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81.
Beşli S Coles SJ Davies DB Eaton RJ Hursthouse MB Kiliç A Shaw RA Yenilmez Ciftçi G Yeşilot S 《Journal of the American Chemical Society》2003,125(16):4943-4950
A problem has arisen in using chiral shift reagents (CSR) and chiral solvating agents (CSA) to determine meso and racemic forms of diastereoisomers in which the stereogenic centers of the molecules are separated by achiral spacers. It is found that NMR signals of both meso and racemic forms of diastereoisomers may exhibit doubling on addition of CSR/CSA, which means that unequivocal assignments cannot be made without characterizing the effects for separate meso and racemic forms; this is particularly important for additions of CSR/CSA at relatively low concentrations, which always result in the splitting of some NMR signals of diastereoisomers. The phenomenon is demonstrated in the (31)P NMR spectra of meso and racemic forms of three spermine-bridged gem-disubstituted cyclotriphosphazatrienes, 1a-c, and compared with analogous achiral molecules, the per-substituted spermine-bridged cyclotriphosphazatrienes 2a-d. As expected, only one set of (31)P NMR signals was observed for the achiral compounds 2a-d, even on addition of CSA. Two sets of (31)P NMR ABX multiplets corresponding to meso and racemic diastereoisomers were observed for compounds 1a-c; on addition of CSA, the signals of at least one of the multiplets for each compound separated into more than the expected groups of three lines with an intensity distribution of 2:1:1. To understand this phenomenon, the meso and racemic forms of 1a and 1b and the meso form of 1c have been separated and characterized by X-ray crystallography. On addition of CSA to the racemic forms of 1a and 1b, the (31)P NMR spectrum shows the expected doubling of signals, but, unexpectedly, the same is observed for each of the meso forms of 1a-c. Analogous results using both CSA and CSR have been obtained for the meso and racemic forms of the diastereoisomeric piperazine-bridged macrocyclic-phosphazene compound, 3, whereas no effect was observed for the two meso forms of the doubly bridged macrocyclic-phosphazene compound 4. The phenomenon of doubling of the (31)P NMR signals of the meso form of singly bridged cyclotriphosphazatrienes, 1a-c and 3, is explained by consideration of the equilibrium in solution of independent complexation of a chiral ligand with molecules that have two chiral cyclophosphazene moieties separated by an achiral spacer group. The results show that the stereogenicity of such diastereoisomeric molecules in solution cannot be characterized unequivocally by NMR measurements on addition of either CSR or CSA. 相似文献
82.
The present paper deals with the electrokinetic characterization of sepiolite. A series of systematic zeta potential measurements have been carried out to determine the isoelectric point (iep) and potential-determining ions (pdi), and the effect of mono-, di-, and trivalent electrolytes such as NaCl, KCl, LiCl, NaNO(3), NaCH(3)COO, MgCl(2), CaCl(2), BaCl(2), CoCl(2), CuCl(2), Pb(NO(3))(2), Na(2)CO(3), Na(2)SO(4), AlCl(3), FeCl(3), and Na(3)PO(4) on the zeta potential of sepiolite. Zeta potential has been calculated with the aid of Smoluchowski's equation. Sepiolite yields an isoelectric point at pH 6.6. The zeta potential for the sepiolite has ranged from +23.3 mV at pH approximately 2 to -22.4 mV at pH approximately 8 at 20 +/- 2 degrees C in water. The valency of the ions have proven to have a great influence on the electrokinetic behavior of the suspension. Monovalent cations were found to have a weak effect, while di- and trivalent cations made the zeta potential positive. Charge reversal was observed for divalent cations at 1 x 10(-2) M and for trivalent cations at 3 x 10(-4) M. As a result, it can be said that monovalent cations are indifferent ions when di- and trivalent cations are potential-determining ions. 相似文献
83.
In this study, the new vic-dioxime ligand (LH2) and its complexes with CoII, NiII, CuII, ZnII, CdII and UO2VI are described. The structures of these complexes were characterized by elemental analyses, i.r., 1H- and 13C-n.m.r. spectra, u.v.–vis. spectroscopy, magnetic susceptibility measurements, conductivity measurements and thermogravimetric
analyses (t.g.a.). 相似文献
84.
Dr. Joice Thomas Dr. Liliana Dobrzańska Prof. Luc Van Meervelt Prof. Mario Alfredo Quevedo Prof. Krzysztof Woźniak Marcin Stachowicz Prof. Mario Smet Prof. Wouter Maes Prof. Wim Dehaen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(3):979-987
A synthetic route towards homodiselenacalix[4]arene macrocycles is presented, based on the dynamic covalent chemistry of diselenides. The calixarene inner rim is decorated with either alkoxy or tert‐butyl ester groups. Single‐crystal X‐ray analysis of two THF solvates with methoxy and ethoxy substituents reveals the high similarity of their molecular structures and alterations on the supramolecular level. In both crystal structures, solvent channels are present and differ in both shape and capacity. Furthermore, the methoxy‐substituted macrocycle undergoes a single‐crystal‐to‐single‐crystal transformation during which the molecular structure changes its conformation from 1,3‐alternate (loaded with THF/water) to 1,2‐alternate (apohost form). Molecular modelling techniques were applied to explore the conformational and energetic behaviour of the macrocycles. 相似文献
85.
John D. Roehling Christopher W. Rochester Hyun Wook Ro Peng Wang Jaroslaw Majewski K. Joost Batenburg Ilke Arslan Dean M. Delongchamp Adam J. Moulé 《Journal of Polymer Science.Polymer Physics》2014,52(19):1291-1300
The morphology in mixed bulk‐heterojunction films are compared using three different quantitative measurement techniques. We compare the vertical composition changes using high‐angle annular dark‐field scanning transmission electron microscopy with electron tomography and neutron and x‐ray reflectometry. The three measurement techniques yield qualitatively comparable vertical concentration measurements. The presence of a metal cathode during thermal annealing is observed to alter the fullerene concentration throughout the thickness of the film for all measurements. However, the absolute vertical concentration of fullerene is quantitatively different for the three measurements. The origin of the quantitative measurement differences is discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1291–1300 相似文献
86.
Laura Pop Pierrik Lassalas László Csaba Bencze Monica Ioana Toşa Botond Nagy Florin Dan Irimie Christophe Hoarau 《Tetrahedron: Asymmetry》2012,23(6-7):474-481
Stereoselective preparative enzymatic acylation and hydrolysis/methanolysis of various C-substituted rac-thiazol-2-yl-methanols were achieved for the preparation of enantiopure or enantiomerically enriched, naturally occurring 2-hydroxymethylthiazoles. The absolute configurations of the resulting secondary alcohols were determined by a detailed 1H NMR study of Mosher’s derivatives. 相似文献
87.
Maja Trček George Cordoyiannis Brigita Rožič Vassilios Tzitzios George Nounesis Samo Kralj 《Liquid crystals》2017,44(10):1575-1581
We report on the stabilisation of the liquid-crystalline, twist-grain boundary A (TGBA) phase in mixtures of a chiral liquid crystal and surface-functionalised spherical Au nanoparticles (NPs) of 10 nm diameter. The results, obtained by calorimetric, optical, small-angle X-ray and plasmon resonance measurements, demonstrate that a TGBA phase, which is metastable for the pure liquid crystal host, can be effectively stabilised for a 3 K range in the presence of NPs. Moreover, the role of NPs size on the TGBA stabilisation is briefly discussed. 相似文献
88.
The semicontinuous emulsion polymerization of vinyl acetate has been studied. Poly(vinyl alcohol) as a protective colloid and ethoxylated cetyl alcohol as a coemulsifier were used. The conversion and particle diameter were affected by the stirring speed and the coemulsifier distribution between initial reactor charge and continuously introduced monomer. The amount of unreacted monomer oscillates with time. 相似文献
89.
A short-term aerobic stabilization of digested waste in the final methane phase was studied. The effect of aeration rate on
the reduction of leachate parameters and on the rate of CO2 production and O2 assimilation was investigated. Experimental simulation of aerobic landfill stabilization was carried out using lysimeters.
When testing the effect of aeration rate on the reduction of leachate indices (BOD5, COD, N-NH4+), it was reported that the most significant reduction was obtained at the highest rate of aeration and the smallest reduction
of leachate indices was attained not at the lowest but at medium aeration rates. Both the rate of CO2 production and the O2 assimilation reached their highest values in the lysimeters aerated at a high rate of aeration. The proposed mathematical
model which consists of a system of five differential equations describing CO2 production, O2 assimilation and the changes of organic carbon content in the leachate correspond well with the experimental data. 相似文献
90.
J. M. Ferreira Liliana Caramelo R. P. Chhabra 《International Journal of Mathematical Education in Science & Technology》2013,44(4):545-552
A curve fitting model is presented which minimizes the sum of squares of relative residues and expressions for the fit coefficients and their respective errors are derived. The new model is compared to the normal least squares model, using as an example the Reynolds number-drag coefficient data for a sphere. The results show that the best fit was obtained with the new model, indicating it may provide a useful tool for data analysis. 相似文献