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961.
Goldcamp MJ Edison SE Squires LN Rosa DT Vowels NK Coker NL Krause Bauer JA Baldwin MJ 《Inorganic chemistry》2003,42(3):717-728
A library of tripodal amine ligands with two oxime donor arms and a variable coordinating or noncoordinating third arm has been synthesized, including two chiral ligands based on l-phenylalanine. Their Ni(II) complexes have been synthesized and characterized by X-ray crystallography, UV-vis absorption, circular dichroism, and FTIR spectroscopy, mass spectrometry, and room-temperature magnetic susceptibility. At least one crystal structure is reported for all but one Ni/ligand combination. All show a six-coordinate pseudo-octahedral coordination geometry around the nickel center, with the bis(oxime)amine unit coordinating in a facial mode. Three distinct structure types are observed: (1) for tetradentate ligands, six-coordinate monomers are formed, with anions and/or solvent filling out the coordination sphere; (2) for tridentate ligands, six-coordinate monomers are formed with Ni(II)(NO(3))(2), with one monodentate and one bidentate nitrate filling the remaining coordination positions; (3) for tridentate ligands, six-coordinate, bis(mu-Cl) dimers are formed with Ni(II)Cl(2), with one terminal and two bridging chlorides filling the coordination sphere. The UV-vis absorption spectra of the complexes show that the value of 10 Dq varies according to the nature of the third arm of the ligand. The trend based on the third arm follows the order alkyl/aryl < amide < carboxylate < alcohol < pyridyl < oxime. 相似文献
962.
I. Yavari D. Tahmassebi D. Nori-Shargh M. Heydari 《Monatshefte für Chemie / Chemical Monthly》1996,127(10):1021-1025
Summary AM1 semi-empirical SCF MO calculations are reported for important conformations of oxocane (1) and 1,3-dioxocane (2). The boat-chair conformation of1 (BC-1) is found to be the most stable form, whereas the crown family conformation is calculated to be 3.7 kJ·mol–1 less stable. The boat-boat form of1 is 15.9 kJ·mol–1 less stable thanBC-1. The boat-chair conformation of2 (BC-1,3) is calculated to be the most stable form of 1,3-Dioxocane. The crown-family conformation and the boat-boat geometry of this compound are 4.2 and 8.3 kJ mol–1 less stable thanBC-1,3.
AM1-Rechnungen zu den Konformationen von Oxocane und 1,3-Dioxocan
Zusammenfassung Die wesentlichen Konformationen von Oxocan (1) und 1,3-Dioxocan (2) wurden mittels semiempirischer AM1-Rechnungen (SCF MO) untersucht. Die Wanne-Sessel-Konformation von1 (BC-1) ist am stabilsten; Konformationen aus der Klasse der Kronen sind um 3.7 kJ·mol–1 energiereicher. Die Wanne-Wanne-Konformation von1 ist um 15.9 kJ·mol–1 instabiler alsBC-1. Die Wanne-Sessel-Konformation von2 (BC-1,3) ist das stabilste Konformer von 1,3-Dioxocan. Kronenkonformationen und Wanne-Wanne-Geometrien sind um 4.2 und 8.3 kJ·mol–1 energiereicher alsBC-1,3.相似文献
963.
Shi Shun AL Chernick ET Eisler S Tykwinski RR 《The Journal of organic chemistry》2003,68(4):1339-1347
Unsymmetrically substituted 1,3-butadiynes and 1,3,5-hexatriynes are synthesized in four steps from commercially available aldehydes or carboxylic acids. The key step in this process involves a Fritsch-Buttenberg-Wiechell rearrangement, in which an alkylidene carbenoid intermediate subsequently rearranges to the desired polyyne. This rearrangement proceeds under mild conditions, and it is tolerant of a range of functionalities. In general, the procedurally facile formation of the dibromoolefinic precursors, in combination with the effectiveness of the rearrangement step, makes this procedure an attractive alternative to traditional methods for di- and triyne synthesis that utilize palladium or copper catalysis. 相似文献
964.
Stereoselective preparation of beta-C-glycosides has been developed from acetylated glycopyranosyl 2-pyridyl sulfones, involving a samarium-Barbier coupling procedureoxidation-isomerization sequence. 相似文献
965.
Tests were conducted by a Task Force on Disinfectant Test Methods that was appointed to investigate controversies regarding the accuracy of AOAC test methods for disinfectants as presented in AOAC's Official Methods of Analysis, Chapter 6. The general principles for new and improved AOAC tests are discussed, and a disinfectant test using microbes labeled onto a polyester fiber surface is described. The quantitative test measures the survival of test microbes as a function of exposure time as well as the exposure conditions required to kill 6 log10 of the test microbes. The time required was similar to that for the kinetics of the kill of Bacillus subtilis-labeled cylinders as tested by methods of the AOAC Sporicidal Test 966.04. 相似文献
966.
Vijgen S Nauwelaerts K Wang J Van Aerschot A Lagoja I Herdewijn P 《The Journal of organic chemistry》2005,70(12):4591-4597
A straightforward approach to a novel class of ribo-type cyclohexenyl nucleosides is described. An electron-demand Diels-Alder reaction forms the key-step of the chosen synthetic pathway. Although the difference is small, conformational analysis using NMR shows that this nucleoside analogue adopts preferentially an 2H3 conformation (S-type), while the "deoxy" cyclohexenyl analogue has a preference for a C3' endo conformation (N-type). Analyses of the conformational equilibrium reveal that, in the given experimental conditions, the difference between adenosine and its cyclohexenyl congener resides in their different DeltaG values; furthermore, in adenosine, the conformational preference is of enthalpic origin, whereas in the cyclohexenyl congener, the conformational preference is of entropic origin. 相似文献
967.
Sara Grecchi Serena Arnaboldi Simona Rizzo Patrizia Romana Mussini 《Current Opinion in Electrochemistry》2021
An increasing number of strategies and tools have been proposed to endow the electrochemical interphase with chirality, to achieve enantiodiscrimination in analytical and/or preparative applications. So far, chirality has mostly been implemented not only at the electrode surface side but also on the medium one. Recently, the attractiveness of the latter approach has remarkably increased on account of the increasing availability of advanced chiral molecular media with intrinsic attractive features for electrochemistry applications, such as chiral ionic liquids, chiral ionic liquid crystals, and chiral deep eutectic solvents. With respect to solid layer/fixed chiral networks, advanced chiral media can still offer a reasonably high degree of local structuring, while being less demanding concerning preparation and management protocols, as well as less sensitive to fouling/regeneration issues. Different ways to implement chirality in advanced molecular media, including cases of powerful ‘inherent chirality,’ will be presented and discussed, particularly focusing on recent applications in the electrochemical field. 相似文献
968.
Electrophoretic conditions to separate sodium dodecyl sulfate (SDS)-protein complexes according to their relative molecular mass by capillary electrophoresis (CE) using linear polyacrylamide as a sieving matrix were examined. Five purified proteins with relative molecular masses between 14 400 and 66 200 Da were separated on a coated fused-silica capillary with an internal diameter of 100 microm and an effective length of 24 cm (total length, 32.5 cm). Benzoic acid was added to the solution of purified proteins as internal standard; beta-mercaptoethanol was also added as reducing agent. The running buffer composition was 0.05 M tris(hydroxymethyl)aminomethane (Tris), 0.035 M aspartic acid, 0.1% m/v SDS, 4% m/v acrylamide, the resulting pH being 8.0. The applied voltage was 7 kV (reversed voltage polarity) in order to avoid high current intensities. Under optimized conditions, the five proteins were separated in less than 15 min, with a % relative standard deviation (RSD) between 0.2 and 0.4 for migration times in the same day. Good efficiency (values between 150 000 and 40 000 N/m) and resolution (values between 2 and 2.8) were obtained. The inverse of relative migration times was found to correlate with the logarithm of their relative molecular mass. Finally, cider proteins were analyzed and their relative molecular masses were determined. These results were compared with those obtained by SDS-polyacrylamide gel electrophoresis (SDS-PAGE). 相似文献
969.
Thorslund S Sanchez J Larsson R Nikolajeff F Bergquist J 《Colloids and surfaces. B, Biointerfaces》2005,46(4):240-247
A new composition of heparin coating for microfluidic systems made out of poly(dimethylsiloxane) (PDMS) was developed and evaluated. The coating that consists of a conditioning polyamine layer followed by two heparin/glutaraldehyde layers, resulted in channel surfaces with sufficient wettability to obtain flow of human normal plasma by capillary force alone. Hydrophilic channel walls are a desirable characteristic in microfluidic devices, since alternative pumping mechanisms must otherwise be included into the system. The immobilized heparin showed high antithrombin-binding capacity and a low degree of blood–material interaction. Plasma in contact with heparin-coated PDMS formed no detectable fibrin in a spectrophotometric assay by which plasma in contact with non-treated PDMS showed complete coagulation. The quartz crystal microbalance technique with energy dissipation monitoring (QCM-D) was utilized to obtain detailed information regarding adsorption kinetics and structural properties of the different layers composing the heparin coating. 相似文献
970.
Fuente A Reyes M Alvarez YM Ruiz JA Vélez H Viñas-Bravo O Montiel-Smith S Meza-Reyes S Sandoval-Ramírez J 《Magnetic resonance in chemistry : MRC》2005,43(8):676-678
(1)H and (13)C NMR spectroscopic data for 5alpha-androstanes and halo-5alpha-androstanes with different substituents at positions C-3, C-9, C-11 and C-17 were examined and assigned by a combination of 1D and 2D NMR experiments. The substituent effects on the (13)C chemical shifts were compared with those of epi-androsterone, used as a reference compound. The coupling constants (n)J((19)F,(13)C) were measured for compounds 6, 8, 11 and 14. 相似文献