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1.
Patrina Paraskevopoulou Eleftheria Petalidou Nikos Psaroudakis Pericles Stavropoulos Konstantinos Mertis 《Monatshefte für Chemie / Chemical Monthly》2005,136(12):2035-2039
Summary. Primary phenylmethanols are selectively and efficiently oxidized to the corresponding aldehydes by the system C6H5IO/(C6H5)4PBr/CH2Cl2, T = 298 K under aerobic conditions. The use of the relatively stable iodosobenzene, an iodine(III) compound, in place of the
usually employed and potentially explosive iodine(V) reagents, the easy work-up procedure, and the facile recycling of solvent
and oxidant provides a convenient and environmentally benign oxidation method. 相似文献
2.
Papoutsis I Nikolaou P Athanaselis S Alevizopoulos G Pistos C Paraskevopoulou C Spiliopoulou C 《Journal of separation science》2011,34(21):3037-3042
Sildenafil (SDL) is a phosphodiesterase type 5 inhibitor and it is approved for the treatment of erectile dysfunction and pulmonary hypertension. SDL is extensively metabolized to its pharmacologically active metabolite, desmethyl‐sildenafil (DSDL). A sensitive and specific GC/MS method for the determination of SDL and DSDL in whole blood was developed and validated to support therapeutic drug monitoring of SDL patients. The combination of solid‐phase extraction with derivatization using BSTFA with 1% TMCS in acetonitrile efficiently reduced matrix effect and improved sensitivity of the method. In this assay, protriptyline was used as internal standard for both analytes. The LODs were 1.50 and 5.00 ng/mL for SDL and DSDL, respectively, whereas the respective LOQs were 5.00 and 15.0 ng/mL. The calibration curves were linear up to 500.0 ng/mL (SDL: R2 0.992, DSDL: R2 0.990). Absolute recovery values for both analytes ranged from 83.1 to 93.2%. Within‐ and between‐batch accuracy was less than 11.8 and 10.2%, respectively, whereas within‐ and between‐batch precision was less than 8.1 and 10.8%, correspondingly. The developed method is suitable for the determination of SDL and DSDL concentrations in blood samples obtained from patients under Viagra® treatment, for pharmacokinetic studies or for the investigation of related forensic cases. 相似文献
3.
Adamantini Kyriacou Costas Balis Milton A. Typas 《Applied biochemistry and biotechnology》1997,66(3):281-289
An acetylene utilizingGordona (Rhodococcus) bronchialis strain, screened for the production of fine chemicals, was found to be capable of producing small amounts of lysine. Attempts
to produce amino-acid analogresistant and/or sensitive mutants and auxotrophs of this strain with increased lysine production
were made following UV-irradiation orN-methyl-N’-nitro-N-nitrosoguanidine (MNNG) treatment. The bacterium exhibited surprisingly high resistance levels to the aforementioned mutagens
which is attributed to highly effective inborn-repair systems. Natural resistance to high levels ofS-(2-aminoethyl)-l-cysteine (AEC) (2%) was observed, in contrast withd, l-aspartic acid hydroxamate (AAH),l-lysine hydroxamate (LHX) and β-fluoropyruvate (FP). A variety of amino-acid analog-resistant (AAHr, LHXr) or analog-sensitive (FPs) mutants were produced following UV-irradiation or MNNG treatment. Similarly, a large number of auxotrophs (68) of different
types were also obtained. From these, one FPs mono-auxotroph and two poly-auxotrophs (with at least one requirement for the aspartic acid family) showed an increased lysine
production (~1.8 g/L) comparable (4 g/L) to that found in other bacteria capable of utilizing long-chain hydrocarbons(1). 相似文献
4.
Celenligil-Cetin R Paraskevopoulou P Lalioti N Sanakis Y Staples RJ Rath NP Stavropoulos P 《Inorganic chemistry》2008,47(23):10998-11009
Redox events involving both metal and ligand sites are receiving increased attention since a number of biological processes direct redox equivalents toward functional residues. Metalloradical synthetic analogues remain scarce and require better definition of their mode of formation and subsequent operation. The trisamido-amine ligand [(RNC6H4)3N]3-, where R is the electron-rich 4-t-Bu Ph, is employed in this study to generate redox active residues in manganese and chromium complexes. Solutions of [(L1)Mn(II)-THF]- in THF are oxidized by dioxygen to afford [(L1re-1)Mn(III)-(O)2-Mn(III)(L1 re-1)]2-as the major product. The rare dinuclear manganese (III,III) core is stabilized by a rearranged ligand that has undergone an one-electron oxidative transformation, followed by retention of the oxidation equivalent as a pi radical in ano-diiminobenzosemiquinonate moiety. Magnetic studies indicate that the ligand-centered radical is stabilized by means of extended antiferromagnetic coupling between the S ) 1/2 radical and the adjacent S ) 2 Mn(III) site, as well as between the two Mn(III) centers via the dioxo bridge. Electrochemical and EPR data suggest that this system can store higher levels of oxidation potency. Entry to the corresponding Cr(III) chemistry is achieved by employing CrCl3 to access both[(L1)Cr(III)-THF] and [(L1re-1)Cr(III)-THF(Cl)], featuring the intact and the oxidatively rearranged ligands, respectively. The latter is generated by ligand-centered oxidation of the former compound. The rearranged ligand is perceived to be the product of an one-electron oxidation of the intact ligand to afford a metal-bound aminyl radical that subsequently mediates a radical 1,4-(N-to-N) aryl migration. 相似文献
5.
Margarita Droulia Athina Anastasaki Alexandros Rokotas Marinos Pitsikalis Patrina Paraskevopoulou 《Journal of polymer science. Part A, Polymer chemistry》2011,49(14):3080-3089
Statistical copolymers of methyl methacrylate (MMA) with 2‐methacryloyloxyethyl ferrocenecarboxylate (MAEFC) were prepared by free radical polymerization. The reactivity ratios were estimated using the Fineman‐Ross, inverted Fineman‐Ross, Kelen‐Tüdos, and extended Kelen‐Tüdos graphical methods. Structural parameters of the copolymers were obtained by calculating the dyad monomer sequence fractions and the mean sequence length. The glass‐transition temperature (Tg) values of the copolymers were measured and examined by means of several theoretical equations, allowing the prediction of these Tg values. The thermal degradation behavior of the copolymers was also studied and compared with the respective homopolymers. Cyclic voltammetry was employed to study the electrochemical properties of the copolymers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
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7.
Celenligil-Cetin R Paraskevopoulou P Dinda R Staples RJ Sinn E Rath NP Stavropoulos P 《Inorganic chemistry》2008,47(3):1165-1172
Functional systems that combine redox-active metals and noninnocent ligands are no longer rare chemical oddities; they are instead emerging as significant components of catalytic and enzymatic reactions. The present work examines the synthetic and functional aspects of iron compounds ligated by a family of new trisamidoamine ligands of the type [(RNC6H4)3N]3- (L1). When R is the electron-rich 4-t-Bu-Ph moiety, the ligand can undergo oxidative rearrangement and store oxidizing equivalents under specific conditions. Starting ferrous complexes of the general formula [(L1)FeIIsolv]- (solv=CH3CN, dimethylformamide) can be easily oxidized (a) by dioxygen to afford the corresponding [(L1)FeIIIOH]- complexes, featuring several cases of terminal hydroxo units, and (b) by organochlorides (R-Cl) to provide [(L1)FeIIIsolv] congeners and coupled R-R products. Efforts to synthesize [(L1)FeIII-O-FeIII(L1)]2- by using [Cl3FeIII-O-FeIIICl3]2- indicate that intrinsic FeIIICl units can oxidatively rearrange the ligand to afford [(L1re)(Cl)FeII][Et4N]2, although the oxidizing equivalent is not retained. Compound [(L1re)(Cl)FeII][Et4N]2 can be further oxidized to [(L1re-2)(Cl)FeIII][Et4N] by CH2Cl2. Finally, oxidation of [(L1)FeIIIsolv] by FeCl3 affords [(L1reH)(Cl)FeII(micro-Cl)2FeII(Cl)(L1re-2H)], which features a similar ligand rearrangement that also gives rise to a diamagnetic, doubly oxidized moiety. These results underscore the complexity of chemical transformations available to systems in which both the metal and the ligand are redox-active entities. 相似文献
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9.
Neuman D Paraskevopoulou P Psaroudakis N Mertis K Staples RJ Stavropoulos P 《Inorganic chemistry》2000,39(24):5530-5537
The present study investigates structural and functional aspects of the redox chemistry of rhenium(III) chloride [Re3Cl9] (1) in aqueous and organic solvents, with emphasis on the dioxygen-activating capabilities of reduced rhenium clusters bearing the Re3(8+) core. Dissolution of 1 in HCl (6 M) generates [Re3(mu-Cl)3Cl9]3- (2a), which can be isolated as the tetraphenylphosphonium salt (2b). Anaerobic one-electron reduction of 1 by Hg in HCl (6-12 M) produces [(C6H5)4P]2[Re3(mu-Cl)3Cl7(H2O)2].H2O (3), the structure of which features a planar [Re3(mu-Cl)3Cl3] framework (Re3(8+) core), involving two water ligands that occupy out-of-plane positions in a trans arrangement. Compound 3 dissociates in the presence of CO, yielding [(C6H5)4P]2[ReIII2Cl8] (4) and an unidentified red carbonyl species. In situ oxidation (O2) of the reduced Re3(8+)-containing cluster in HCl (6 M) produces quantitatively 2a, whereas oxidation of 3 in organic media results in the formation of [(C6H5)4P]4[(Re3(mu-Cl)3Cl7(mu-OH))2].2CH2Cl2 (5). The structure of 5 reveals that two oxygen ligands (hydroxo units) bridge asymmetrically two Re3(9+) triangular clusters. The origin of these hydroxo units derives from the aquo ligands, rather than O2, as shown by 18O2 labeling studies. The hydroxo bridges of 5 can be replaced by chlorides upon treatment with Me3SiCl to afford the analogous [(C6H5)4P]4[(Re3(mu-Cl)3Cl7(mu-Cl))2].10CH2Cl2 (6). The reaction of 5 with Hg in HCl (6 M)/tetrahydrofuran regenerates compound 3. Complexes 1-3 exhibit nitrile hydratase type activity, inducing hydrolysis of CH3CN to acetamide. The reaction of 3 with CH3CN yields [(C6H5)4P]2[Re3(mu-Cl)3Cl6.5(CH3CN)1.5(CH3C(O)NH)0.5] (7), the structure of which is composed of [Re3(mu-Cl)3Cl7(CH3CN)2]2- (7a) and [Re3(mu-Cl)3Cl6(CH3CN)(CH3C(O)NH)]2- (7b) (Re3(8+) cores) as a disordered mixture (1:1). Oxidation of 7 with O2 in CH3CN affords [(C6H5)4P]2[Re3(mu-Cl)3Cl7(CH3C(O)NH)].CH3CN (8) and small amounts of [(C6H5)4P][ReO4] (9). Compound 8 is also independently isolated from the reaction of 2b with wet CH3CN, or by dissolving 5 in CH3CN. In MeOH, 5 dissociates to afford [(C6H5)4P]2[Re3(mu-Cl)3Cl8(MeOH)].MeOH (10). 相似文献
10.
Patrina Paraskevopoulou Nikos Psaroudakis Spyros Koinis Pericles Stavropoulos Konstantinos Mertis 《Journal of molecular catalysis. A, Chemical》2005,240(1-2):27-32
The system (nBu4N)ReO4 5/PhIO/CH2Cl2, T = 298 K catalyses effectively and with total selectivity the anaerobic oxidation of a range of primary substituted benzyl alcohols (o-, m-, p-X-C6H4-CH2OH, X = H, Me, MeO, Cl, NO2, CF3) to the corresponding aldehydes; in contrast, it is unreactive towards secondary benzyl and aliphatic (primary and secondary) alcohols. This may prove of interest in synthetic organic transformations, when several alcoholic functionalities are present in the same molecule. 相似文献