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Electrospray ionization mass spectrometric detection of low polar compounds by adding NaAuCl4 下载免费PDF全文
Hiroshi Moriwaki 《Journal of mass spectrometry : JMS》2016,51(11):1096-1102
Liquid chromatography electrospray ionization mass spectrometry (LC/ESI/MS) has been widely used for various analyses. However, it is difficult to use LC/ESI/MS for the analysis of low polar compounds, such as polycyclic aromatic hydrocarbons. It is well known that AuCl4? ion decomposes to AuCl3 by heating, and AuCl3 is a strong π‐electrophilic Lewis acid. Low polar compounds (pyrene, benzo[a]pyrene, perylene, benzo[ghi]perylene, dibenzothiophene and p‐dimethoxybenzene) were detected by ESI/MS in the positive ion mode by adding NaAuCl4. The low polar compound interacts with AuCl3 formed at the ESI interface, and undergoes electron transfer to AuCl3. The radical cation of the low polar compound was then detected by MS. In addition, the LC/ESI/MS determination of polycyclic aromatic hydrocarbons by the post‐column addition of NaAuCl4 was studied. © 2016 The Authors Journal of Mass Spectrometry Published by John Wiley & Sons Ltd 相似文献
64.
Kristina Olofsson Michael Malkoch Anders Hult 《Journal of polymer science. Part A, Polymer chemistry》2016,54(15):2370-2378
Since extraction of the naturally occurring mussel‐foot proteins is expensive and time‐consuming, routes towards synthetic analogues are continuously being explored. Often, these methods involve several protection and deprotection steps, making the synthesis of synthetic analogues time‐consuming and expensive as well. Herein, we show that UV‐initiated thiol‐ene coupling between a thiol‐functional dopamine derivative and an allyl‐functional aliphatic polycarbonate can be used as a fast and facile route to dopa‐functional materials. Different thiol‐to‐allyl ratios and irradiation protocols were used and it was found that nearly 50% of the allyl groups could be functionalized with dopa within short reaction times, without the need of protecting the catechol. It is also demonstrated herein that the dopa‐functional polymers can be used to form self‐healing gels through complexation with Fe3+ ions at increased pH. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2370–2378 相似文献
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Cristiam F. Santa Chalarca Todd Emrick 《Journal of polymer science. Part A, Polymer chemistry》2017,55(1):83-92
Sulfonium sulfonate, or sulfothetin, zwitterionic monomers were synthesized by ring‐opening of 1,3‐propanesultone with dialkyl sulfides containing styrenic or methacrylic moieties. Reversible addition‐fragmentation chain‐transfer polymerization of these monomers was achieved in water or trifluoroethanol, and the resulting polymers exhibited higher upper critical solution temperatures than the analogous sulfobetaine polymers. Unlike typical polymer zwitterions, these polymeric sulfothetins possess an inherent reactivity that proved tunable based on their chemical structures. This reactivity makes them amenable to post‐polymerization modification by nucleophilic dealkylation to rapidly access novel substituted polymers and gels. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 83–92 相似文献
66.
《Macromolecular rapid communications》2017,38(21)
Increasing complexity and diversity of polymersomes and their compartments is a key issue for mimicking cellular functions and protocells. Thus, new challenges arise in terms of achieving tunable membrane permeability and combining it with control over the membrane diffusion process, and thus enabling a localized and dynamic control of functionality and docking possibilities within or on the surface of polymeric compartments. This study reports the concept of polymersomes with pH‐tunable membrane permeability for controlling sequential docking and undocking processes of small molecules and nanometer‐sized protein mimics selectively on the inside and outside of the polymersome membrane as a further step toward the design of intelligent multifunctional compartments for use in synthetic biology and as protocells. Host–guest interactions between adamantane and β‐cyclodextrin as well as noncovalent interactions between poly(ethylene glycol) tails and β‐cyclodextrin are used to achieve selective and dynamic functionalization of the inner and outer spheres of the polymersome membrane. 相似文献
67.
Effect of SIMS ionization probability on depth resolution for organic/inorganic interfaces 下载免费PDF全文
Nicholas J. Popczun Lars Breuer Andreas Wucher Nicholas Winograd 《Surface and interface analysis : SIA》2017,49(10):933-939
Secondary ion mass spectrometry (SIMS) relies on the fact that surface particles ejected from a solid surface are ionized under ion bombardment. By comparing the signal of molecular secondary ions desorbed from an organic film with that of the corresponding sputtered neutral precursor molecules, we investigate the variation of the molecular ionization probability when depth profiling through the film to the substrate interface. As a result, we find notable variations of the ionization probability both at the original surface and in the interface region, leading to a strong distortion of the measured SIMS depth profile. The experiments show that the effect can act in two ways, leading either to an apparent broadening or to an artificial sharpening of the observed film‐substrate transition. As a consequence, we conclude that care must be taken when assessing interface location, width, or depth resolution from a molecular SIMS depth profile. 相似文献
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A useful application for copula functions is modeling the dynamics in the conditional moments of a time series. Using copulas, one can go beyond the traditional linear ARMA (p,q) modeling, which is solely based on the behavior of the autocorrelation function, and capture the entire dependence structure linking consecutive observations. This type of serial dependence is best represented by a canonical vine decomposition, and we illustrate this idea in the context of emerging stock markets, modeling linear and nonlinear temporal dependences of Brazilian series of realized volatilities. However, the analysis of intraday data collected from e‐markets poses some specific challenges. The large amount of real‐time information calls for heavy data manipulation, which may result in gross errors. Atypical points in high‐frequency intraday transaction prices may contaminate the series of daily realized volatilities, thus affecting classical statistical inference and leading to poor predictions. Therefore, in this paper, we propose to robustly estimate pair‐copula models using the weighted minimum distance and the weighted maximum likelihood estimates (WMLE). The excellent performance of these robust estimates for pair‐copula models are assessed through a comprehensive set of simulations, from which the WMLE emerged as the best option for members of the elliptical copula family. We evaluate and compare alternative volatility forecasts and show that the robustly estimated canonical vine‐based forecasts outperform the competitors. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
69.
讨论了现有的编序式问卷调查排序方法的不足之处;提出了基于模糊偏序关系的编序式问卷调查的排序方法,给出了模糊偏序排序法的数学模型,论证了用模糊偏序关系对编序式问卷调查进行排序是一种较好的方法;并用实例分析了模糊偏序排序法应用于编序式问卷调查的具体操作步骤. 相似文献
70.
为解决国内桥梁检测车全局监控设备以及碰撞警报设备缺乏的问题,设计并实现了基于Android平台的一套智能监控系统.该系统通过倾角传感器采集的数据,用3D模型实时模拟机械臂的姿态,以达到全局监控的目的.同时可以根据实际情况构建虚拟障碍物,实现机械臂与障碍物碰撞的逼真模拟与警报.结果表明,该系统性能可靠、实用性强,不但解决了传统视频监控无法达到全局监控的问题,还对人工规避障碍物提供了可靠的参考. 相似文献