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151.
Melkonian JM Forget N Bretenaker F Drag C Lefebvre M Rosencher E 《Optics letters》2007,32(12):1701-1703
We report on what we believe to be the first active mode locking of near-degenerate, doubly and singly resonant cw-pumped optical parametric oscillators (OPOs). We show experimentally that a steady-state regime of short pulses is reached in a few tens of microseconds under cw pumping. The oscillation buildup dynamics of both OPOs is also explored, evidencing an unusual transient behavior in the mode-locking process. 相似文献
152.
Currently, feature annotation remains one of the main challenges in untargeted metabolomics. In this context, the information provided by high-resolution mass spectrometry (HRMS) in addition to accurate mass can improve the quality of metabolite annotation, and MS/MS fragmentation patterns are widely used. Accurate mass and a separation index, such as retention time or effective mobility (μeff), in chromatographic and electrophoretic approaches, respectively, must be used for unequivocal metabolite identification. The possibility of measuring collision cross-section (CCS) values by using ion mobility (IM) is becoming increasingly popular in metabolomic studies thanks to the new generation of IM mass spectrometers. Based on their similar separation mechanisms involving electric field and the size of the compounds, the complementarity of DTCCSN2 and μeff needs to be evaluated. In this study, a comparison of DTCCSN2 and μeff was achieved in the context of feature identification ability in untargeted metabolomics by capillary zone electrophoresis (CZE) coupled with HRMS. This study confirms the high correlation of DTCCSN2 with the mass of the studied metabolites as well as the orthogonality between accurate mass and μeff, making this combination particularly interesting for the identification of several endogenous metabolites. The use of IM-MS remains of great interest for facilitating the annotation of neutral metabolites present in the electroosmotic flow (EOF) that are poorly or not separated by CZE. 相似文献
153.
154.
Scott B. Ficarro Jessica M. Biagi Jinhua Wang Jenna Scotcher Rositsa I. Koleva Joseph D. Card Guillaume Adelmant Huan He Manor Askenazi Alan G. Marshall Nicolas L. Young Nathanael S. Gray Jarrod A. Marto 《Journal of the American Society for Mass Spectrometry》2014,25(4):636-650
We assemble a versatile molecular scaffold from simple building blocks to create binary and multiplexed stable isotope reagents for quantitative mass spectrometry. Termed Protected Amine Labels (PAL), these reagents offer multiple analytical figures of merit including, (1) robust targeting of peptide N-termini and lysyl side chains, (2) optimal mass spectrometry ionization efficiency through regeneration of primary amines on labeled peptides, (3) an amino acid-based mass tag that incorporates heavy isotopes of carbon, nitrogen, and oxygen to ensure matched physicochemical and MS/MS fragmentation behavior among labeled peptides, and (4) a molecularly efficient architecture, in which the majority of hetero-atom centers can be used to synthesize a variety of nominal mass and sub-Da isotopologue stable isotope reagents. We demonstrate the performance of these reagents in well-established strategies whereby up to four channels of peptide isotopomers, each separated by 4 Da, are quantified in MS-level scans with accuracies comparable to current commercial reagents. In addition, we utilize the PAL scaffold to create isotopologue reagents in which labeled peptide analogs differ in mass based on the binding energy in carbon and nitrogen nuclei, thereby allowing quantification based on MS or MS/MS spectra. We demonstrate accurate quantification for reagents that support 6-plex labeling and propose extension of this scheme to 9-channels based on a similar PAL scaffold. Finally, we provide exemplar data that extend the application of isotopologe-based quantification reagents to medium resolution, quadrupole time-of-flight mass spectrometers. Figure
115F 相似文献
155.
Dr. Zhe Liu Dr. Isolda Romero‐Canelón Bushra Qamar Jessica M. Hearn Dr. Abraha Habtemariam Dr. Nicolas P. E. Barry Dr. Ana M. Pizarro Dr. Guy J. Clarkson Prof. Dr. Peter J. Sadler 《Angewandte Chemie (International ed. in English)》2014,53(15):3941-3946
Platinum complexes are the most widely used anticancer drugs; however, new generations of agents are needed. The organoiridium(III) complex [(η5‐Cpxbiph)Ir(phpy)(Cl)] ( 1‐Cl ), which contains π‐bonded biphenyltetramethylcyclopentadienyl (Cpxbiph) and C^N‐chelated phenylpyridine (phpy) ligands, undergoes rapid hydrolysis of the chlorido ligand. In contrast, the pyridine complex [(η5‐Cpxbiph)Ir(phpy)(py)]+ ( 1‐py ) aquates slowly, and is more potent (in nanomolar amounts) than both 1‐Cl and cisplatin towards a wide range of cancer cells. The pyridine ligand protects 1‐py from rapid reaction with intracellular glutathione. The high potency of 1‐py correlates with its ability to increase substantially the level of reactive oxygen species (ROS) in cancer cells. The unprecedented ability of these iridium complexes to generate H2O2 by catalytic hydride transfer from the coenzyme NADH to oxygen is demonstrated. Such organoiridium complexes are promising as a new generation of anticancer drugs for effective oxidant therapy. 相似文献
156.
High‐Yield Formation of Substituted Tetracyanobutadienes from Reaction of Ynamides with Tetracyanoethylene
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Dr. Marie Betou Nicolas Kerisit Esme Meledje Dr. Yann R. Leroux Dr. Claudine Katan Dr. Jean‐François Halet Dr. Jean‐Claude Guillemin Dr. Yann Trolez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(31):9553-9557
A high‐yielding sequence of [2+2] cycloaddition–retroelectrocyclization of ynamides with tetracyanoethylene (TCNE) is described. The reaction provided tetracyanobutadiene (TCBD) species, which were characterized by various techniques. DFT and TD‐DFT calculations were also performed to complement experimental findings. 相似文献
157.
Dr. Romain Ramozzi Dr. Nicolas Chéron Dr. Laurent El Kaïm Dr. Laurence Grimaud Dr. Paul Fleurat‐Lessard 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(29):9094-9099
Following our previous mechanistic studies of multicomponent Ugi‐type reactions, theoretical calculations have been performed to predict the efficiency of new substrates in Ugi–Smiles couplings. First, as predicted, 2,4,6‐trichlorophenol experimentally gave the corresponding aryl‐imidate. Theoretical predictions of nitrosophenols as good acidic partners were then successfully confirmed by experiments. In the latter case, the reaction offers a new access to benzimidazoles. 相似文献
158.
On the Synthesis,Characterization and Reactivity of N‐Heteroaryl–Boryl Radicals,a New Radical Class Based on Five‐Membered Ring Ligands
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Dr. Mohamad‐Ali Tehfe Dr. Stéphane Schweizer Dr. Anne‐Caroline Chany Dr. Cédric Ysacco Dr. Jean‐Louis Clément Dr. Didier Gigmes Dr. Fabrice Morlet‐Savary Prof. Jean‐Pierre Fouassier Dr. Markus Neuburger Dr. Théophile Tschamber Dr. Nicolas Blanchard Prof. Jacques Lalevée 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(17):5054-5063
The synthesis and physical characterization of a new class of N‐heterocycle–boryl radicals is presented, based on five membered ring ligands with a N(sp2) complexation site. These pyrazole–boranes and pyrazaboles exhibit a low bond dissociation energy (BDE; B?H) and accordingly excellent hydrogen transfer properties. Most importantly, a high modulation of the BDE(B?H) by the fine tuning of the N‐heterocyclic ligand was obtained in this series and could be correlated with the spin density on the boron atom of the corresponding radical. The reactivity of the latter for small molecule chemistry has been studied through the determination of several reaction rate constants corresponding to addition to alkenes and alkynes, addition to O2, oxidation by iodonium salts and halogen abstraction from alkyl halides. Two selected applications of N‐heterocycle–boryl radicals are also proposed herein, for radical polymerization and for radical dehalogenation reactions. 相似文献
159.
Aerobic Double Dehydrogenative Cross Coupling between Cyclic Saturated Ketones and Simple Arenes
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Dr. Nicolas Gigant Prof. Dr. Jan‐E. Bäckvall 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(20):5890-5894
The synthesis of 3‐aryl‐2‐cyclohexenones is a topic of current interest as they are not only privileged structures in bioactive molecules, but they are also relevant feedstocks for the synthesis of substituted phenols or anilines, which are ubiquitous structural elements both in drug design and medicinal chemistry. A simple and sustainable one‐pot aerobic double dehydrogenative reaction under mild conditions for the introduction of arenes in the β‐position of cyclic ketones has been developed. Starting from the corresponding saturated ketone, this reaction sequence proceeds under relatively low Pd catalyst loading and involves catalytic amounts of electron‐transfer mediators (ETMs) under ambient oxygen pressure. 相似文献
160.
Prof. Li Chen Genevieve E. Mullen Myriam Le Roch Cody G. Cassity Prof. Nicolas Gouault Prof. Henry Y. Fadamiro Prof. Robert E. Barletta Prof. Richard A. O'Brien Prof. Richard E. Sykora Prof. Alexandra C. Stenson Prof. Kevin N. West Howard E. Horne Jeffrey M. Hendrich Kang Rui Xiang Prof. James H. Davis Jr. 《Angewandte Chemie (International ed. in English)》2014,53(44):11762-11765
The practical utility of ionic liquids (ILs) makes the absence (heretofore) of reported examples from nature quite puzzling, given the facility with which nature produces many other types of exotic but utilitarian substances. In that vein, we report here the identification and characterization of a naturally occurring protic IL. It can be formed during confrontations between the ants S. invicta and N. fulva. After being sprayed with alkaloid‐based S. invicta venom, N. fulva detoxifies by grooming with its own venom, formic acid. The mixture is a viscous liquid manifestly different from either of the constituents. Further, we find that the change results as a consequence of formic acid protonation of the N centers of the S. invicta venom alkaloids. The resulting mixed‐cation ammonium formate milieu has properties consistent with its classification as a protic IL. 相似文献