Electron impact,electron capture negative ionization and positive chemical ionization mass spectra of organophosphorus flame retardants and plasticizers

Phosphate esters are important commercial products that have been used both as flame retardants and as plasticizers. To analyze these compounds by gas chromatographic mass spectrometry, it is important to understand the mass spectra of these compounds using various ionization modes. This paper is a systematic overview of the electron impact (EI), electron capture negative ionization (ECNI) and positive chemical ionization (PCI) mass spectra of 13 organophosphate esters. These data are useful for developing and optimizing analytical measurements. The EI spectra of these 13 compounds are dominated by ions such as H₄PO₄⁺, (M ? Cl)⁺, (M ? CH₂Cl)⁺ or (M)⁺ depending on specific chemical structures. The ECNI spectra are generally dominated by (M ? R)^?. The PCI spectra are mainly dominated by the protonated molecular ion (M + H)⁺. The branching of the alkyl substituents, the halogenation of the substituents and, for aromatic phosphate esters, ortho alkylation of the ring are all significant factors controlling the details of the fragmentation processes. EI provides the best sensitivity for the quantitative measurement of these compounds, but PCI and ECNI both have considerable qualitative selectivity. Copyright © 2013 John Wiley & Sons, Ltd.     

宽离子能量检测范围垂直引入反射式飞行时间质谱仪的研制

本实验室研制了国内首台宽离子能量检测范围飞行时间质谱仪。仪器采用紧凑式电子轰击源设计,配合离子透镜系统有效的调制离子流,飞行时间质量分析器采用了离子垂直引入式,双场加速和双场反射以及大尺寸MCP检测装置设计。仪器单离子信号半峰宽约2 ns,仪器分辨率优于1600FWHM,检测实际样品质量范围为1~127 amu(仪器理论质量检测上限优于800 amu),可检测离子能量范围优于2个数量级(3~140 eV)。若该TOF质量分析器与短瞬高压脉冲放电离子源耦合联用,可广泛应用于高能离子束的快速检测,如真空阴极放电对制备薄膜、离子注入材料的表征,导电材料的离子电荷态分布以及离子扩散速度的测定等。     

三维介孔氨基三亚甲基膦酸锆的合成及其担载铁催化剂的甲醛催化氧化活性

以氧氯化锆和氨基三亚甲基膦酸(ATMP)为原料合成了一种新型介孔材料氨基三亚甲基膦酸锆(NTAZP)。使用XRD、FTIR、TG-DTA和SEM等手段对所合成的介孔材料进行了结构表征和形貌分析。然后以NTAZP为载体,用Fe(NO3)3水溶液处理,得到担载Fe3+的氨基三亚甲基膦酸锆。研究结果表明,Fe3+被吸附到载体孔道中后,NTAZP结构未被破坏,Fe3+离子与NTAZP孔壁骨架上的N发生了配位作用。铁担载NTAZP(NTAZP-Fe3+)对甲醛氧化具有良好的催化活性,催化反应条件温和,催化剂稳定性良好。以载体NTAZP担载铁还避免了Fe3+进入水体,催化剂得以回收利用,避免造成二次污染。NTAZP-Fe3+是一种高效绿色的新型小分子醛类化合物氧化催化剂。     

基于改进粒子群优化算法的火电厂机组负荷分配

以坑口电厂SIS系统机组负荷优化分配功能模块为应用背景,针对基本粒子群优化算法易陷入局部收敛、收敛速度慢的缺点,提出一种基于惯性权重非线性减小策略的改进粒子群优化算法。并且通过MATLAB与Visual C++混合编程,开发了机组负荷在线优化分配功能模块,提高了算法的计算效率和工程应用价值。     

磨机负荷专家控制系统设计及仿真研究

借鉴生物界的免疫反馈原理和遗传算法,利用模糊控制可以有效地实现对非线性、纯滞后、复杂的对象进行控制的优点,并结合PID与自寻优方法,设计出磨机负荷专家控制系统,用VB编写OPC客户端及控制程序,实现对磨机负荷的动态优化控制。试验结果表明,本文提出的控制策略能够很好的跟踪被控对象的参数变化,在存在干扰的情况下也能有较强的自适应能力,能够提高磨机台时产量,并提高矿厂的经济效益。     

基于Chebyshev多项式的神经网络中长期负荷预测研究

高精度负荷预测在提高电力系统的安全性和经济性方面有着极其重要的意义,而现有的负荷预测方法因参数有限,难以完全反映其内在规律,因而导致预测结果不够准确.为此提出了一种基于Chebyshev多项式神经网络模型的预测方法.该方法使用递推最小二乘法训练神经网络权值系数,以获得高精度的参数估计,从而实现Chebyshev多项式神经网络模型对负荷量的最优拟合,再利用训练好的Chebyshev多项式神经网络模型实现中长期负荷预测.研究结果表明,该方法能较好模拟负荷变化规律,有效提高了负荷预测精度,在电力系统负荷预测中有较大的应用价值.     

Substituent Effects on EI-MS Fragmentation Patterns of 5-Allyloxy-1-aryl-tetrazoles and 4-Allyl-1-aryl-tetrazole-5-ones; Correlation with UV-Induced Fragmentation Channels

1,4- and 1,5-disubstituted tetrazoles possess enriched structures and versatile chemistry, representing a challenge for chemists. In the present work, we unravel the fragmentation patterns of a chemically diverse range of 5-allyloxy-1-aryl-tetrazoles and 4-allyl-1-aryl-tetrazolole-5-ones when subjected to electron impact mass spectrometry (EI-MS) and investigate the correlation with the UV-induced fragmentation channels of the matrix-isolated tetrazole derivatives. Our results indicate that the fragmentation pathways of the selected tetrazoles in EI-MS are highly influenced by the electronic effects induced by substitution. Multiple pathways can be envisaged to explain the mechanisms of fragmentation, frequently awarding common final species, namely arylisocyanate, arylazide, arylnitrene, isocyanic acid and hydrogen azide radical cations, as well as allyl/aryl cations. The identified fragments are consistent with those found in previous investigations concerning the photochemical stability of the same class of molecules. This parallelism showcases a similarity in the behaviour of tetrazoles under EI-MS and UV-irradiation in the inert environment of cryogenic matrices of noble gases, providing efficient tools for reactivity predictions, whether for analytical ends or more in-depth studies. Theoretical calculations provide complementary information to articulate predictions of resulting products.     

基于AHP权重和灰色服务器负载预测的云计算On-line迁移策略

为了克服云计算环境下由于实时用户任务的不确定性到来和服务器性能差异而导致的云计算环境的负载不均衡问题,提出了一种AHP权重获取和灰度算法预测服务器负载的云计算on-line虚拟机迁移策略。首先,设计了基于AHP和灰色服务器预测的虚拟机on-line迁移模型,提出了采用AHP获取虚拟机各资源需求权重,然后,采用灰色模型预测下一时刻的服务器负载,采用此权值向量与各无需迁移的服务器的空闲资源向量进行加权得到加权和,将具有最小加权和的物理服务器作为迁移的目标宿主机。最后,定义了基于AHP权重和灰色服务器负载预测的云计算on-line迁移算法。在CloudSim环境下进行实验,结果表明文中的迁移策略使得云计算在响应用户任务时,具有任务失败次数少、SLA违约率低和迁移成功率高的优点,同时与其它方法相比,具有负载均衡程度高的优点,具有较强的可行性。     

Impact resistance analysis of flexible fabric by 3D shape of impact basin in low-speed impact test

Hopkinson non-penetrating low-speed impact test was carried out on Kevlar flexible fabrics. The impact basin was formed by the clay on the back of the fabric, and the ultimate deformation of the fabric was recorded completely. The 3D shape of the clay impact basin was measured by fringe projection profilometry and converted into the impact basin volume. At the same time, the relationship between the indentation volume and the deformation energy of the clay was calibrated using the clay intrusion test. The clay impact basin volume is then converted into the residual energy of the flexible fabric subjected to the low-speed impact, and a new index of the impact basin volume is established to evaluate the energy absorption efficiency of fabric under the low-speed impact. Finally, combined with the deformation of single-layer fabric, the stress wave propagation in the impact deformation process of fabric is discussed, which is helpful to understand the impact energy absorption mechanism of flexible fabric.