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121.
Elettra L. Piacentino Edwin Rodriguez Kevin Parker Thomas M. Gilbert Richard A. J. O'Hair Victor Ryzhov 《Journal of mass spectrometry : JMS》2019,54(6):520-526
Gas‐phase C―C coupling reactions mediated by Ni (II) complexes were studied using a linear quadrupole ion trap mass spectrometer. Ternary nickel cationic carboxylate complexes, [(phen)Ni (OOCR1)]+ (where phen = 1,10‐phenanthroline), were formed by electrospray ionization. Upon collision‐induced dissociation (CID), they extrude CO2 forming the organometallic cation [(phen)Ni(R1)]+, which undergoes gas‐phase ion‐molecule reactions (IMR) with acetate esters CH3COOR2 to yield the acetate complex [(phen)Ni (OOCCH3)]+ and a C―C coupling product R1‐R2. These Ni(II)/phenanthroline‐mediated coupling reactions can be performed with a variety of carbon substituents R1 and R2 (sp3, sp2, or aromatic), some of them functionalized. Reaction rates do not seem to be strongly dependent on the nature of the substituents, as sp3‐sp3 or sp2‐sp2 coupling reactions proceed rapidly. Experimental results are supported by density functional theory calculations, which provide insights into the energetics associated with the C―C bond coupling step. 相似文献
122.
Leandro Marcondes-Alves Victor Fattori Sergio M. Borghi Yuri Lourenco-Gonzalez Allan J.C. Bussmann Elisa Y. Hirooka 《Natural product research》2019,33(6):921-924
Acetaminophen (paracetamol) is a widely used analgesic and antipyretic drug that is safe at therapeutic doses. However, acetaminophen overdose can be fatal. Currently, the only treatment available is the N-acetyl cysteine. The diterpene kaurenoic acid (ent-kaur-16-en-19-oic acid, KA) is the major constituent of Sphagneticola trilobata (L.) Pruski. KA presents anti-inflammatory, anti-nociceptive and antioxidant properties. In this study, we evaluated the efficacy of KA in a model of acetaminophen-induced hepatotoxicity. KA increased, in a dose-dependent manner, the survival rate after acetaminophen overdose. KA reduced acetaminophen-induced hepatic necrosis and ALT and AST levels. KA decreased acetaminophen-induced neutrophil and macrophage recruitment, oxidative stress and the production of IL-33, TNF-α and IL-1β, alongside with normalisation of IL-10 levels in the liver. Therefore, KA showed preclinical efficacy in acetaminophen-induced hepatotoxicity and lethality. 相似文献
123.
Tatiana Monaretto Andre Souza Tiago Bueno Moraes Victor Bertucci-Neto Corinne Rondeau-Mouro Luiz Alberto Colnago 《Magnetic resonance in chemistry : MRC》2019,57(9):616-625
The traditional way to enhance signal-to-noise ratio (SNR) of nuclear magnetic resonance (NMR) signals is to increase the number of scans. However, this procedure increases the measuring time that can be prohibitive for some applications. Therefore, we have tested the use of several post-acquisition digital filters to enhance SNR up to one order of magnitude in time domain NMR (TD-NMR) relaxation measurements. The procedures were studied using continuous wave free precession (CWFP-T1) signals, acquired with very low flip angles that contain six times more noise than the Carr–Purcell–Meiboom–Gill (CPMG) signal of the same sample and experimental time. Linear (LI) and logarithmic (LO) data compression, low-pass infinity impulse response (LP), Savitzky–Golay (SG), and wavelet transform (WA) post-acquisition filters enhanced the SNR of the CWFP-T1 signals by at least six times. The best filters were LO, SG, and WA that have high enhancement in SNR without significant distortions in the ILT relaxation distribution data. Therefore, it was demonstrated that these post-acquisition digital filters could be a useful way to denoise CWFP-T1, as well as CPMG noisy signals, and consequently reducing the experimental time. It was also demonstrated that filtered CWFP-T1 method has the potential to be a rapid and nondestructive method to measure fat content in beef and certainly in other meat samples. 相似文献
124.
Herbert Barthel Michael Dreyer Torsten Gottschalk-Gaudig Victor Litvinov Ekaterina Nikitina 《Macromolecular Symposia》2002,187(1):573-584
Fumed silica, a synthetic silicon dioxide, is a powerful rheological additive for resins and paints to introduce thixotropy or even a yield point. The rheological effectiveness of fumed silica is based on its ability to form percolating networks which immobilize large volumes of liquid. By a combination of advanced rheological experiments, spectroscopical investigations, and quantum chemical calculations it could be demonstrated that the formation and stability of the silica network is strongly influenced by particle-resin interactions. The results can be used to develop comprehensive models, which explain the rheological performance of different grades of fumed silica in different resins. 相似文献
125.
Gold electrodes were chemically modified with thioctic acid monolayer designed to mimic biological ion-channel membranes. The technique was then used in the determination of alkali, alkaline earth, thallium(I), and lanthanum metal cations as analytes. Cyclic voltammograms (CV) of [Fe(CN)6]3− an electroactive marker, were measured in the presence of the various types of analyte cations. In the absence of the analyte cation, electrostatic repulsion between the marker anions and the carboxylate groups of the receptor monolayer hindered the approach of the marker anion to the electrode surface and hence hindered its reduction. The modified electrodes responded well to the metal cations except the alkali metal cations. The sensors could detect the trivalent cation La3+ at concentrations as low as 10−8 M. The response of the sensor to the metal cations increase in the order alkali metal3+ can be discriminated in the ratio 1:100. This makes it possible to determine the trivalent ion in a sample matrix containing monovalent and divalent cations. Thallium(I) ion showed marked deviation in its response as compared to monovalent ions of the alkali metals. The ion-channel sensor based on self-assembled monolayer of thioctic acid therefore offers a potential alternative technique for the selective determination of metal ions. 相似文献
126.
Wouters J Oudjama Y Ghosh S Stalon V Droogmans L Oldfield E 《Journal of the American Chemical Society》2003,125(11):3198-3199
We have obtained the three-dimensional X-ray crystallographic structure of a C67A mutant Escherichia coli isopentenylpyrophosphate-dimethylallylpyrophosphate isomerase (EC 5.3.3.2) complexed with the bromohydrin of isopentenylpyrophosphate, at 1.93 A resolution. The overall backbone fold is very similar to that obtained previously for the wild-type enzyme in the presence of a divalent metal cation (Mn2+ or Mg2+). However, in the new structure, there are two metal binding sites, not just one. The first metal binding site is occupied by Mn2+, coordinated to three histidine and two glutamate residues, while the second is occupied by Mg2+, coordinated to two bromohydrin-ligand phosphate oxygens, the carbonyl oxygen of A67, a carboxyl oxygen of E87, and two water molecules. The C3 hydroxyl group of the bromohydrin inhibitor is involved in a short hydrogen bond to the carboxyl group of E116, one of the two Mn-bound glutamates. The structure obtained is consistent with a mechanism of action of the enzyme in which the carboxyl group of E116 protonates the double bond in isopentenylpyrophosphate, forming a carbocation, followed by removal of a C2 proton by the thiolate of C67, in the wild-type enzyme. The inhibition of the enzyme by a wide variety of other potent inhibitors is also readily explained on the basis of the bromohydrin inhibitor structure. 相似文献
127.
Victor Adebomi Ryan D. Cohen Rachel Wills Holland Andrew Hays Chavers Gary E. Martin Monika Raj 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(52):19249-19256
Here, we report a novel “CyClick” strategy for the macrocyclization of peptides that works in an exclusively intramolecular fashion thereby precluding the formation of dimers and oligomers via intermolecular reactions. The CyClick chemistry is highly chemoselective for the N‐terminus of the peptide with a C‐terminal aldehyde. In this protocol, the peptide conformation internally directs activation of the backbone amide bond and thereby facilitates formation of a stable 4‐imidazolidinone‐fused cyclic peptide with high diastereoselectivity (>99 %). This method is tolerant to a variety of peptide aldehydes and has been applied for the synthesis of 12‐ to 23‐membered rings with varying amino acid compositions in one pot under mild reaction conditions. The reaction generated peptide macrocycles featuring a 4‐imidazolidinone in their scaffolds, which acts as an endocyclic control element that promotes intramolecular hydrogen bonding and leads to macrocycles with conformationally rigid turn structures. 相似文献
128.
Dr. Dmitry B. Eremin Ekaterina A. Denisova Dr. Alexander Yu. Kostyukovich Dr. Jonathan Martens Dr. Giel Berden Prof. Dr. Jos Oomens Prof. Dr. Victor N. Khrustalev Prof. Dr. Victor M. Chernyshev Prof. Dr. Valentine P. Ananikov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(72):16564-16572
N-Heterocyclic carbene (NHC) ligands are ubiquitously utilized in catalysis. A common catalyst design model assumes strong M–NHC binding in this metal–ligand framework. In contrast to this common assumption, we demonstrate here that lability and controlled cleavage of the M−NHC bond (rather than its stabilization) could be more important for high-performance catalysis at low catalyst concentrations. The present study reveals a dynamic stabilization mechanism with labile metal–NHC binding and [PdX3]−[NHC-R]+ ion pair formation. Access to reactive anionic palladium intermediates formed by dissociation of the NHC ligands and plausible stabilization of the molecular catalyst in solution by interaction with the [NHC-R]+ azolium ion is of particular importance for an efficient and recyclable catalyst. These ionic Pd/NHC complexes allowed for the first time the recycling of the complex in a well-defined form with isolation at each cycle. Computational investigation of the reaction mechanism confirms a facile formation of NHC-free anionic Pd in polar media through either Ph–NHC coupling or reversible H–NHC coupling. The present study formulates novel ideas for M/NHC catalyst design. 相似文献
129.
Grigor’ev Arthur A. Kayukov Yakov S. Nikiforova Anastasiya L. Karpov Sergey V. Shchegravina Ekaterina S. Kayukova Olga V. Tafeenko Victor A. 《Chemistry of Heterocyclic Compounds》2019,55(2):167-171
Chemistry of Heterocyclic Compounds - 4-Acyl-2-amino-6-chloropyridine-3,5-dicarbonitriles underwent heterocyclization in the presence of ammonia in aqueous dioxane medium, involving the... 相似文献
130.
Menger FM Zhang H Caran KL Seredyuk VA Apkarian RP 《Journal of the American Chemical Society》2002,124(7):1140-1141
A gemini surfactant is able to promote columnar jointing in vitreous ice where long pillars, often of hexagonal cross section, are formed. This jointing is visible by cryo-high-resolution scanning electron microscopy (cryo-HRSEM), in which colloidal suspensions in bulk water are cooled rapidly in liquid ethane, thereby avoiding the potential artifacts with other types of EM. The jointing is proposed to arise from a new type of colloidal morphology where the surfactant self-assembles into hexagonal columns. Evidence for this mechanism comes from a cryo-HRSEM photo of an ice-free hexagonal "skeleton" composed of surfactant. Cryo-HRSEM, a method that is just beginning to realize its potential, would seem to have a promising future in the discovery of additional and as yet unimagined colloidal structures. 相似文献