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51.
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53.
A stereoselective ion-pair nonaqueous capillary electrophoresis (NACE) method employing the partial filling technique with N-derivatized amino acids, e.g., (R)- and (S)-3,5-dinitrobenzoyl-leucine (DNB-Leu), as chiral selector for the separation of "pseudoenantiomeric" cinchona alkaloid derivatives and other structurally related basic compounds like the enantiomers of mefloquine is presented. Originating from NACE with cinchona alkaloid derivatives as chiral counterions, this method was developed by application of the reciprocity principle of chiral recognition, which was proven to be valid for stereoselective ion-pair capillary electrophoresis (CE). A variety of basic and amphoteric selectands (SAs) could be well resolved. Thereby, the separation was primarily based on stereoselective ion-pair formation of corresponding SA stereoisomers and mobility differences of free and complexed (ion-paired) SAs. Additionally, in the case of diastereomeric SAs, naturally existing mobility differences between the diastereomers played also a role, but was shown by control experiments with racemic DNB-Leu and without selector (SO) to be of minor contribution to overall separation selectivity. Due to its simplicity, speed, and good reproducibility, the established method can be utilized for fast screening of cationic as well as amphoteric chiral compounds, and therefore is a valuable tool in the development of new chiral selectors and chiral stationary phases. Small sample amounts of the SO (4-5 mg) and only analytical amounts of SAs are needed, and about 20-50 compounds per day can be tested. 相似文献
54.
Gino Bontempelli Franco Magno Benedetto Corain Gilberto Schiavon 《Transition Metal Chemistry》1985,10(1):8-11
Summary The reduction of nickel perchlorate in the presence of carbon monoxide and substituted phosphines or diphosphines has been studied in acetonitrile by cyclic voltammetry. The results show that only mono- and bis-carbonylphosphinenickel(O) complexes are formed, while no evidence for the formation of carbonyl-nickel(I) and -nickel(II) species was obtained. Although the oxidation processes are not reversible, a good correlation between the anodic peak potentials relative to nickel(O) complexes and the -donor--acceptor abilities of the phosphines employed was observed. 相似文献
55.
Galli C Gentili P Lanzalunga O Lucarini M Pedulli GF 《Chemical communications (Cambridge, England)》2004,(20):2356-2357
Characterisation of the aminoxyl (>N-O*) radical BTNO, generated from 1-hydroxybenzotriazole (HBT) by the one-electron oxidant CAN (a Ce(IV) salt), confirms BTNO as the reactive intermediate in oxidations run with the laccase/HBT system. 相似文献
56.
J. Mullens G. Reggers M. Ruysen R. Carleer J. Yperman D. Franco L. C. Van Poucke 《Journal of Thermal Analysis and Calorimetry》1997,49(2):1061-1067
The oxidative degradation of HET-acid (1,4,5,6,7,7-hexachlorobicyclo [2.2.1] hept-5-en-2, 3-dicarboxylic acid) is studied by the combination of TG, FTIR, MS and GC-MS. The gases evolved during the decomposition of this flame retardant are investigated on-line by FTIR and by MS. Simultaneously the evolved gases are collected by an adsorbent and, after the thermal experiment, desorbed to release the volatile products for identification using GC-MS. The combination of these techniques offers the unambiguous identification of the evolved products as a function of temperature. The main identified products are CO2, H2O, Cl2, HCl, C2Cl4, maleic acid anhydride, HET-acid anhydride, chlorinated cyclic hydrocarbons and chlorinated unsaturated linear hydrocarbons. 相似文献
57.
Maria Rosaria Del Giudice Anna Borioni Carlo Mustazza Franco Gatta 《Journal of heterocyclic chemistry》1994,31(6):1503-1507
A number of 2-aryl-substituted pyrido[3,2-e] and [4,3-e][1,2,4]triazolo[1,5-c]pyrimidines and [1,2,4]triazolo[1,5-c]pteridines 11,12a,b,e , their corresponding 5-carbonyl derivatives 7,8a,b,e and some pyrimido[5,4-e][1,2,4]triazolo[1,5-c]pyrimidin-5-ones 7,8c,d have been synthesized, according to different pathways. The new tricyclic heterocycles were prepared with the aim of studying their possible benzodiazepine receptors affinity. 相似文献
58.
Franco Cecconi Carlo A. Ghilardi Stefano Midollini Annabella Orlandini Piero Zanello 《Polyhedron》1986,5(12):2021-2031
The reaction of hydrogen sulphide with [Co(H2O)6](BF4)2 and triethylphosphine in the presence of sodium tetraphenylborate or tetrabutylammonium hexafluorophosphate gave the paramagnetic clusters [Co6(μ3-S)8(PEt3)6](Y) (Y = BPh4, (1), PF6, (2)). These compounds can be easily reduced by sodium napthalenide to the diamagnetic species [Co6(μ3-S)8(PEt3)6] · 2C4H8O (3). The molecular structures of 1 and 3 have been established by single-crystal X-ray diffraction methods. Crystal data: (1) space group P
, a = 19.481(9), b = 15.562(7), c = 12.390(b) Å, α = 92.70(8), β = 94.50(7), γ = 94.10(9)°, Z = 2, (3) space group R
, a = 11.780(6) Å, α = 92.50(7)°, Z = 1. Both structures were solved by the heavy atom method and refined by full-matrix least-squares techniques to the conventional R factors values of 0.050 for 1 and 0.044 for 3 on the basis of 4251 and 1918 observed reflections, respectively. The two clusters [Co6(μ3-S)8)(PEt3)6]1+,0 are isostructural, the inner core consisting of an octahedron of cobalt atoms with all the faces symmetrically capped by triply bridging sulphur atoms. Each metal centre is additionally linked to a triethylphosphine group so that each cobalt atom is co-ordinated by four sulphur atoms and one phosphorus in a distorted square pyramidal environment. The addition of one electron whilst leaving unchanged the geometry of the inner framework, induces small changes in the structural parameters, the average Co---Co and Co---P distances being 2.794 (3) and 2.162 (2) Å for 1 and 2.817 (3) and 2.138 (2) Å for 3 respectively. Electrochemistry in non-aqueous solvents shows the electron-transfer sequence
The tricationic species is stable only in the short time of cyclic voltammetric tests. 相似文献
Full-size image (3K)
59.
Rodella Cristiane B. Franco Roberto W.A. Magon Claudio J. Donoso Jose P. Nunes Luis A.O. Saeki Margarida J. Aegerter Michel A. Sargentelli Vagner Florentino Ariovaldo O. 《Journal of Sol-Gel Science and Technology》2002,25(1):83-88
Raman spectroscopy and Electron Paramagnetic Resonance (EPR) studies were performed on a series of V2O5/TiO2 catalysts prepared by a modified sol-gel method in order to identify the vanadium species. Two species of surface vanadium were identified by Raman measurements, monomeric vanadyls and polymeric vanadates. Monomeric vanadyls are characterized by a narrow Raman band at 1030 cm–1 and polymeric vanadates by two broad bands in the region from 900 to 960 cm–1 and 770 to 850 cm–1. The Raman spectra do not exhibit characteristic peaks of crystalline V2O5. These results are in agreement with those of X-ray Diffractometry (XRD) and Fourier Transform Infrared (FT-IR) previously reported (C.B. Rodella et al., J. Sol-Gel Sci. Techn., submitted). At least three families of V4+ ions were identified by EPR investigations. The analysis of the EPR spectra suggests that isolated V4+ ions are located in sites with octahedral symmetry substituting for Ti4+ ions in the rutile structure. Magnetically interacting V4+ ions are also present as pairs or clusters giving rise to a broad and structureless EPR line. At higher concentration of V2O5, a partial oxidation of V4+ to V5+ is apparent from the EPR results. 相似文献
60.
The oxidation of some 3-(methoxy- and ethoxycarbonyl)tetrahydro-β-carboline derivatives with sodium periodate led to the formation of 1, 4-benzodiazonine derivatives or fully aromatic β-carbolines depending on both nature and number of substituents at 1-position. 相似文献