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11.
Dai QH Tommos C Fuentes EJ Blomberg MR Dutton PL Wand AJ 《Journal of the American Chemical Society》2002,124(37):10952-10953
The use of side chains as catalytic cofactors for protein mediated redox chemistry raises significant mechanistic issues as to how these amino acids are activated toward radical chemistry in a controlled manner. De novo protein design has been used to examine the structural basis for the creation and maintenance of a tryptophanyl radical in a three-helix bundle protein maquette. Here we report the detailed structural analysis of the protein by multidimensional NMR methods. An interesting feature of the structure is an apparent pi-cation interaction involving the sole tryptophan and a lysine side chain. Hybrid density functional calculations support the notion that this interaction raises the reduction potential of the W degrees /WH redox pair and helps explain the redox characteristics of the protein. This model protein system therefore provides a powerful model for exploring the structural basis for controlled radical chemistry in protein. 相似文献
12.
Silvia E. Asías Ana M. Bruno Diego A. Dominici Mariela Bollini Carlos H. Gaozza 《Journal of heterocyclic chemistry》2003,40(1):107-112
In order to find new antimalarial drugs, an exploration about the chemical properties of the starting compounds 3‐amino‐6‐chloro‐4‐phenyl‐1H‐quinolin‐2‐one ( 1 ) and 3‐amino‐4‐methyl‐1H‐quinolin‐2‐one ( 2 ) was developed. Acylation with acyl chloride, sulfonyl chloride and acetic anhydride were carried out. Despite a previous report [2], when acetyl chloride or acetic anhydride were assayed on 1 , only the diacetyl derivative 7 was obtained. When this compound was heated at reflux temperature in a mixture of acetic acid and acetic anhydride, it was transformed in the oxazoloquinoline 8 . Further reactions of the acyl derivatives with diazomethane afforded 1‐methylated compounds. Compound 2 gave the imine 16 by condensation with 4‐nitrobenzaldehyde. 相似文献
13.
Carmona AT Fuentes J Robina I García ER Demange R Vogel P Winters AL 《The Journal of organic chemistry》2003,68(10):3874-3883
A new route for the preparation of four new indolizidines, (1R,2S,6S,7S,8aS)- and (1R,2S,6R,7R,8aS)-1,2,6,7-tetrahydroxyindolizidine (30 and 32) and (1S,2R,7S,8S,8aR)- and (1S,2R,7R,8R,8aR)-1,2,7,8-tetrahydroxyindolizidine (44 and 46), is reported. The synthesis is based on Knoevenagel homologation of the readily available enantiomerically pure pyrrolidin-carbaldehydes 13 and 37followed by asymmetric dihydroxylation of the subsequent alkenyl pyrrolidines and cyclization of the corresponding imino-octitols. The new indolizidines and their precursors (imino-octitols 20, 25, 26) and indolizidinones 28a and 28b have been tested for inhibitory activities toward 26 glycosidases. The enzymatic inhibition of trans-7-hydroxy-d-(-)-swainsonine (44) toward alpha-mannosidases is similar to that described for trans-7-hydroxy-l-(+)-swainsonine (11b) toward naringinase (alpha-l-rhamnosidase from Penicillium decumbens). 相似文献
14.
This stability of Sb(III) and Sb(V) species was studied during single extraction from soils by water. EDTA, diluted H2SO4 and H3PO4, and oxalic acid/oxalate solutions, with and without ascorbic acid, were used as stabilizing reagent of both Sb species. Antimony redox speciation in soil extracts was performed by selective hydride generation-atomic fluorescence spectrometry. Simulated extraction procedures (without soil) showed that, except in oxalate medium, Sb(III) was oxidized to Sb(V), and this reaction was avoided with ascorbic acid. Recovery studies from a spiked agricultural soil showed that no oxidation but sorption of Sb(III) occurred during the extraction process in water and H2SO4 medium, and quantitative oxidation in EDTA and oxalate medium. With ascorbic acid, this oxidation was totally avoided in EDTA and partially avoided in oxalate solution. A new sequential extraction procedure was proposed and applied to the fractionation and redox speciation of antimony in agricultural soils, using EDTA + ascorbic acid, pH 7 (available under complexing and moderately reducible conditions); oxalic acid/oxalate + ascorbic acid (extractable in reducible conditions) and HNO3 + HCl + HF (residual fraction). The proposed extraction scheme can provide information about the availability and mobility of antimony redox species in agricultural soils. 相似文献
15.
Inés Maya Óscar LópezSusana Maza José G. Fernández-BolañosJosé Fuentes 《Tetrahedron letters》2003,44(47):8539-8543
The preparation of a urea-bridged β-cyclodextrin dimer and of a 6-monodeoxy-6-mono[3-(β-d-glucopyranos-2-yl)ureido]-β-cyclodextrin has been developed, using triphosgene as the isocyanation agent in an aqueous two-phase system. Per-O-acetylated β-d-gluco and mannopyranosylamines and 2-amino-2-deoxy-α- and β-d-glucose were also transformed into the corresponding isocyanates and converted in situ into ureas by coupling with aromatic and aliphatic amines. 相似文献
16.
In order to make the lab-on-a-chip concept a reality, it is desirable to have an integrated component capable of pumping fluids through microchannels. We have developed novel, electrically actuated micropumps and have integrated them with microfluidic systems. These devices utilize the build-up of electrolysis gases to achieve pressure-driven pumping, only require small voltages (approximately 10 V), and have approximate dimensions of 5 cm x 3 cm x 2 cm. Furthermore, these micropumps are composed of relatively inexpensive materials, and the reversible sealability of their poly(dimethylsiloxane) body to different microfluidic arrays enables repeated uses of the same pump. Under an applied potential of 10 V, three different micropumps had average flow rates of 8-13 microL min(-1) for water being pumped through five different 2 cm-long, 5500 microm(2) cross-sectional-area channels in poly(methyl methacrylate), in approximate agreement with predicted pump rates. We have also evaluated pump operation at the lower applied potential of 8 V and observed an average flow rate of 6.1 microL min(-1) for a pump-channel system. The current micropump design is capable of sustaining pumping pressures in the range of 300 kPa. The various advantages of these micropumps make them well suited for use in lab-on-a-chip analysis techniques. 相似文献
17.
Francisco Batista-Viera Mariela Barbieri Karen Ovsejevi Carmen Manta Jan Carlsson 《Applied biochemistry and biotechnology》1991,31(2):175-195
A new method for the reversible immobilization of thiol bimolecules, e.g., thiolpeptides and thiolproteins, to beaded agarose
and other solid phases is reported. The method consists of an activation and a coupling step. The activation is based on oxidation
of disulfides (or thiol groups via disulfides) present in a solid phase by hydrogen peroxide at moderately acidic pH. This
oxidation leads to disulfide oxides (thiolsulfinate groups of which the majority are further oxidized to thiolsulfonate).
The thiolsulfonate groups react easily with thiol compounds, which become immobilized via disulfide bonds. The pH range for
thiol coupling is wide (pH 5-8), but for most thiols the reaction seems to proceed faster at pH>7. The stability of the reactive
group to hydrolysis, especially at neutral and weakly acidic pH, is very high. The activated gel, therefore, can be stored
as a suspension at pH 5 for extended periods. The method has been used to reversibly immobilize glutathione, β-galactosidase,
alcohol dehydrogenase, urease, and papain, all with exposed thiol groups as well as thiolated bovine serum albumin and sweet-potato
β-amylase.
Depending on the thiol content of starting thiol-agarose, thiol-sulfonate-agarose derivatives with different binding capacities
can be obtained. Thus, up to 5.0 mg (16 μmol) glutathione and 15 mg thiol-protein/mL gel derivative have been immobilized. 相似文献
18.
Giovana Ferronato Mariela S. Viera Osmar D. Prestes Martha B. Adaime 《International journal of environmental analytical chemistry》2013,93(11):1005-1016
ABSTRACTThe food chain is the main source of exposure to humans by organochlorine pesticides (OCPs) due to the bioaccumulation. Breast milk can accumulate OCPs, so this matrix is often used as an environmental bioindicator. The currently available methods for the determination of several OCPs and metabolites in breast milk involve, in general, multi-step sample preparation and quantification techniques with low selectivity, high cost and much time and labour. Thus, a fast and efficient method based on sample preparation using the quick, easy, cheap, effective, rugged and safe (QuEChERS) method combined with gas chromatography coupled to mass spectrometry with negative chemical ionisation (GC-NCI-MS) was developed, validated and applied for determination of 16 OCPs and metabolites in breast milk samples. The extract was cleaned by dispersive solid-phase extraction (d-SPE) using MgSO4 and C18, evaporated in a Turbovap® system, redissolved and analysed by GC-NCI-MS. The method was validated showing acceptable recoveries (72–118%) and precision (RSD <19%). Method limits of detection (LODs) and quantification (LOQs) ranged from 0.75 to 7.5 ng g?1 and from 2.5 to 25 ng g?1 lipid, respectively. The method was successfully applied to 20 samples of breast milk from different regions of the Rio Grande do Sul state, Brazil, of which 75% contained residues below the LOQs. 相似文献
19.
Inmaculada Robina Silvia Gómez-Bujedo José G. Fernández-Bolaños José Fuentes 《合成通讯》2013,43(13):2379-2397
To prepare C-sulfonate derivatives of disaccharides two different strategies were followed. Thus 6- and 6′-C-sulfocellobiosides 4 and 10–12 were prepared starting from a suitably protected cellobioside. The 6′-C-sulfoaminocellobioside 18 was prepared by construction of the molecule through a glycosylation reaction. In both cases, the synthetic pathway involves regioselective tosylation, introduction of a sulfur atom by nucleophilic displacement with potassium thioacetate and oxidation with hydrogen peroxide. 相似文献
20.
José J. Garrido-González Irene Boya del Teso Dr. Ángel L. Fuentes de Arriba Dr. Francisca Sanz Dr. Eva M. Martín del Valle Dr. Joaquín R. Morán Dr. Victoria Alcázar 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(59):14605-14609
Cleft type receptors showing the oxyanion hole motif have been prepared in a straightforward synthesis starting from the commercial 3,7-dihidroxy-2-naphthoic acid. The double H-bond donor pattern is achieved by the introduction of a sulfonamide group in the C-8 position of naphthalene and a carboxamide at the C-2 position. This cleft, for which the geometry resembles that of an oxyanion hole, is able to adjust to different guests, as shown by the analysis of the X-ray crystal structures of associates with methanol or acetic acid. Combination of hydrogen bonds and charge-transfer interactions led to further stabilization of the complexes, in which the electron-rich aromatic ring of the receptor was close in space to the electron-deficient dinitroaromatic guests. Modelling studies and bidimensional NMR experiments have been carried out to provide additional information. 相似文献