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81.
The nature of the bonding in the above carbonyls was studied using the analysis of domain averaged Fermi holes (DAFH). The results straightforwardly confirm the conclusions of earlier theoretical studies in which the existence of direct metal-metal bond, anticipated for the above carbonyls on the basis of 18-electron rule, was questioned. In addition to indicating the lack of direct metal-metal bond, the DAFH analysis also allowed to characterize the nature of the electron pairs involved in the bonding of the bridging ligands. The analysis has shown that because the number of available electron pairs is not sufficient for the formation of ordinary localized 2c-2e bonds between terminal M(CO)(3) fragments and the bridging ligands, the bonding in both carbonyls exhibits typical features of electron deficiency and one bonding electron pair is effectively involved in multicenter 3c-2e bonding. Because of the symmetry of the complexes the bridging ligands are not distinguishable and all M-C-M bridges have a partial 3c-2e nature via resonance of the localized structures. 相似文献
82.
Antonio C Pinheiro C Chaves MM Ricardo CP Ortuño MF Thomas-Oates J 《Journal of chromatography. A》2008,1187(1-2):111-118
This work reports the development and application of a negative ion mode online LC-ESI-MS method for studying the effect of water deficit on the carbohydrate content of Lupinus albus stems, using a porous graphitic carbon (PGC) stationary phase and an ion trap mass spectrometer. Using this method, separation and detection of several water soluble carbohydrates, ranging from mono-, di-, and oligosaccharides (raffinose, stachyose, and verbascose) to sugar alcohols was achieved in approximately 10 min. This on-line PGC-LC-ESI-MS method shows good linearity with correlation coefficients R(2)>0.99, selectivity, short analysis time, and limits of detection (LOD) ranging from 0.4 to 9 pmol for sugars and 4-20 pmol for sugar alcohols. This PGC-LC-ESI-MS method is sensitive and allowed us to detect even small alterations in carbohydrate levels in L. albus stems that resulted from a mild/early water deficit (nmol g(-1)DW). This paper describes details of our method and its application to the quantitative analysis of water soluble underivatised carbohydrates extracted from L. albus stem tissues that have been subjected to early and severe water deficit conditions, followed by a rewatering period. 相似文献
83.
84.
Kézia Santana de Moura Hugo Rafael Chaves da Silva Leonardo Prezzi Dornelles Luana Cassandra Breitenbach Barroso Coelho Thiago Henrique Napoleão Maria Danielly Lima de Oliveira Patrícia Maria Guedes Paiva 《Applied biochemistry and biotechnology》2016,180(7):1361-1371
Moringa oleifera seeds contain a water-soluble lectin [water-soluble M. oleifera lectin (WSMoL)] that has shown coagulant activity. Magnesium ions are able to interfere with the ability of this lectin to bind carbohydrates. In this study, we performed structural characterization of WSMoL and analyzed its effect on the electrical resistance of a kaolin clay suspension in both presence and absence of monosaccharides (N-acetylglucosamine, glucose, or fructose) and magnesium ions. The coagulant activity of WSMoL was monitored by measuring optical density and electrical resistance over a period of 60 min. Native WSMoL had a molecular mass of 60 kDa and exhibited anionic nature (pI 5.5). In sodium dodecyl sulfate–polyacrylamide gel electrophoresis (SDS-PAGE), it appeared as three polypeptide bands of 30, 20, and 10 kDa. WSMoL reduced the optical density and electrical resistance of the kaolin suspension, which suggests that suspended particles are destabilized and that this is followed by formation of complexes. The coagulant activity of lectin decreased in the presence of Mg2+ ions and carbohydrates at concentrations that also inhibited hemagglutinating activity. This was most likely due to conformational changes in lectin structure. Our findings suggest that the coagulant activity of WSMoL is enhanced by lowering of electrical resistance of the medium and is impaired by lectin–carbohydrate and lectin–Mg2+ interactions. 相似文献
85.
An N‐Acetyl Cysteine Ruthenium Tricarbonyl Conjugate Enables Simultaneous Release of CO and Ablation of Reactive Oxygen Species 下载免费PDF全文
Dr. João D. Seixas Dr. Miguel Chaves‐Ferreira Diana Montes‐Grajales Ana M. Gonçalves Dr. Ana R. Marques Dr. Lígia M. Saraiva Prof. Jesus Olivero‐Verbel Prof. Carlos C. Romão Dr. Gonçalo J. L. Bernardes 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(42):14708-14712
We have designed and synthesised a [Ru(CO)3Cl2(NAC)] pro‐drug that features an N‐acetyl cysteine (NAC) ligand. This NAC carbon monoxide releasing molecule (CORM) conjugate is able to simultaneously release biologically active CO and to ablate the concurrent formation of reactive oxygen species (ROS). Complexes of the general formulae [Ru(CO)3(L)3]2+, including [Ru(CO)3Cl(glycinate)] (CORM‐3), have been shown to produce ROS through a water–gas shift reaction, which contributes significantly, for example, to their antibacterial activity. In contrast, NAC‐CORM conjugates do not produce ROS or possess antibacterial activity. In addition, we demonstrate the synergistic effect of CO and NAC both for the inhibition of nitric oxide (formation) and in the expression of tumour‐necrosis factor (TNF)‐α. This work highlights the advantages of combining a CO‐releasing scaffold with the anti‐oxidant and anti‐inflammatory drug NAC in a unique pro‐drug. 相似文献
86.
Simultaneous Determination of Caffeine,Ibuprofen, and Paracetamol by Flow‐injection Analysis with Multiple‐pulse Amperometric Detection on Boron‐doped Diamond Electrode 下载免费PDF全文
Sandro C. Chaves Priscila N. C. Aguiar Lívia M. F. C. Torres Eric S. Gil Rita C. S. Luz Flávio S. Damos Rodrigo A. A. Munoz Eduardo M. Richter Wallans T. P. dos Santos 《Electroanalysis》2015,27(12):2785-2791
This work presents a simple, fast and low‐cost method for the simultaneous determination of three drugs by flow‐injection analysis with multiple‐pulse amperometric (MPA) detection using a wall‐jet flow cell with a boron‐doped diamond electrode. The amperometric determination of caffeine (CF), ibuprofen (IB) and paracetamol (PC) was performed by the application of a four‐potential waveform using the MPA technique. PC is oxidized at E1 (1.20 V/70 ms) and thus selectively detected; PC and CF are oxidized at E2 (1.49 V/40 ms); PC, CF and IB are oxidized at E3 (1.70 V/70 ms); and E4 (1.80 V/100 ms) is applied for electrode cleaning. The subtraction of currents obtained at the different potentials did not provide accurate determinations of CF and IB, thus it was required to investigate correction factors to determine CF and IB without the interference from PC and CF using the respective amperometric signals obtained at E2 and E3. The proposed method was successfully applied for the determination of three drugs in pharmaceutical samples with low generation of residues and a high analytical frequency (150 h?1) in comparison with HPLC‐DAD method. 相似文献
87.
Simultaneous determination of caffeine,paracetamol, and ibuprofen in pharmaceutical formulations by high‐performance liquid chromatography with UV detection and by capillary electrophoresis with conductivity detection 下载免费PDF全文
Rafael R. Cunha Sandro C. Chaves Michelle M. A. C. Ribeiro Lívia M. F. C. Torres Rodrigo A. A. Muñoz Wallans T. P. Dos Santos Eduardo M. Richter 《Journal of separation science》2015,38(10):1657-1662
Paracetamol, caffeine and ibuprofen are found in over‐the‐counter pharmaceutical formulations. In this work, we propose two new methods for simultaneous determination of paracetamol, caffeine and ibuprofen in pharmaceutical formulations. One method is based on high‐performance liquid chromatography with diode‐array detection and the other on capillary electrophoresis with capacitively coupled contactless conductivity detection. The separation by high‐performance liquid chromatography with diode‐array detection was achieved on a C18 column (250×4.6 mm2, 5 μm) with a gradient mobile phase comprising 20–100% acetonitrile in 40 mmol L?1 phosphate buffer pH 7.0. The separation by capillary electrophoresis with capacitively coupled contactless conductivity detection was achieved on a fused‐silica capillary (40 cm length, 50 μm i.d.) using 10 mmol L?1 3,4‐dimethoxycinnamate and 10 mmol L?1 β‐alanine with pH adjustment to 10.4 with lithium hydroxide as background electrolyte. The determination of all three pharmaceuticals was carried out in 9.6 min by liquid chromatography and in 2.2 min by capillary electrophoresis. Detection limits for caffeine, paracetamol and ibuprofen were 4.4, 0.7, and 3.4 μmol L?1 by liquid chromatography and 39, 32, and 49 μmol L?1 by capillary electrophoresis, respectively. Recovery values for spiked samples were between 92–107% for both proposed methods. 相似文献
88.
89.
Filipe J.P. Chaves M.F.S.F. de Moura L.F.M. da Silva D.A. Dillard 《International Journal of Solids and Structures》2011,48(10):1572-1578
The dual actuator load test was numerically analyzed in order to assess its adequacy for fracture characterization of bonded joints under different mixed-mode loading conditions. This test enables asymmetric loading of double cantilever beam specimens, thus providing a large range of mixed-mode combinations. A new data reduction scheme based on specimen compliance, beam theory and crack equivalent concept was proposed to overcome several difficulties inherent to the test. The method assumes that the dual actuator test can be viewed as a combination of the double cantilever beam and end loaded split tests, which are used for pure modes I and II fracture characterization, respectively. A numerical analysis including a cohesive mixed-mode damage model was performed considering different mixed-mode loading conditions to evaluate the test performance. Some conclusions were drawn about the advantages and drawbacks of the test. 相似文献
90.
The present work demonstrates the successful application of automated biocompatible in-tube solid-phase microextraction coupled with liquid chromatography (in-tube SPME/LC) for determination of interferon alpha(2a) (IFN α(2a)) in plasma samples for therapeutic drug monitoring. A restricted access material (RAM, protein-coated silica) was employed for preparation of a lab-made biocompatible in-tube SPME capillary that enables the direct injection of biological fluids as well as the simultaneous exclusion of macromolecules by chemical diffusion barrier and drug pre-concentration. The in-tube SPME variables, such as sample volume, draw/eject volume, number of draw-eject cycles, and desorption mode were optimized, to improve the sensitivity of the proposed method. The IFN α(2a) analyses in plasma sample were carried out within 25min (sample preparation and LC analyses). The response of the proposed method was linear over a dynamic range, from 0.06 to 3.0MIUmL(-1), with correlation coefficient equal to 0.998. The interday precision of the method presented coefficient of variation lower than 8%. The proposed automated method has adequate analytical sensitivity and selectivity for determination of IFN α(2a) in plasma samples for therapeutic drug monitoring. 相似文献