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91.
Aitor Carretero Zacarías León Juan Carlos García-Cañaveras Ángela Zaragoza María José Gómez-Lechón María Teresa Donato Agustín Lahoz 《Analytical and bioanalytical chemistry》2014,406(22):5465-5476
Multiple analytical methods are required to comprehensively assess oxidative homeostasis and specific damage to macromolecules. Our aim was to develop a straightforward strategy for the fast assessment of global oxidative status and specific damage to DNA, proteins, and lipids. To this end, an analytical method, based on ultra-performance liquid chromatography coupled to mass spectrometry (UPLC-MS/MS), was developed and validated for the quantification of 16 oxidative stress (OS) biomarkers. Some of these markers were unstable; thus, an easy sample treatment procedure, including fractionation and derivatization, was set up. The method was validated according to Food and Drug Administration (FDA) guidelines, and it provided good results in terms of intra- and inter-day precision (≤17.2 and 16 %, respectively), accuracy (relative error measurement between ?16.6 and 19.8 %), and linearity (R 2?>?0.994). The approach was applied to determine the oxidative insult provoked to cultured rat hepatocytes by cumene hydroperoxide and to analyze the liver and serum samples from patients diagnosed with nonalcoholic steatohepatitis. In both studies, significant differences were found if compared to the corresponding control groups; interestingly, ophthalmic acid was shown as an OS biomarker in both models for the first time. A key advantage of the novel approach in comparison with former multi-method approaches is that now a single method is applied to assess the 16 OS biomarkers. Its comprehensive capacity to profile oxidative homeostasis and damage in both in vitro and clinical samples has been illustrated, which indicates that the proposed approach is a good choice to evaluate whether OS is involved in physiological signals, diseases, or toxic events and to what extent. 相似文献
92.
Tejel C Ciriano MA Ríos-Moreno G Dobrinovitch IT Lahoz FJ Oro LA Parra-Hake M 《Inorganic chemistry》2004,43(15):4719-4726
Reaction of [[Rh(mu-Cl)(CO)2]2] with the triazene ArNNNHAr (Ar = o-CO2MeC6H4) produced the mononuclear complex [RhCl(ArNNNHAr)(CO)2] (1). Complex 1 reacted with KOH in methanol to give the dinuclear compound [[Rh(mu-ArNNNAr)(CO)2]2] (2), which showed a "mu-(1kappaN1,2kappaN3)-ArNNNAr" coordination mode for both bridging ligands. The dinuclear complex [[Rh(mu-ArNNNAr)(CO)2]2] (2) easily undergoes redistribution reactions in which the eight-membered "Rh2(NNN)2" core is broken. Thus, reaction of 2 with the anionic complex (NHEt3)[RhCl2(CO)2] gave the single-bridged complex (NHEt3)[Rh2(mu-ArNNNAr)Cl2(CO)4] (4), while the trinuclear complexes [Rh3(mu-ArNNNAr)(mu-Cl)(mu-CO)Cl(CO)4] (5) and [Rh3(mu-ArNNNAr)2(mu-Cl)(mu-CO)(CO)3] (6) were isolated by addition of the neutral compound [[Rh(mu-Cl)(CO)2]2] to 2, depending on the molar ratio employed. The formation of 5 and 6 involved the loss of carbonyl groups and the coordination of the oxygen atoms of the CO2Me groups. The structures of 4, 5, and 6 have been determined by X-ray diffraction methods, which show the ability of bis(o-carboxymethylphenyl)triazenide to act as bi-, tri-, and tetra-dentate ligand-spanning dinuclear moieties in trinuclear complexes. 相似文献
93.
In previous work, (E)-2-enynyl pyridines were reported to yield indolizinyl singlet carbenes through base-catalyzed E/Z isomerization followed by a 5-exo-dig pseudocoarctate cyclization. We report herein that in the presence of ethyl acrylate these carbenes undergo stereoselective cis-cyclopropanation due mainly to electrostatic interactions in the transition state. The scope of this carbene generation scheme has been further explored through the preparation of a symmetric bis(pyridylenyl)alkyne which spontaneously furnished the biindolizine core in a one-pot reaction. Computational characterization of this transformation suggests a highly asynchronous double cyclization. 相似文献
94.
Determination of free serotonin and its metabolite 5‐HIAA in blood human samples with consideration to pre‐analytical factors 下载免费PDF全文
Samanta Yubero‐Lahoz Joan Rodríguez Anna Faura Julio Pascual Anna Oliveras Higini Cao Magí Farré Rafael de la Torre 《Biomedical chromatography : BMC》2014,28(12):1641-1646
Significant differences have been reported over the years in measuring physiological levels of free circulating serotonin (f5‐HT) in platelet‐poor plasma (PPP). This work shows that there are crucial pre‐analytical factors in sample manipulation that can provoke an artifactual release of 5‐HT from platelets, and that, even when the sample is accurately processed to obtain PPP, f5‐HT levels are approximately 2.8 times higher than those of f5‐HT in blood. An alternative methodology consisting of ex vivo blood microdialysis coupled to high‐performance liquid chromatography–electrochemical detection is proposed and validated. It is considered the most accurate technique to measure physiological circulating f5‐HT and its metabolite 5‐hydroxyindoleacetic acid (f5‐HIAA), owing to its sensitivity (limits of quantification of 0.08 ng/mL) and reliability since there is no sample manipulation. The f5‐HT and f5‐HIAA levels in blood and in PPP were studied in control subjects, hypertensive and end‐stage renal disease patients, who have a deregulated serotonergic system. This work reveals that blood is the best matrix to determine f5‐HT concentrations, and the clinical relevance of the accuracy of f5‐HT determination is discussed. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
95.
Dr. Karin Garcés Dr. Ralte Lalrempuia Dr. Víctor Polo Dr. Francisco J. Fernández‐Alvarez Dr. Pilar García‐Orduña Prof. Fernando J. Lahoz Prof. Jesús J. Pérez‐Torrente Prof. Luis A. Oro 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(41):14717-14729
A series of rhodium–NSiN complexes (NSiN=bis (pyridine‐2‐yloxy)methylsilyl fac‐coordinated) is reported, including the solid‐state structures of [Rh(H)(Cl)(NSiN)(PCy3)] (Cy=cyclohexane) and [Rh(H)(CF3SO3)(NSiN)(coe)] (coe=cis‐cyclooctene). The [Rh(H)(CF3SO3)(NSiN)(coe)]‐catalyzed reaction of acetophenone with silanes performed in an open system was studied. Interestingly, in most of the cases the formation of the corresponding silyl enol ether as major reaction product was observed. However, when the catalytic reactions were performed in closed systems, formation of the corresponding silyl ether was favored. Moreover, theoretical calculations on the reaction of [Rh(H)(CF3SO3)(NSiN)(coe)] with HSiMe3 and acetophenone showed that formation of the silyl enol ether is kinetically favored, while the silyl ether is the thermodynamic product. The dehydrogenative silylation entails heterolytic cleavage of the Si?H bond by a metal–ligand cooperative mechanism as the rate‐determining step. Silyl transfer from a coordinated trimethylsilyltriflate molecule to the acetophenone followed by proton transfer from the activated acetophenone to the hydride ligand results in the formation of H2 and the corresponding silyl enol ether. 相似文献
96.
Dipl.‐Chem. Inmaculada Mena Dr. Miguel A. Casado Dr. Víctor Polo Dr. Pilar García‐Orduña Prof. Fernando J. Lahoz Prof. Luis A. Oro 《Angewandte Chemie (International ed. in English)》2014,53(36):9627-9631
In the presence of phosphanes (PR3), the amido‐bridged trinuclear complex [{Ir(μ‐NH2)(tfbb)}3] (tfbb=tetrafluorobenzobarrelene) transforms into mononuclear discrete compounds [Ir(1,2‐η2‐4‐κ‐C12H8F4N)(PR3)3], which are the products of the C? N coupling between the amido moiety and a vinylic carbon of the diolefin. An alternative synthetic approach to these species involves the reaction of the 18 e? complex [Ir(Cl)(tfbb)(PMePh2)2] with gaseous ammonia and additional phosphane. DFT studies show that both transformations occur through nucleophilic attack. In the first case the amido moiety attacks a diolefin coordinated to a neighboring molecule following a bimolecular mechanism induced by the highly basic NH2 moiety; the second pathway involves a direct nucleophilic attack of ammonia to a coordinated tfbb molecule. 相似文献
97.
This article reports the transformation of O-acetylisophotosantonin, obtained by photochemical rearrangement of santonin, into plagiochiline N, an ent-2,3-secoaromadendrane isolated from Plagiochila ovalifolia. The synthesis was carried out in a sequence involving as the key steps (a) the substitution of the lactone moiety by a gem-dimethylcyclopropane ring through a synthetic intermediate having a C(6)-C(7) double bond and (b) the ozonolysis of the C(2)-C(3) bond followed by cyclization to the dihydropyran ring characteristic of plagiochiline N. Spectroscopic data of the synthetic product fully coincided with the reported data for the natural product. 相似文献
98.
P. Haro-González F. Lahoz J. González-Platas J.M. Cáceres S. González-Pérez D. Marrero-López N. Capuj I.R. Martín 《Journal of luminescence》2008,128(5-6):908-910
Measurements of the optical properties of Er3+ ions in strontium barium niobate glass and glass ceramics have been carried out. The glasses have been fabricated using a melt-quenching method, and the glass ceramic samples have been obtained from the glass precursor by a thermal treatment. The ceramic samples formed by a glassy phase, and a crystalline phase contains nanocrystals of Sr1?xBaxNb2O6 (SBN) doped with Er3+ ions with a mean size of ~50 nm, as confirmed with XRD. Green up-conversion emission has been obtained under excitation at 800 nm, and the temporal evolution of this emission has been reported with the purpose of determining the involved up-conversion mechanism. These optical measures have confirmed that the Er3+ ions have been incorporated into the SBN matrix, after a thermal treatment, which produced an increment of the up-conversion efficiency. 相似文献
99.
100.
Inmaculada R. Lahoz Dr. Armando Navarro‐Vázquez Dr. Antonio L. Llamas‐Saiz Dr. José Lorenzo Alonso‐Gómez Prof. M. Magdalena Cid 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(43):13836-13843
New 2,6‐disubstituted pyrido‐allenophanes with locked rotation of aromatic spacers were designed and synthesized. The synthesis was accomplished by Pd‐catalyzed C(sp2)–C(sp) Sonogashira cross‐coupling reaction between 1,3‐diethynylallene (DEA) and 2,6‐dibromopyridine followed by an intermolecular ring closure. Because racemic DEA was employed, pyrido‐allenophanes were obtained as mixtures of stereoisomers that were resolved by preparative HPLC. The conformational space of all these diastereoisomers was explored at the CAM‐B3LYP/6‐31+G*//AM1 level of theory. The isomers were characterized through their symmetry properties revealed in NMR, circular dichroism, and chiral stationary‐phase HPLC experiments. X‐ray diffraction was used to assign and to corroborate the configuration of several diastereoisomers. The unexpected encapsulation of two molecules of CHCl3 in the crystal structures shows the potential of these conformationally hampered allenophanes as encapsulating hosts. 相似文献