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71.
Silva R Boldt S Costa VM Carmo H Carvalho M Carvalho F Bastos Mde L Lemos-Amado F Remião F 《Biomedical chromatography : BMC》2007,21(7):670-679
The sustained high release of catecholamines to circulation is a deleterious condition that may induce toxicity, which seems to be partially related to the products formed by oxidation of catecholamines that can be further conjugated with glutathione (GSH). The aim of the present study was to develop a method for the determination of GSH adducts of adrenaline in biological samples. Two position isomers of the glutathion-S-yl-adrenaline were synthesized and characterized by HPLC using diode array, coulometric and mass detectors. A method for the extraction of these adducts from human plasma was also developed, based on adsorption to activated alumina, which showed adequate recoveries and proved to be crucial in removing interferences from plasma. The selectivity, precision and linearity of the method were all within the accepted values for these parameters. Furthermore, the sensitivity of this method allows the detection of adduct amounts that are within the range of the expected concentrations for these adducts under certain pathophysiological conditions and/or drug treatments. In conclusion, the development of this method allows the direct analysis of GSH adducts of adrenaline in human plasma, providing a valuable tool for the study of the catecholamine oxidation process and its related toxicity. 相似文献
72.
Preparation of Tetramethylammonium Azidosulfite and Tetramethylammonium Cyanate Sulfur Dioxide‐Adduct, [(CH3)4N]+[SO2N3]–, [(CH3)4N]+[SO2OCN]– and Crystal Structure of [(CH3)4N]+[SO2N3]– Tetramethylammonium azide forms with sulfur dioxide an azidosulfite salt. It is characterized by NMR and vibrational spectroscopy and the crystal structure analysis. [(CH3)4N]+[SO2N3]– crystallizes in the monoclinic space group P21/c with a = 551.3(1) pm, b = 1095.2(1) pm, c = 1465.0(1) pm, β = 100.63(1)°, and four formula units in the unit cell. The crystal structure possesses a strong S–N interaction between the N3– anions and the SO2 molecules. The S–N distance of 200.5(2) pm is longer than a covalent single S–N bond. The structure is compared with ab initio calculated data. Furthermore an adduct of tetrametylammonium cyanate and sulfur dioxide is reported. It is characterised by NMR and vibrational spectroscopy. The structure is calculated by ab initio methods. 相似文献
73.
Two Tetrachlorothiotantalates: [Na‐15‐crown‐5][TaSCl4 · dioxane] and [Na‐15‐crown‐5]2[(TaSCl4)2dioxane] · S8 During the reaction of Na2S4, TaCl5 and 15‐crown‐5 in dichloromethane the crown ether partly suffers degradation to 1,4‐dioxane. Aside from sulfur, [Na‐15‐crown‐5][TaSCl4 · dioxane] was the first product obtained. It crystallizes in the monoclinic space group P21/n with a = 1066.1, b = 1781.3, c = 1258.3 pm, β = 97.14°, Z = 4. In the [TaSCl4 · dioxane]– ion a dioxane molecule is loosely bonded to a square‐pyramidal TaSCl4– unit; two chlorine atoms are in contact with an Na+ ion. Upon standing with the mother liquor [Na‐15‐crown‐5]2[(TaSCl4)2dioxane] · S8 was formed. It crystallizes in the monoclinic space group C2/m; a = 1768.5, b = 1084.0, c = 1517.3 pm, β = 118.46°, Z = 4. In this case a dioxane molecule is coordinated with two TaSCl4– units. The [(TaSCl4)2 · dioxane]2– ions and S8 molecules alternate in the stacking direction b. 相似文献
74.
Bovine serum albumin (BSA)–squaraine supramolecular adducts with aggregation‐induced emission (AIE) properties were prepared and characterized by spectroscopic methods. While squaraine dyes showed a very low fluorescence quantum yield in water, a great enhancement in the fluorescence of the aggregated BSA adducts was achieved due to the abnormal aggregation‐induced emission properties of squaraines. The adducts formation was studied from a kinetic point of view showing unexpected structure–properties relationships. 相似文献
75.
The first example of tandem oxidation and 1,2-acetoxysulfenylation/1,2-disulfenylation of Baylis-Hillman (BH) alcohols to afford 1,2-acetoxysulfides/1,2-dithioethers is reported. The reaction involves oxidation of BH alcohols with IBX in [bmim]Br to give β-ketomethylene compounds in situ followed by CuI-imidazole-catalyzed 1,2-acetoxysulfenylation with an organodisulfide and acetic acid under air to afford vicinal acetoxysulfides in excellent yields with complete regioselectivity. In the absence of the Cu(I) catalyst, 1,2-disulfenylation takes place to give vicinal dithioethers in 81-90% yields. 相似文献
76.
Hyun Seung Lee 《Tetrahedron letters》2009,50(47):6480-6483
The reaction of Baylis-Hillman acetates and ethyl mercaptoacetate in the presence of DBU in DMF produced 2,3,4-trisubstituted tetrahydrothiophenes at room temperature as a diastereomeric mixture via the sequential SN2′ and Michael addition. Aromatization of tetrahydrothiophenes by DDQ oxidation produced 2,3,4-trisubstituted thiophenes in good yields. 相似文献
77.
The first example of one-pot oxidative anti-Markownikov bromohydroxylation and bromoalkoxylation of Baylis-Hillman (BH) adducts (olefins) is reported. The reaction is performed at rt using LiBr as the bromine source and 2-iodoxybenzoic acid (IBX) as the oxidant. The process involves oxidation of BH adducts with IBX to give β-ketomethylene compounds in situ, which undergo highly regioselective vicinal functionalization with LiBr/H2O or LiBr/ROH in the same vessel to afford α-bromo-β-hydroxy or α-bromo-β-alkoxy compounds, respectively, in excellent yields. The α-bromo-β-hydroxy compounds are readily transformed into epoxides in aq NaOH. 相似文献
78.
E. Balaraman 《Tetrahedron》2009,65(36):7603-5326
A simple transition metal-free hydro/hydrothiophosphonylation of Baylis-Hillman adducts, substituted allyl bromides, allenylphosphonates and alkynes, promoted by fluoride ion in ionic liquid, is described. Clear-cut evidence for fluoride activation of the phosphite via pentacoordinate phosphorus is provided for the first time. Also, in a comparative reaction, the product obtained was different from that from the palladium catalyzed one. Structures of key products are proven by X-ray crystallography. 相似文献
79.
80.
Barbara Chiavarino Dr. Maria Elisa Crestoni Prof. Simonetta Fornarini Prof. Francesco Lanucara Dr. Joel Lemaire Dr. Philippe Maître Prof. Debora Scuderi Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(33):8185-8195
Anion–π interactions between a π‐acidic aromatic system and an anion are gaining increasing recognition in chemistry and biology. Herein, the binding features of an electron‐deficient aromatic system (1,3,5‐trinitrobenzene (TNB)) and selected anions (OH?, Br?, and I?) are examined in the gas phase by using the combined information derived from collision‐induced dissociation experiments at variable energy, infrared multiple‐photon dissociation spectroscopy, and quantum chemical calculations. We provide spectroscopic evidence for two different structural motifs of anion–arene complexes depending on the nature of the anion. The TNB–OR? complexes (R=H, or alkyl groups which were studied earlier) adopt an anionic σ‐complex structure whereby RO? attacks the aromatic ring with covalent bond formation, and develops a tetrahedral ring carbon bound to H and OR. The halide complexes rather conform to a structure in which the TNB moiety is hardly altered, and the halogen is placed on an unsubstituted carbon atom over the periphery of the ring at a C–X distance that is appreciably longer than a typical covalent bond length. The ensuing structural motif, previously characterized in the solid state and named weak σ interaction, is now confirmed by an IR spectroscopic assay in the gas phase, in which the sampled species are unperturbed by crystal packing or solvation effects. 相似文献