N_2-DART-Orbitrap中的特征气相离子反应及在西药快速检测中的应用

采用实时直接分析(DART)离子源串联高分辨质谱Orbitrap技术(DART-Orbitrap MS),对8种市售常见西药进行有效成分分析,建立了一种快速、简便、准确测定西药中有效成分的方法.对DART离子源的离子化温度、扫描模式、操作气体种类、辅助溶剂种类及其酸碱性等实验条件进行了优化,得到最佳实验条件.实验结果表明,正谱条件下,采用N_2气作为操作气体时,待测组分准分子离子峰[M+H]+同样具有较高的灵敏度和谱图辨识度.因此,N2气可以替代昂贵的He气作为DART离子源的操作气体用于8种药物有效成分的现场实时检测.该方法具备成本低、快速和操作简便的特点.通过分析待测组分的特征碎片离子,发现了N2-DART离子源中的特征离子反应,包括氧化反应和重排反应.根据获得的特征碎片离子对N_2-DART-MS中发生的反应机理进行推导,并结合理论计算对其进行验证.N_2-DART-MS技术有望应用于复杂基质混合物的现场快速检测中.     

Experimental Study on Purification of Diesel Particulate Matter by Non-thermal Plasma Technology

In order to investigate the effects of non-thermal plasma (NTP) on diesel particulate matter (PM), an engine test bench was built up. An engine exhaust particle sizer (EEPS) was introduced to analyze the emission concentration and size distribution of PM and a thermo-gravimetric analyzer was used to analyze the effects of NTP on the composition of the particulate matter in the exhaust gas. The results show that the size distribution interval of the particle mass concentration falls behind that of the quantity concentration under various loads. When the diesel engine operating speed is 2400 rpm and the load is 25%, after NTP, the proportions of the nucleation mode particles and the accumulative mode particles exhibit a small fluctuation while the proportion of ultrafine particles decreases by 10% due to their large quantity concentration. Under the dual effect of DPF and NTP, the particle quantity concentration decreases by 98%. In order to investigate the effect of NTP on the composition of the PM, a thermo-gravimetric analysis of the particles obtained before and after NTP was carried out. The results show that the proportion of volatile matter falls by 16.05% and solid carbon accounts for an increase of 7.29%. NTP has the ability to improve reduction activity of particles and make particles easier to be oxidized at a lower temperature.     

Self‐Assembly of Discrete Homochiral,Helical, Hydrogen‐Bonded Nanocages: From Vesicles to Microspheres and Tubules Capable of Gelating Solvents

The chiral tris‐monodentate imidazolinyl ligands 1 a – c exhibit a strong tendency to form the discrete, helical [2+3] nanocages 3 ([ 1 ₂ ?2 ₃]) with tartaric acids 2 . Circular dichroism (CD) spectra and theoretical calculations reveal that supramolecular handedness of capsulelike architectures is determined only by the chirality of the imidazolinyl ligands rather than tartaric acids. The chirality of imidazolinyl ligands is transferred to the helicity of the complexes through the directed hydrogen bonds between the N3 atom of imidazoline rings and the carboxyl of tartaric acids. These hydrogen‐bonded nanocages can spontaneously self‐assemble into spherical vesicles, during which the hydrogen bonding that arises from the hydroxyl groups of tartaric acids plays a crucial issue. The vesicles formed by [{(S,S,S)‐ 1 a }₂( 2 ^L)₃] ( 3 a ) may further evolve into microspheres that gelate organic solvents after being aged at ?20 °C for 24 h, and can also be unprecedentedly transformed to tubular assemblies capable of rigidifying the solvents when subjected to ultrasound irradiation.     

基于DCSBM模型的受访者驱动抽样调查估计量改进

大数据背景下,将受访者驱动抽样(RDS)用于网络抽样调查,解决了传统抽样调查难以获得可用抽样框、难以接触被调查者以及难以获得回答等问题,也使得网络调查可以实现概率抽样,得到一定误差范围内的总体参数估计.然而,在实际抽样过程中,同质性问题(即样本单元在推荐同伴时倾向于推荐那些与自己有相同属性的同伴)会导致RDS估计量的方...     

铁苯基膦配合物均相催化乙酰丙酸乙酯与甲酸反应转化为γ-戊内酯的分子机制

本文基于密度泛函理论,计算了Fe(CF3SO3)2/PP3催化乙酰丙酸乙酯与甲酸反应转化为γ-戊内酯的反应机理。分析了单重态和三重态反应路径的热力学和动力学性质,结果表明除了预催化剂活化出现势能面交叉外,反应主要在三重态势能面上进行,包括以下几个步骤：甲酸盐配位方式重置,β-H消除得到活性催化剂[FeH(PP3)]+,接着乙酰丙酸乙酯的羰基碳和羰基氧接连被质子化得到中间体4-羟基戊酸乙酯,最后质子化的反离子CF3SO3H作为氢转移梭子协助分子内脱醇—关环生成目标产物γ-戊内酯。进一步探讨不同金属苯基膦配合物的催化活性,证实金属适宜的配位能力是筛选催化剂的关键。理论计算结果为优化设计高性能的生物质转化催化剂提供一定的理论指导。     

Zr基载体负载Pd催化剂用于贫燃天然气汽车尾气净化

 采用共沉淀法制备了 ZrO2, Y0.1Zr0.9Ox, Ce0.1Zr0.9Ox 和 Al0.1Zr0.9Ox 系列 Zr 基载体, 并用 N2 吸附-脱附和 X 射线衍射对其进行了表征. 再以此为载体, 采用浸渍法制备了整体式负载 Pd 催化剂, 催化剂涂层的涂覆量为 180 g/L 左右, Pd 含量为 1.25%. 测定了催化剂上 Pd 的分散度. 在模拟的贫燃天然气汽车尾气中考察了催化剂的活性, 并在尾气中有或无 SO2 存在的条件下比较了催化剂活性的差异. 结果表明, Y3+, Ce4+ 或 Al3+ 改性载体负载的 Pd 催化剂的耐硫性能明显改善; 无论尾气中是否存在 SO2, 以 Y3+ 或 Al3+ 改性载体负载的 Pd 催化剂的活性均明显高于 ZrO2 负载体的 Pd 催化剂.     

制备均一性靶丸过程中的影响因素

在激光聚变实验中,高球形度、高厚度均一性的靶丸经常通过乳液微封装方法来制备。利用T.Norimatsu的模型研究在靶丸制备过程中,界面间表面张力、油相粘度、壳层尺寸、壳层厚度的影响。结果显示:较大的表面张力,较小的壳层尺寸,会使胶囊具有更好的均一性。当外部变形形式不同的时候,油相的粘度对于壳层均一性会有不同作用。     

大型激光装置束间能量平衡能力综合分析方法

 针对大型激光装置输出能量平衡能力,建立了束间均方根分析方法。构建了大型激光装置的光束能量观测数据变换过程,得到服从近似正态分布的变换数据,从而建立简便的束间能量平衡能力的均方根计算方法;基于全控图和选图,针对装置能量平衡能力短期变化提出均方差控制图,并定义装置平均失效强度函数,用于描述装置整体的能量平衡能力长期变化趋势。通过对调试数据的分析,验证了综合分析方法的可视性和高效性。     

Study on the bubble transport mechanism in an acoustic standing wave field

The use of bubbles in applications such as surface chemistry, drug delivery, and ultrasonic cleaning etc. has been enormously popular in the past two decades. It has been recognized that acoustically-driven bubbles can be used to disturb the flow field near a boundary in order to accelerate physical or chemical reactions on the surface. The interactions between bubbles and a surface have been studied experimentally and analytically. However, most of the investigations focused on violently oscillating bubbles (also known as cavitation bubble), less attention has been given to understand the interactions between moderately oscillating bubbles and a boundary. Moreover, cavitation bubbles were normally generated in situ by a high intensity laser beam, little experimental work has been carried out to study the translational trajectory of a moderately oscillating bubble in an acoustic field and subsequent interactions with the surface. This paper describes the design of an ultrasonic test cell and explores the mechanism of bubble manipulation within the test cell. The test cell consists of a transducer, a liquid medium and a glass backing plate. The acoustic field within the multi-layered stack was designed in such a way that it was effectively one dimensional. This was then successfully simulated by a one dimensional network model. The model can accurately predict the impedance of the test cell as well as the mode shape (distribution of particle velocity and stress/pressure field) within the whole assembly. The mode shape of the stack was designed so that bubbles can be pushed from their injection point onto a backing glass plate. Bubble radial oscillation was simulated by a modified Keller–Miksis equation and bubble translational motion was derived from an equation obtained by applying Newton’s second law to a bubble in a liquid medium. Results indicated that the bubble trajectory depends on the acoustic pressure amplitude and initial bubble size: an increase of pressure amplitude or a decrease of bubble size forces bubbles larger than their resonant size to arrive at the target plate at lower heights, while the trajectories of smaller bubbles are less influenced by these factors. The test cell is also suitable for testing the effects of drag force on the bubble motion and for studying the bubble behavior near a surface.     

Risk assessment for crosswind stability of vehicles on exposed sites

The main purpose of this paper is to provide a reliable evaluation for the crosswind stability of different road vehicles in a realistic physical scenario. Unlike existing approaches, we analyze the wind-vehicle system by probabilistic methods. The aerodynamic coefficients together with the gust parameters are considered as random variables. In addition, on-site measured wind data are used to calibrate the gust model. As the excitation of the vehicle is a stochastic process, risk analyses have to be carried out and failure probabilities are computed. Based on the failure probabilities, guidelines for speed limitations or traffic restrictions can be developed. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)