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991.
Ion tree‐based structure elucidation of acetophenone dimers (AtA) from Acronychia pedunculata and their identification in extracts by liquid chromatography electrospray ionization LTQ‐Orbitrap mass spectrometry 下载免费PDF全文
Eirini Kouloura Alexios‐Leandros Skaltsounis Sylvie Michel Maria Halabalaki 《Journal of mass spectrometry : JMS》2015,50(3):495-512
Acronychia‐type acetophenones (AtA) is a chemical group of compounds of important structural and biological interest, abundant in Acronychia species. However, there are no data available for their characterization using mass spectrometry. In the current work, AtA have been investigated by multistage high resolution mass spectrometry and both electrospray ionization and atmospheric pressure chemical ionization, in positive and negative mode, were utilized for their structure elucidation and identification. The analysis of AtA using a linear ion trap‐Orbitrap analyzer enabled the structural determination of key fragment ions and cleavages, which can be used for the structural characterization thereof. A systematic nomenclature based on protonated and deprotonated fragment ions under collision‐induced dissociation conditions and decision trees for the structural determination of AtA are proposed. Furthermore, taking advantage of the characteristic fragmentation patterns, a selective Ultra High Performance Liquid Chromatography Electrospray Ionization multistage Mass Spectrometry (UHPLC‐ESI(‐)‐MSn) method was developed and successfully applied for the dereplication of known AtA and the identification of potentially new ones in Acronychia extracts. Despite the structure similarity and the presence of isomers, accurate characterization of known and unknown AtA derivatives was possible. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
992.
Direct chemical profiling of olive (Olea europaea) fruit epicuticular waxes by direct electrospray‐ultrahigh resolution mass spectrometry 下载免费PDF全文
Stefania Vichi Nuria Cortés‐Francisco Agustí Romero Josep Caixach 《Journal of mass spectrometry : JMS》2015,50(3):558-566
In the present paper, an electrospray ionization (ESI)‐Orbitrap method is proposed for the direct chemical profiling of epicuticular wax (EW) from Olea europaea fruit. It constitutes a rapid and efficient tool suitable for a wide‐ranging screening of a large number of samples. In a few minutes, the method provides a comprehensive characterization of total EW extracts, based on the molecular formula of their components. Accurate mass measurements are obtained by ultrahigh resolution mass spectrometry, and compositional restrictions are set on the basis of the information available from previous studies of olive EW. By alternating positive and negative ESI modes within the same analysis, complementary results are obtained and a wide range of chemical species is covered. This provides a detailed compositional overview that otherwise would only be available by applying multiple analytical techniques. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
993.
Separation and characterization of oxidized isomeric lipid–peptide adducts by ion mobility mass spectrometry 下载免费PDF全文
Ivana Milic Marc Kipping Ralf Hoffmann Maria Fedorova 《Journal of mass spectrometry : JMS》2015,50(12):1386-1392
Phospholipids are major components of cell membranes and lipoprotein complexes. They are prone to oxidation by endogenous and exogenous reactive oxygen species yielding a large variety of modified lipids including small aliphatic and phospholipid bound aldehydes and ketones. These carbonyls are strong electrophiles that can modify proteins and, thereby, alter their structures and functions triggering various pathophysiological conditions. The analysis of lipid–protein adducts by liquid chromatography‐MS is challenged by their mixed chemical nature (polar peptide and hydrophobic lipid), low abundance in biological samples, and formation of multiple isomers. Thus, we investigated traveling wave ion mobility mass spectrometry (TWIMS) to analyze lipid–peptide adducts generated by incubating model peptides corresponding to the amphipathic β1 sheet sequence of apolipoprotein B‐100 with 1‐palmitoyl‐2‐(oxo‐nonanoyl)‐sn‐glycerophosphatidylcholine (PONPC). The complex mixture of peptides, lipids, and peptide–lipid adducts was separated by TWIMS, which was especially important for the identification of two mono‐PONPC‐peptide isomers containing Schiff bases at different lysine residues. Moreover, TWIMS separated structural conformers of one peptide–lipid adduct possessing most likely different orientations of the hydrophobic sn‐1 fatty acyl residue and head group of PONPC, relative to the peptide backbone. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
994.
Insights into the Catalytic Activity of Nitridated Fibrous Silica (KCC‐1) Nanocatalysts from 15N and 29Si NMR Spectroscopy Enhanced by Dynamic Nuclear Polarization 下载免费PDF全文
Dr. Aany Sofia Lilly Thankamony Dr. Cédric Lion Dr. Frédérique Pourpoint Baljeet Singh Dr. Angel J. Perez Linde Dr. Diego Carnevale Prof. Geoffrey Bodenhausen Dr. Hervé Vezin Prof. Olivier Lafon Prof. Vivek Polshettiwar 《Angewandte Chemie (International ed. in English)》2015,54(7):2190-2193
Fibrous nanosilica (KCC‐1) oxynitrides are promising solid‐base catalysts. Paradoxically, when their nitrogen content increases, their catalytic activity decreases. This counterintuitive observation is explained here for the first time using 15N‐solid‐state NMR spectroscopy enhanced by dynamic nuclear polarization. 相似文献
995.
Ana M. Geer Ángel L. Serrano Prof. Bas de Bruin Prof. Miguel A. Ciriano Dr. Cristina Tejel 《Angewandte Chemie (International ed. in English)》2015,54(2):472-475
Complexes with terminal phosphanido (M? PR2) functionalities are believed to be crucial intermediates in new catalytic processes involving the formation of P? P and P? C bonds. We showcase here the isolation and characterization of mononuclear phosphanide rhodium complexes ([RhTp(H)(PR2)L]) that result from the oxidative addition of secondary phosphanes, a reaction that was also explored computationally. These compounds are active catalysts for the dehydrocoupling of PHPh2 to Ph2P? PPh2. The hydrophosphination of dimethyl maleate and the unactivated olefin ethylene is also reported. Reliable evidence for the prominent role of mononuclear phosphanido rhodium species in these reactions is also provided. 相似文献
996.
Chun‐Feng Wang Dr. Ren‐Fu Li Prof. Dr. Xue‐Yuan Chen Dr. Rong‐Jia Wei Prof. Dr. Lan‐Sun Zheng Prof. Dr. Jun Tao 《Angewandte Chemie (International ed. in English)》2015,54(5):1574-1577
Hybrid materials integrated with a variety of physical properties, such as spin crossover (SCO) and fluorescence, may show synergetic effects that find applications in many fields. Herein we demonstrate a promising post‐synthetic approach to achieve such materials by grafting fluorophores (1‐pyrenecarboxaldehyde and Rhodamine B) on one‐dimensional SCO FeII structures. The resulting hybrid materials display expected one‐step SCO behavior and fluorescent properties, in particular showing a coupling between the transition temperature of SCO and the temperature where the fluorescent intensity reverses. Consequently, synergetic effect between SCO and fluorescence is incorporated into materials despite different fluorophores. This study provides an effective strategy for the design and development of novel magnetic and optical materials. 相似文献
997.
Cooperative Crystallization of Heterometallic Indium–Chromium Metal–Organic Polyhedra and Their Fast Proton Conductivity 下载免费PDF全文
Dr. Quan‐Guo Zhai Chengyu Mao Dr. Xiang Zhao Dr. Qipu Lin Fei Bu Xitong Chen Prof. Dr. Xianhui Bu Prof. Dr. Pingyun Feng 《Angewandte Chemie (International ed. in English)》2015,54(27):7886-7890
Metal–organic polyhedra (MOPs) or frameworks (MOFs) based on Cr3+ are notoriously difficult to synthesize, especially as crystals large enough to be suitable for characterization of the structure or properties. It is now shown that the co‐existence of In3+ and Cr3+ induces a rapid crystal growth of large single crystals of heterometallic In‐Cr‐MOPs with the [M8L12] (M=In/Cr, L=dinegative 4,5‐imidazole‐dicarboxylate) cubane‐like structure. With a high concentration of protons from 12 carboxyl groups decorating every edge of the cube and an extensive H‐bonded network between cubes and surrounding H2O molecules, the newly synthesized In‐Cr‐MOPs exhibit an exceptionally high proton conductivity (up to 5.8×10?2 S cm?1 at 22.5 °C and 98 % relative humidity, single crystal). 相似文献
998.
Mechanistic Insight into the Stereochemical Control of Lactide Polymerization by Salan–Aluminum Catalysts 下载免费PDF全文
Konstantin Press Prof. Israel Goldberg Prof. Moshe Kol 《Angewandte Chemie (International ed. in English)》2015,54(49):14858-14861
Alkyl aluminum complexes of chiral salan ligands assembled around the 2,2′‐bipyrrolidine core form as single diastereomers that have identical configurations of the N donors. Active catalysts for the polymerization of lactide were formed upon the addition of benzyl alcohol. Polymeryl exchange between enantiomorphous aluminum species had a dramatic effect on the tacticity of the poly(lactic acid) (PLA) in the polymerization of racemic lactide (rac‐LA): The enantiomerically pure catalyst of the nonsubstituted salan ligand led to isotactic PLA, and the racemic catalyst exhibited lower stereocontrol. The enantiomerically pure catalyst of the chloro‐substituted salan ligand led to PLA with a slight tendency toward heterotacticity, whereas the racemic catalyst led to PLA of almost perfect heterotacticity following an insertion/auto‐inhibition/exchange mechanism. 相似文献
999.
Cover Picture: Metal‐Free Addition/Head‐to‐Tail Polymerization of Transient Phosphinoboranes,RPH‐BH2: A Route to Poly(alkylphosphinoboranes) (Angew. Chem. Int. Ed. 46/2015) 下载免费PDF全文
1000.
随机结构正交展开分析的Ritz动力聚缩法 总被引:1,自引:0,他引:1
针对随机结果正交展开理论计算上的弱点 ,本文在分析扩阶矩阵特性的基础上 ,于 Ritz模态向量子空间中对扩阶方程实现动力聚缩 ,大大提高了正交展开理论对实际工程问题的分析能力。分析实例表明 :即使结构参数具有很大变异性 (如δ =0 .4 )时 ,该算法依然能理想地与 Monte Carlo法模拟结果相吻合 ,计算时间则远远小于 Monte Carlo模拟法。同时 ,分析例证再一次强化了在结构动力分析中考虑结构参数随机性的必要性 相似文献