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排序方式: 共有1177条查询结果,搜索用时 15 毫秒
31.
4-n-Butylamino-5-ethyl-1,2-benzoquinone (1(ox)) has been synthesized as a model compound for the LTQ (lysine tyrosyl quinone) cofactor of lysyl oxidase (LOX). At pH 7, 1(ox) has a lambda(max) at 504 nm and exists as a neutral o-quinone in contrast to a TPQ (2,4,5-trihydroxyphenylalanine quinone) model compound, 4, which is a resonance-stabilized monoanion. Despite these structural differences 1(ox) and 4 have the same redox potential (ca. -180 mV vs SCE). The structure of the phenylhydrazine adduct of 1(ox) (2) is reported, and 2D NMR spectroscopy has been used to show that the position of nucleophilic addition is at C(1). UV-vis spectroscopic pH titration of phenylhydrazine adducts of 1(ox) and 4, 2, and 11, respectively, reveals a similar red shift in lambda(max) at alkaline pH with the same pK(a) (approximately 11.8). In contrast, the red shift in lambda(max) at acidic pH conditions yields different pK(a) values (2.12 for 2 vs -0.28 for 11), providing a means to distinguish LTQ from TPQ. Reactions between in situ generated 4-ethyl-1,2-benzoquinone and primary amines give a mixture of products, indicating that the protein environment must play an essential role in LTQ biogenesis by directing the nucleophilic addition of the epsilon-amino group of a lysine residue to the C(4) position of a putative dopaquinone intermediate. Characterization of a 1,6-adduct between an o-quinone and butylamine (3-n-butylamino-5-ethyl-1,2-benzoquinone, 13) confirms the assignment of LTQ as a 1,4-addition product. 相似文献
32.
Jones AK Lamle SE Pershad HR Vincent KA Albracht SP Armstrong FA 《Journal of the American Chemical Society》2003,125(28):8505-8514
The cycling between active and inactive states of the catalytic center of [NiFe]-hydrogenase from Allochromatium vinosum has been investigated by dynamic electrochemical techniques. Adsorbed on a rotating disk pyrolytic graphite "edge" electrode, the enzyme is highly electroactive: this allows precise manipulations of the complex redox chemistry and facilitates quantitative measurements of the interconversions between active catalytic states and the inactive oxidized form Ni(r) (also called Ni-B or "ready") as functions of pH, H(2) partial pressure, temperature, and electrode potential. Cyclic voltammograms for catalytic H(2) oxidation (current is directly related to turnover rate) are highly asymmetric (except at pH > 8 and high temperature) due to inactivation being much slower than activation. Controlled potential-step experiments show that the rate of oxidative inactivation increases at high pH but is independent of potential, whereas the rate of reductive activation increases as the potential becomes more negative. Indeed, at 45 degrees C, activation takes just a few seconds at -288 mV. The cyclic asymmetry arises because interconversion is a two-stage reaction, as expected if the reduced inactive Ni(r)-S state is an intermediate. The rate of inactivation depends on a chemical process (rearrangement and uptake of a ligand) that is independent of potential, but sensitive to pH, while activation is driven by an electron-transfer process, Ni(III) to Ni(II), that responds directly to the driving force. The potentials at which fast activation occurs under different conditions have been analyzed to yield the potential-pH dependence and the corresponding entropies and enthalpies. The reduced (active) enzyme shows a pK of 7.6; thus, when a one-electron process is assumed, reductive activation at pH < 7 involves a net uptake of one proton (or release of one hydroxide), whereas, at pH > 8, there is no net exchange of protons with solvent. Activation is favored by a large positive entropy, consistent with the release of a ligand and/or relaxation of the structure around the active site. 相似文献
33.
Impurity profiles of 3,4-methylenedioxymethylamphetamine (MDMA) tablets seized in France have been examined. The samples were extracted with methylene chloride under basic conditions and then analyzed by capillary gas chromatography. Almost 30 compounds were identified as precursors, intermediates and by-products. Palmitic and stearic acid were also found as tableting materials. The comparison of the different profiles obtained by the reported procedure provided very useful information about the synthetic processes used by clandestine laboratories and enabled a classification into several groups of profiles. According to these results, the reductive amination route appears to be the most common synthetic pathway in Western Europe. Furthermore, 3,4-methylenedioxyphenyl-2-propanone seems to be the most used precursor in clandestine laboratories. 相似文献
34.
Marianayagam NJ Khan F Male L Jackson SE 《Journal of the American Chemical Society》2002,124(33):9744-9750
The FK506-FKBP12 binding-domain of the kinase FRAP (FRB) forms a classic up-down four-helical bundle. The folding pathway of this protein has been investigated using a combination of equilibrium and kinetic studies. The native state of the protein is stable with respect to the unfolded state by some 7 kcal mol(-1) at pH 6.0, 10 degrees C. A kinetic analysis of unfolding and refolding rate constants as a function of chemical denaturant concentration suggests that an intermediate state may be populated during folding at low concentrations of denaturant. The presence of this intermediate state is confirmed by refolding experiments performed in the presence of the hydrophobic dye 8-anilinonaphthalene-1 sulfonate (ANS). ANS binds to the partially folded intermediate state populated during the folding of FRB and undergoes a large change in fluorescence that can be detected using stopped-flow techniques. Analysis of the kinetic data suggests that the intermediate state is compact and it may even be a misfolded species that has to partially unfold before it can reach the transition state. Folding and unfolding rate constants in water are approximately 150-200 s(-1) and 0.005-0.06 s(-1), respectively, at neutral pH and 10 degrees C. The folding of FRB is somewhat slower than for other all-helical proteins, probably as a consequence of the formation of a metastable intermediate state. The folding rate constant in the absence of any populated intermediate can be estimated to be 8800 s(-1). Despite the presence of an intermediate state, which effectively slows folding, the protein still folds rapidly with a half-life of 5 ms at 10 degrees C. The dependence of the rate constants on denaturant concentration indicates that the transition state for folding is compact with some 80% of the surface area exposed in the unfolded state buried in the transition state. Data presented for FRB is compared with kinetic data obtained for other all-helical proteins. 相似文献
35.
Khaled Beyaz Carlos Vaca-Garcia Emeline Vedrenne Nabila Haddadine Ahmed Benaboura Sophie Thiebaud-Roux 《International Journal of Polymer Analysis and Characterization》2019,24(3):245-256
In this work, we reported the preparation of a novel biomaterial, by graft-polymerization of 2-2-dimethyl-1-3-dioxolan-4-yl methyl acrylate (solketalacrylate, DMDMA) on hydroxyethyl cellulose (HEC) using KPS as initiator. Several experiments were performed to found the optimum conditions for the preparation of this biopolymer, by varying the time of the reaction as well as the initiator and the monomer ratio. Results showed that the highest grafting yield was 25%, obtained after 72?minutes at 65?°C, using THF as solvent. The structure of the grafted copolymer was confirmed by X-ray diffraction patterns which showed, besides the characteristic peaks of HEC at 2θ?=?31.74° and 44.63° a new peak at 2θ?=?30.72° related to an organized structure of the grafted polymer on the HEC backbone. The DSC analysis showed a single glass transition temperature Tg, intermediate between the corresponding values for HEC and neat poly(solketal acrylate). Moreover, the grafted biomaterial presented two-fold more moisture absorption ability by comparison with HEC, making this new synthetic biomaterial highly promising for dryness applications. In our knowledge, the synthesized monomer: 2-2-dimethyl-1-3-dioxolan-4-yl methyl acrylate, (solketal acrylate, DMDMA), has never been grafted on the HEC backbones before that is what makes the novelty of the present work. 相似文献
36.
Billon Sophie Sardini Paul Leblond Sylvain Fichet Pascal 《Journal of Radioanalytical and Nuclear Chemistry》2019,320(3):699-709
Journal of Radioanalytical and Nuclear Chemistry - A large set of key parameters is provided to use in decommissioning operations, the conversion method fully described in the companion paper... 相似文献
37.
Antonin Desmecht Dr. Debobrata Sheet Claude Poleunis Prof. Sophie Hermans Prof. Olivier Riant 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(6):1436-1440
The chemical functionalization of carbon nanotubes is often a prerequisite prior to their use in various applications. The covalent grafting of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (BPin) functional groups directly on the surface of multi- and single-walled carbon nanotubes, activated by nucleophilic addition of nBuLi, was carried out. Thermogravimetric analysis (TGA) coupled with mass spectrometry, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ions mass spectrometry (ToF-SIMS) confirmed the efficiency of this methodology and proved the integrity and covalent grafting of the BPin functional groups. These groups were further reacted with various nucleophiles in the presence of a copper(II) source in the conditions of the aerobic Chan–Lam–Evans coupling. The resulting materials were characterized by TGA, XPS and ToF-SIMS. This route is efficient, reliable and among the scarce reactions that enable the direct grafting of heteroatoms at carbonaceous material surfaces. 相似文献
38.
Sandra E. Dann Mark R.J. Elsegood Paul M. Staniland Sophie H. Dale 《Journal of organometallic chemistry》2006,691(23):4829-4842
A new series of neutral organometallic building blocks based on piano-stool ruthenium(II) complexes, RuCl2(p-cymene)Ph2PCH2Y [Y = -NHC6H4(2-CO2H) (2a), -NHC6H4(3-CO2H) (2b), -NHC6H3(3-CO2H)(6-OCH3) (2c), -NHC6H4(4-CO2H) (2d), -NHC6H3(2-CO2H)(4-OH) (2e), -NHC6H3(3-OH)(4-CO2H) (2f), -NHC6H3(2-CO2H)(5-CO2H) (2g) and -OH (2h)], were synthesised in high yields (>88%) from {RuCl2(p-cymene)}2 and the appropriate phosphines 1a-1h. The new tertiary phosphine 1b was prepared by Mannich condensation of NH2C6H4(3-CO2H) with Ph2PCH2OH in MeOH. Solution NMR (31P{1H}, 1H), FT-IR and microanalytical data are in full agreement with the proposed structures. Single crystal X-ray studies confirm that, in each case, compounds 2a, 2b and 2d-2h have piano-stool arrangements with typical Ru-P, Ru-Cl and Ru-Ccentroid bond lengths. From our crystallographic studies, factors that influence the supramolecular assemblies of these ruthenium(II) complexes include: (i) the type of functional group present, (ii) the geometric disposition of the -N(H)CH2PPh2, -CO2H and -OH groups around the central benzene scaffold, and (iii) the solvents used in the recrystallisations. Hence in isomers 2a and 2b, molecules are associated into head-to-tail dimer pairs through classical intermolecular O-H?O hydrogen bonding. This feature is also observed in isomer 2d but dimer pairs are further associated to give a 1-D chain through assisted intermolecular N-H?Cl hydrogen bonding. The additional 4-hydroxo group in 2e promotes a ladder arrangement via intermolecular O-H?O and O-H?Cl hydrogen bonding. In contrast the isomeric compound 2f does not show head-to-tail O-H?O hydrogen bonding but instead O-H?Cl and N-H?O intermolecular hydrogen bonding is observed. Depending on the choice of solvent (MeOH or DMSO), 2g forms extended networks based on chains (2g · DMSO · 1.5MeOH) or tapes (2g · 3MeOH). In 2h, a single intramolecular O-H?Cl hydrogen bond is observed for each independent molecule. The X-ray structure of one representative tertiary phosphine, 1f, has also been determined. 相似文献
39.
Fascione MA Adshead SJ Mandal PK Kilner CA Leach AG Turnbull WB 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(10):2987-2997
Sulfoxides are frequently used in organic synthesis as chiral auxiliaries and reagents to mediate a wide variety of chemical transformations. For example, diphenyl sulfoxide and triflic anhydride can be used to activate a wide range of glycosyl donors including hemiacetals, glycals and thioglycosides. In this way, an alcohol, enol or sulfide is converted into a good leaving group for subsequent reaction with an acceptor alcohol. However, reaction of diphenyl sulfoxide and triflic anhydride with oxathiane-based thioglycosides, and other oxathianes, leads to a different process in which the thioglycoside is oxidised to a sulfoxide. This unexpected oxidation reaction is very stereoselective and proceeds under anhydrous conditions in which the diphenyl sulfoxide acts both as oxidant and as the source of the oxygen atom. Isotopic labelling experiments support a reaction mechanism that involves the formation of oxodisulfonium (S-O-S) dication intermediates. These intermediates undergo oxygen-exchange reactions with other sulfoxides and also allow interconversion of axial and equatorial sulfoxides in oxathiane rings. The reversibility of the oxygen-exchange reaction suggests that the stereochemical outcome of the oxidation reaction may be under thermodynamic control, which potentially presents a novel strategy for the stereoselective synthesis of sulfoxides. 相似文献
40.
Guillerm B Darcos V Lapinte V Monge S Coudane J Robin JJ 《Chemical communications (Cambridge, England)》2012,48(23):2879-2881
Well-defined graft copolymers were obtained using a copper-catalysed azide-alkyne Huisgen's cycloaddition click reaction from both biocompatible and non-toxic poly(ε-caprolactone) and poly(2-methyl-2-oxazoline) homopolymers. Resulting amphiphilic copolymers proved to form micelles that could be used as potential drug carriers. 相似文献