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131.
Jones Limberger Bárbara C. Leal Adriano L. Monteiro Jairton Dupont 《Chemical science》2015,6(1):77-94
In recent years, charge-tagged ligands (CTLs) have become valuable tools in organometallic catalysis. Insertion of an ionic side chain into the molecular skeleton of a known ligand has become a useful protocol for anchoring ligands, and consequently catalysts, in polar and ionic liquid phases. In addition, the insertion of a cationic moiety into a ligand is a powerful tool that can be used to detect reaction intermediates in organometallic catalysis through electrospray ionisation mass spectrometry (ESI-MS) experiments. The insertion of an ionic tag ensures the charge in the intermediates independently of the ESI-MS. For this reason, these ligands have been used as ionic probes in mechanistic studies for several catalytic reactions. Here, we summarise selected examples on the use of CTLs as immobilising agents in organometallic catalysis and as probes for studying mechanisms through ESI-MS. 相似文献
132.
We study the maximum possible multiplicity of an eigenvalue of a matrix whose graph is a tree, expressing that maximum multiplicity in terms of certain parameters associated with the tree. 相似文献
133.
B García S Ibeas F J Hoyuelos J M Leal F Secco M Venturini 《The Journal of organic chemistry》2001,66(24):7986-7993
The protonation equilibria of N-phenylbenzohydroxamic, benzohydroxamic, salicylhydroxamic, and N-p-tolylcinnamohydroxamic acids have been studied at 25 degrees C in concentrated sulfuric, hydrochloric, and perchloric acid media; the UV-vis spectral measurements were analyzed using the Hammett equation and the Bunnett-Olsen and excess acidity methods. The medium effects observed in the UV spectral curves were corrected with the Cox-Yates and vector analysis methods. The H(A) acidity function based on benzamides provided the best results. The range of variation of the solvation coefficient m is similar to that of amides, this indicating similar solvation requirements for amides and hydroxamic acids. For the same substrate, the observed variations of pK(BH)(+) with the mineral acid used was justified by formation of solvent-separated ion pairs; for the same mineral acid, the observed changes in pK(BH)(+) can be explained by the solvation of BH(+). The change of the pK(BH)(+) values was in reasonably good agreement with the sequence of the catalytic efficiency of the mineral acids used, HCl > H(2)SO(4) > HClO(4). 相似文献
134.
135.
Rodrigo Leal de Paiva Carvalho Ernesto Cesar Pinto Leal‐Junior Maria Carla Petrellis Rodrigo Labat Marcos Maria Helena Catelli de Carvalho Gilberto De Nucci Rodrigo Alvaro Brandão Lopes‐Martins 《Photochemistry and photobiology》2013,89(2):508-512
Muscle injuries represent ca 30% of sports injuries and excessive stretching of muscle causes more than 90% of injuries. Currently the most used treatments are nonsteroidal anti‐inflammatory drugs (NSAIDs), however, in last years, low‐level laser therapy (LLLT) is becoming an interesting therapeutic modality. The aim of this study was to evaluate the effect of single and combined therapies (LLLT, topical application of diclofenac and intramuscular diclofenac) on functional and biochemical aspects in an experimental model of controlled muscle strain in rats. Muscle strain was induced by overloading tibialis anterior muscle of rats. Injured groups received either no treatment, or a single treatment with topical or intramuscular diclofenac (TD and ID), or LLLT (3 J, 810 nm, 100 mW) 1 h after injury. Walking track analysis was the functional outcome and biochemical analyses included mRNA expression of COX‐1 and COX‐2 and blood levels of prostaglandin E2 (PGE2). All treatments significantly decreased COX‐1 and COX‐2 gene expression compared with injury group (P < 0.05). However, LLLT showed better effects than TD and ID regarding PGE2 levels and walking track analysis (P < 0.05). We can conclude that LLLT has more efficacy than topical and intramuscular diclofenac in treatment of muscle strain injury in acute stage. 相似文献
136.
Iaralice Medeiros de Souza Milton Neto da Silva Elza Scott Figueira Maria de Lourdes Leal Ellen Jessouroun Shirley de Mello Pereira Abrantes Ivna Alana Freitas Brasileiro da Silveira 《Electrophoresis》2013,34(22-23):3221-3226
Neisseria meningitidis group C is an encapsulated bacterium that causes several diseases and is associated with high mortality rates, thereby constituting a serious public health problem. Bio‐Manguinhos/Fiocruz is developing a conjugate vaccine by covalent attachment of capsular polysaccharide to hydrazide‐activated tetanus toxoid through reductive amination. It is necessary to quantify free components as a quality control process to prevent exacerbated adverse reactions and/or attenuation of vaccine immunogenicity. Thus, this study aimed to develop and validate a quality control method appropriate for the separation and quantification of free polysaccharide present in this conjugate N. meningitidis group C vaccine using CE. CZE was used to remove unbound polysaccharide, and the electrophoretic conditions were varied to optimize resolution. We were able to develop and validate the proposed method, which was linear and showed a matrix effect. Repeatability and partial reproducibility of the method were also evaluated. The robustness results showed that control of temperature is required for reliable results. The validated method will be used to evaluate the conjugate batches submitted for Phase III clinical studies and for routine quality control of the conjugate vaccine. 相似文献
137.
In this work we attempt to determine the origin of damped stress oscillations upon flow start-up of a nematic liquid crystalline
monodomain. These damped stress oscillations were first observed by Gu et al. (1993) in the cone-plate flow cell and have
since also been observed by Mather et al. (1997) in the parallel disk cell. Although Mather's work explained the cause of
the stress oscillation damping in the torsional flow cell, the origin of the damping in the cone-plate device remains a mystery.
Here we report finding similar damped stress oscillations in the cylindrical Couette cell and combined with the optical experiments
reported earlier by Cladis and Torza (1975, 1976) we are able to propose an explanation for the damping in this geometry.
We also report new optical experiments using the cone-plate cell in hopes of determining a cause to the damping in the cone-plate
cell.
Received: 11 August 2000 Accepted: 31 October 2000 相似文献
138.
139.
Fernando Antonio Simas Vaz Arthur Damásio Moutinho Jose Paulo Rodrigues Furtado de Mendonça Ricardo Tavares de Araújo Sidney José Lima Ribeiro Ferminio César Polachini Younes Messaddeq Marcone Augusto Leal de Oliveira 《Microchemical Journal》2012
The preparation of photo-polymerized sol–gel monolithic stationary phases (MSP) within 100 μm internal diameter polyacrylate-coated fused-silica capillaries for use in capillary electrochromatography (CEC) was optimized. Eight mixtures containing different amounts of methacryloxypropyltrimethoxysilane (MPTMS) as the polymeric precursor, hydrochloric acid solution as the catalyst, toluene as the porogen and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819) as the photo-initiator were irradiated at 370 nm inside the capillaries in order to complete the MSP polymerization, according to a fractional factorial experimental design 2IV4-1. All the preparation procedure, from capillary pretreatment until the MSP is ready to use in CEC, were made in less than four hours in mild conditions. A high pressurization injection device (HPID) useful for micro-volume syringes was built in order to achieve practical, controlled and precise injections of sols, solvents and electrolytes in the capillaries. The eight MSP were equally washed, conditioned and submitted to CEC procedures via short-end injection, which showed higher efficiency and peak height taking shorter analysis time. Electrochromatographic behaviors of the MSP were corroborated with morphological characterizations by scanning electron microscopy. The optimum condition, which allowed the separation of standard mixture containing thiourea (marker compound), naphthalene, acenaphthene, fluorene, phenanthrene and anthracene in twelve minutes without external pressure assistance, showed efficiencies up to 51,460 N/m, relative standard deviation from 0.05 to 3.3% for migration/retention time and from 0.14 to 1.6% for relative area (considering thiourea as an internal standard) and also showed no statistical evidence that three MSP prepared at the same condition are different within 95% confidence interval. 相似文献