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91.
Andersson M Hedin J Johansson P Nordström J Nydén M 《The journal of physical chemistry. A》2010,114(50):13146-13153
Synthetic imidazole ligands are typically substituted at the N(1) ((1)-Im) position while natural imidazole ligands are substituted at the C(4) ((4)-Im) position. To outline the difference in coordination properties, the methyl-substituted imidazoles Me(4)-Im and Me(1)-Im were complexed with CuCl(2) and ZnCl(2) and investigated by NMR relaxometry, electron paramagnetic resonance, far-Fourier transform IR vibrational spectroscopy, and ab initio calculations. Me(4)-Im, Me(1)-Im, and Im in excess form the usual tetragonal D(4h) [CuL(4)X(2)] complexes with CuCl(2) whereas the methylated imidazoles form pseudotetrahedral C(2v) complexes instead of the usual octahedral O(h) [ZnIm(6)](2+) complex. All imidazoles display a high degree of covalence in the M-L σ- and π-bonds and the π-interaction strength affects the relative energies of complexation. Opportunities to tailor complexes by the chemical properties of the substituents are envisaged due to the role of the inductive and hyperconjugative effects, rather than position. 相似文献
92.
Magnus Rogeberg Steven Ray WilsonTyge Greibrokk Elsa Lundanes 《Journal of chromatography. A》2010,1217(17):2782-2786
Porous layer open tubular (PLOT) polystyrene divinylbenzene columns have been used for separating intact proteins with gradient elution. The 10 μm I.D. × 3 m columns were easily coupled to standard liquid chromatography–mass spectrometry (LC–MS) instrumentation with commercially available fittings. Standard proteins separated on PLOT columns appeared as narrow and symmetrical peaks with good resolution. Average peak width increased linearly with gradient time (tG) from 0.14 to 0.33 min (tG 20 and 120 min, respectively) using a 3 m column. With shorter columns, peak widths were larger and increased more steeply with gradient time. Theoretical peak capacity (nc) increased with column length (tested up to 3 m). The nc increased with tG until a plateau was reached. The highest peak capacity achieved (nc = 185) was obtained with a 3 m column, where a plateau was reached with tG 90 min. The within- and between column retention time repeatabilities were below 0.6% and below 2.5% (relative standard deviation, RSD), respectively. The carry-over following injection of 0.5 ng per protein was less than 1.1%. The retention time dependence on column temperature was investigated in the range 20–50 °C. Proteins in a skimmed milk sample were separated using the method. 相似文献
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We reformulate the leaky mode condition of planar Bragg waveguides as two simple, separate conditions on the propagation constant; a phase match condition and a loss formula. These relations enable efficient numerical calculations of the mode properties. Furthermore, we use the phase match condition as a starting point to discuss the dispersion of waveguides with advanced cladding structures. In particular, we point out that chirped claddings, where the effective reflection point is dependent on frequency, do not give dispersion characteristics significantly different from metallic waveguides or waveguides with periodic claddings. 相似文献
96.
The efficiency of thermoelectric power generators and the coefficient of performance of thermoelectric refrigerators increase rapidly in the region of small ZT, and then level off to a flat curve in the region of large ZT, where ZT is the figure of merit. Therefore, simply because one-dimensional thermoelectric materials have high ZT predicted theoretically does not imply that efficient thermoelectric devices can be built with such one-dimensional systems. Our numerical analysis, based on the fundamental thermodynamics which is independent of material systems, with emphasis on energy transport has confirmed this conjecture. 相似文献
97.
Ortho‐Quinone Methides as Reactive Intermediates in Asymmetric Brønsted Acid Catalyzed Cycloadditions with Unactivated Alkenes by Exclusive Activation of the Electrophile
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MSc. Chien‐Chi Hsiao Dr. Sadiya Raja MSc. Hsuan‐Hung Liao Prof. Dr. Magnus Rueping 《Angewandte Chemie (International ed. in English)》2015,54(19):5762-5765
An efficient method for the highly enantioselective synthesis of chiral chromanes bearing multiple stereogenic centers was developed. A chiral BINOL‐based N‐triflylphosphoramide proved to be an effective catalyst for the in situ generation of ortho‐quinone methides (o‐QMs) and their subsequent cycloaddition reaction with unactivated alkenes provided chromanes with excellent diastereo‐ and enantioselectivity. 相似文献
98.
Trifa M. Ahmed Christoffer Bergvall Magnus Åberg Roger Westerholm 《Analytical and bioanalytical chemistry》2015,407(2):427-438
The objective of this study was to develop a novel analytical chemistry method, comprised of a coupled high-performance liquid chromatography–gas chromatography/mass spectrometry system (LC–GC/MS) with low detection limits and high selectivity, for the identification and determination of oxygenated polycyclic aromatic hydrocarbons (OPAHs) and polycyclic aromatic hydrocarbons (PAHs) in urban air and diesel particulate matter. The linear range of the four OPAHs, which include 9,10-anthraquinone, 4H-cyclopenta[def]phenanthrene-4-one, benzanthrone, and 7,12-benz[a]anthraquinone, was 0.7 pg–43.3 ng with limits of detection (LODs) and limits of quantification (LOQs) on the order of 0.2–0.8 and 0.7–1.3 pg, respectively. The LODs in this study are generally lower than values reported in the literature, which can be explained by using large-volume injection. The recoveries of the OPAHs spiked onto glass fiber filters using two different pressurized liquid extraction (PLE) methods were in the ranges of 84–107 and 67–110 %, respectively. The analytical protocols were validated using the following National Institute of Standards and Technology standard reference materials: SRM 1649a (Urban Dust), SRM 1650b (Diesel Particulate Matter), and SRM 2975 (Diesel Particulate Matter, Industrial Forklift). The measured mass fractions of the OPAHs in the standard reference materials (SRMs) in this present study are higher than the values from the literature, except for benzanthrone in SRM 1649a (Urban Dust). In addition to the OPAHs, 44 PAHs could be detected and quantified from the same particulate extract used in this protocol. Using data from the literature and applying a two-sided t test at the 5 % level using Bonferroni correction, significant differences were found between the tested PLE methods for individual PAHs. However, the measured mass fractions of the PAHs were comparable, similar to, or higher than those previously reported in the literature. 相似文献
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100.
Nicola Bellomo Nils Calander Eugen Mamontov Magnus Willander 《Comptes Rendus Mecanique》2003,331(7):461-467