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91.
Adam J. McShane Yuanyuan Shen Mary Joan Castillo Xudong Yao 《Journal of the American Society for Mass Spectrometry》2014,25(10):1694-1704
Direct reductive methylation of peptides is a common method for quantitative proteomics. It is an active derivatization technique; with participation of the dimethylamino group, the derivatized peptides preferentially release intense a1 ions. The advantageous generation of a1 ions for quantitative proteomic profiling, however, is not desirable for targeted proteomic quantitation using multiple reaction monitoring mass spectrometry; this mass spectrometric method prefers the derivatizing group to stay with the intact peptide ions and multiple fragments as passive mass tags. This work investigated collisional fragmentation of peptides whose amine groups were derivatized with five linear ω-dimethylamino acids, from 2-(dimethylamino)-acetic acid to 6-(dimethylamino)-hexanoic acid. Tandem mass spectra of the derivatized tryptic peptides revealed different preferential breakdown pathways. Together with energy resolved mass spectrometry, it was found that shutting down the active participation of the terminal dimethylamino group in fragmentation of derivatized peptides is possible. However, it took a separation of five methylene groups between the terminal dimethylamino group and the amide formed upon peptide derivatization. For the first time, the gas-phase fragmentation of peptides derivatized with linear ω-dimethylamino acids of systematically increasing alkyl chain lengths is reported. Figure
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92.
An Efficient RuII–RhIII–RuII Polypyridyl Photocatalyst for Visible‐Light‐Driven Hydrogen Production in Aqueous Solution 下载免费PDF全文
Dr. Thibaut Stoll Dr. Marcello Gennari Dr. Jérôme Fortage Dr. Carmen E. Castillo Dr. Mateusz Rebarz Dr. Michel Sliwa Dr. Olivier Poizat Dr. Fabrice Odobel Dr. Alain Deronzier Dr. Marie‐Noëlle Collomb 《Angewandte Chemie (International ed. in English)》2014,53(6):1654-1658
The development of multicomponent molecular systems for the photocatalytic reduction of water to hydrogen has experienced considerable growth since the end of the 1970s. Recently, with the aim of improving the efficiency of the catalysis, single‐component photocatalysts have been developed in which the photosensitizer is chemically coupled to the hydrogen‐evolving catalyst in the same molecule through a bridging ligand. Until now, none of these photocatalysts has operated efficiently in pure aqueous solution: a highly desirable medium for energy‐conversion applications. Herein, we introduce a new ruthenium–rhodium polypyridyl complex as the first efficient homogeneous photocatalyst for H2 production in water with turnover numbers of several hundred. This study also demonstrates unambiguously that the catalytic performance of such systems linked through a nonconjugated bridge is significantly improved as compared to that of a mixture of the separate components. 相似文献
93.
94.
Molecular Recognition of Nucleotides in Water by Scorpiand‐Type Receptors Based on Nucleobase Discrimination 下载免费PDF全文
Mario Inclán Dr. M. Teresa Albelda Dr. Esther Carbonell Dr. Salvador Blasco Antonio Bauzá Prof. Antonio Frontera Prof. Enrique García‐España 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(13):3730-3741
The detection of nucleotides is of crucial importance because they are the basic building blocks of nucleic acids. Scorpiand‐based polyamine receptors functionalized with pyridine or anthracene units are able to form stable complexes with nucleotides in water, based on coulombic, π–π stacking, and hydrogen‐bonding interactions. This behavior has been rationalized by means of an exploration with NMR spectroscopy and DFT calculations. Binding constants were determined by potentiometry. Fluorescence spectroscopy studies have revealed the potential of these receptors as sensors to effectively and selectively distinguish guanosine‐5′‐triphosphate (GTP) from adenosine‐5′‐triphosphate (ATP). 相似文献
95.
Manuel A. Ortuño Dr. Pietro Vidossich Dr. Salvador Conejero Prof. Dr. Agustí Lledós 《Angewandte Chemie (International ed. in English)》2014,53(51):14158-14161
Hydrogen atoms in the coordination sphere of a transition metal are highly mobile ligands. Here, a new type of dynamic process involving hydrides has been characterized by computational means. This dynamic event consists of an orbital‐like motion of hydride ligands around low‐coordinate metal centers containing N‐heterocyclic carbenes. The hydride movement around the carbene–metal–carbene axis is the lowest energy mode connecting energy equivalent isomers. This understanding provides crucial information for the interpretation of NMR spectra. 相似文献
96.
Salvador G. Hernndez‐Vargas Carlos Alberto Cevallos‐Morillo Julio C. Aguilar‐Cordero 《Electroanalysis》2020,32(9):1938-1948
In this work 12 different ionic liquids (ILs) have been used added as co‐binders in the preparation of modified carbon paste electrodes (IL–CPEs) used for the voltammetric analysis of dopamine in Britton‐Robinson buffer. The ionic liquids studied were selected based on three main criteria: (1) increasing chain length of alkyl substituents (studying 1‐ethylimidazolium and ethyl, propyl, butyl, hexyl and decylmethylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquids); (2) nature of the counter ion (dicyanamide, bis(trifluoromethylsulfonyl)imide and hexafluorophosphate) in 1‐butyl‐3‐methylimidazolium ionic liquids; and (3) cation ring structures (1‐butyl‐3‐methylimidazolium, 1‐butyl‐1‐methylpiperidinium, 1‐butyl‐1‐methylpyrrolidinium and 1‐butyl‐3‐methylpyridinium) in bis(trifluoromethylsulfonyl)imide or hexafluorophosphate (1‐butyl‐3‐methylimidazolium or 1‐butyl‐3‐methylpyridinium as cations) ionic liquids. The use of IL as co‐binders in IL–CPE results in a general enhancement of both the sensitivity and the reversibility of dopamine oxidation. In square wave voltammetry experiments, the peak current increased up to a 400 % when 1‐ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide was used as co‐binder, as compared to the response found with the unmodified CPE. Experimental data provide evidence that electrostatic and steric effects are the most important ones vis‐à‐vis these electrocatalytic effects on the anodic oxidation of dopamine on IL–CPE. The relative hydrophilicity of dicyanamide anions reduced the electrocatalytic effects of the corresponding ionic liquids, while the use of 1‐ethyl‐3‐methylimidazolium hexafluorophosphate or 1‐ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide (two relatively small and highly hydrophobic ionic liquids) as co‐binders in IL–CPE resulted in the highest electrocatalytic activity among all of the IL–CPE studied. 相似文献
97.
Back Cover: Experimental and Theoretical Study of the Reactivity of Gold Nanoparticles Towards Benzimidazole‐2‐ylidene Ligands (Chem. Eur. J. 30/2016) 下载免费PDF全文
Dr. María Rodríguez‐Castillo Gustavo Lugo‐Preciado Dr. Danielle Laurencin Dr. Frederik Tielens Dr. Arie van der Lee Dr. Sébastien Clément Dr. Yannick Guari Dr. José M. López‐de‐Luzuriaga Dr. Miguel Monge Dr. Françoise Remacle Dr. Sébastien Richeter 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(30):10680-10680
98.
Dr. Carmen E. Castillo Dr. Ilaria Gamba Laia Vicens Dr. Martin Clémancey Prof. Dr. Jean-Marc Latour Prof. Dr. Miquel Costas Prof. Dr. Manuel G. Basallote 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(15):4946-4954
Oxoiron(IV) complexes bearing tetradentate ligands have been extensively studied as models for the active oxidants in non-heme iron-dependent enzymes. These species are commonly generated by oxidation of their ferrous precursors. The mechanisms of these reactions have seldom been investigated. In this work, the reaction kinetics of complexes [FeII(CH3CN)2L](SbF6)2 ( [1](SbF6)2 and [2](SbF6)2 ) and [FeII(CF3SO3)2L] ( [1](OTf)2 and [2](OTf)2 ( 1 , L=Me,HPytacn; 2 , L=nP,HPytacn; R,R′Pytacn=1-[(6-R′-2-pyridyl)methyl]-4,7- di-R-1,4,7-triazacyclononane) with Bu4NIO4 to form the corresponding [FeIV(O)(CH3CN)L]2+ ( 3 , L=Me,HPytacn; 4 , L=nP,HPytacn) species was studied in acetonitrile/acetone at low temperatures. The reactions occur in a single kinetic step with activation parameters independent of the nature of the anion and similar to those obtained for the substitution reaction with Cl− as entering ligand, which indicates that formation of [FeIV(O)(CH3CN)L]2+ is kinetically controlled by substitution in the starting complex to form [FeII(IO4)(CH3CN)L]+ intermediates that are converted rapidly to oxo complexes 3 and 4 . The kinetics of the reaction is strongly dependent on the spin state of the starting complex. A detailed analysis of the magnetic susceptibility and kinetic data for the triflate complexes reveals that the experimental values of the activation parameters for both complexes are the result of partial compensation of the contributions from the thermodynamic parameters for the spin-crossover equilibrium and the activation parameters for substitution. The observation of these opposite and compensating effects by modifying the steric hindrance at the ligand illustrates so far unconsidered factors governing the mechanism of oxygen atom transfer leading to high-valent iron oxo species. 相似文献
99.
100.
Hunter CA Jones PS Tiger P Tomas S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(23):5435-5446
Chemical double-mutant cycles have been used to quantify intermolecular functional-group interactions in H-bonded zipper complexes in chloroform. If the same interaction is measured in zippers of different overall stability, the double-mutant cycles can be combined to produce a triple-mutant box. This construct quantifies cooperativity between the functional group interaction of interest and the other interactions that are used to change the overall stability of the complexes. The sum of two edge-to-face aromatic interactions (-2.9 +/- 0.5 kJ mol-1) is shown to be insensitive to changes of up to 13.7 +/- 0.2 kJ mol-1 in the overall stability of the complex. In principle, enthalpic cooperative effects caused by entropy-enthalpy compensation could perturb the measurement of intermolecular interactions when using the double-mutant cycle approach, but these experiments show that, for this system, the magnitude of the effect lies within the error of the measurements. 相似文献