN薄膜中存在着应力所致.     

环形嵌段共聚物的胶束化行为模拟

利用Monte Carlo模拟, 对比了相同组成下环形二嵌段共聚物AB和线形三嵌段共聚物ABA在选择性溶剂中的胶束化行为. 结果发现, 相同链组成的环形和线形嵌段共聚物的临界胶束浓度(cmc)的差别与A嵌段的比例(f_A)及B嵌段间的吸引强度(ε)密切相关. 在f_A较小、 ε较大的情况下, 相应环形嵌段共聚物的cmc值更小; 而在f_A较大、 ε较小的情况下, 线形嵌段共聚物的cmc值更小. 为了进一步理解胶束化行为同f_A及ε的关系, 计算了胶束化过程中熵和势能部分对自由能的贡献. 结果表明, 在所研究的f_A和ε范围内, 环形嵌段共聚物形成胶束时的熵损失更小, 因而从熵贡献角度来看, 环形嵌段共聚物更易发生胶束化. 而从势能贡献角度来看, 当f_A较小、 ε较大时, 环形嵌段共聚物形成胶束时势能有较大程度的降低, 对自由能的贡献更大, 因而此时环形嵌段共聚物更易发生胶束化. 而当f_A较大、 ε较小时, 线形嵌段共聚物形成胶束时势能有较大程度的降低, 对自由能的贡献更大, 因而此时线形嵌段共聚物更易发生胶束化. 由此可见, 对体系的胶束化自由能进行系统分析, 有助于更好地理解环形和线形嵌段共聚物的胶束化行为.     

苯甲醇氧化制苯甲酸钠反应中金钯双金属催化剂的协同效应

研究了不同Au/Pd摩尔比的AuPd/CeO2双金属催化剂在苯甲醇氧化制苯甲酸及其钠盐反应中的催化活性,利用XRD,UV-Vis DRS,TEM和XPS等手段对催化剂的结构进行了系统考察.结果表明,Au-Pd纳米颗粒以合金形式分散在CeO2载体上,不同Au/Pd摩尔比会影响催化剂表面活性物种的粒径大小和尺寸分布,并改变催化剂表面物种的组成.Au-Pd之间的电子效应和协同效应显著影响其催化活性.当Au/Pd摩尔比为3时催化剂表现出最好的催化活性,苯甲酸产率可达92%.此外,双金属催化剂的催化活性显著优于单金属催化剂,主要归因于Au和Pd之间的协同效应.AuPd/CeO2催化剂还具有良好的稳定性,Au/Pd摩尔比为3的AuPd/CeO2催化剂使用7次后仍然具有较高的催化活性.     

Complex-wave retrieval based on blind signal separation

In the process of the reconstruction of digital holography, the traditional methods of diffraction and filtration are commonly adopted to recover the original complex-wave signal. Influenced by twin-image and zero-order terms, the above-mentioned methods, however, either limit the field of vision or result in the loss of the amplitude and phase. A new method for complex-wave retrieval is presented, which is based on blind signal separation. Three frames of holograms are captured by a charge coupled device (CCD)camera to form an observation signal. The term containing only amplitude and phase of complex-wave is separated, by means of independent component analysis, from the observation signal, which effectively eliminates the zero-order term. Finally, the complex-wave retrieval of pure phase wavefront is achieved.Experimental results show that this method can better recover the amplitude and phase of the original complex-wave even when there is a frequency spectrum mixture in the hologram.     

Physical mechanisms of phonation onset: a linear stability analysis of an aeroelastic continuum model of phonation

In an investigation of phonation onset, a linear stability analysis was performed on a two-dimensional, aeroelastic, continuum model of phonation. The model consisted of a vocal fold-shaped constriction situated in a rigid pipe coupled to a potential flow which separated at the superior edge of the vocal fold. The vocal fold constriction was modeled as a plane-strain linear elastic layer. The dominant eigenvalues and eigenmodes of the fluid-structure-interaction system were investigated as a function of glottal airflow. To investigate specific aerodynamic mechanisms of phonation onset, individual components of the glottal airflow (e.g., flow-induced stiffness, inertia, and damping) were systematically added to the driving force. The investigations suggested that flow-induced stiffness was the primary mechanism of phonation onset, involving the synchronization of two structural eigenmodes. Only under conditions of negligible structural damping and a restricted set of vocal fold geometries did flow-induced damping become the primary mechanism of phonation onset. However, for moderate to high structural damping and a more generalized set of vocal fold geometries, flow-induced stiffness remained the primary mechanism of phonation onset.