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51.
The enantiomeric excess (ee) can be determined by many methods; one among them is nuclear magnetic resonance in solid-state (SS NMR). In this study we used the SS NMR ODESSA experiment for determination of the ee of valine. 相似文献
52.
Ma H Proctor DJ Kierzek E Kierzek R Bevilacqua PC Gruebele M 《Journal of the American Chemical Society》2006,128(5):1523-1530
The energy landscape of a small RNA tetraloop hairpin is explored by temperature jump kinetics and base-substitution. The folding kinetics are single-exponential near the folding transition midpoint T(m). An additional fast phase appears below the midpoint, and an additional slow phase appears above the midpoint. Stem mutation affects the high-temperature phase, while loop mutation affects the low-temperature phase. An adjusted 2-D lattice model reproduces the temperature-dependent phases, although it oversimplifies the structural interpretation. A four-state free energy landscape model is generated based on the lattice model. This model explains the thermodynamics and multiphase kinetics over the full temperature range of the experiments. An analysis of three variants shows that one of the intermediate RNA structures is a stacking-related trap affected by stem but not loop modification, while the other is an early intermediate that forms some stem and loop structure. Even a very fast-folding 8-mer RNA with an ideal tetraloop sequence has a rugged energy landscape, ideal for testing analytical and computational models. 相似文献
53.
Makal A Benedict J Trzop E Sokolow J Fournier B Chen Y Kalinowski JA Graber T Henning R Coppens P 《The journal of physical chemistry. A》2012,116(13):3359-3365
The excited-state structure of [Cu(I)[(1,10-phenanthroline-N,N') bis(triphenylphosphine)] cations in their crystalline [BF(4)] salt has been determined at both 180 and 90 K by single-pulse time-resolved synchrotron experiments with the modified polychromatic Laue method. The two independent molecules in the crystal show distortions on MLCT excitation that differ in magnitude and direction, a difference attributed to a pronounced difference in the molecular environment of the two complexes. As the excited states differ, the decay of the emission is biexponential with two strongly different lifetimes, the longer lifetime, assigned to the more restricted molecule, becoming more prevalent as the temperature increases. Standard deviations in the current Laue study are very much lower than those achieved in a previous monochromatic study of a Cu(I) 2,9-dimethylphenanthroline substituted complex ( J. Am. Chem. Soc. 2009 , 131 , 6566 ), but the magnitudes of the shifts on excitation are similar, indicating that lattice restrictions dominate over the steric effect of the methyl substitution. Above all, the study illustrates emphatically that molecules in solids have physical properties different from those of isolated molecules and that their properties depend on the specific molecular environment. This conclusion is relevant for the understanding of the properties of molecular solid-state devices, which are increasingly used in current technology. 相似文献
54.
Azothia- and Azoxythiacrown Ethers as Ion Carriers. Part I. Cationic Response of Membrane Electrodes
Katarzyna Wygladacz Elzbieta Malinowska Jolanta Szcztygelska-Tao Jan F. Biernat 《Journal of inclusion phenomena and macrocyclic chemistry》2001,39(3-4):303-307
13-Membered azothia- and azoxythiacrown ethers have been applied as ion carriers in ion-selective membrane electrodes. Their sensitivity and selectivity were studied towards alkali, alkaline earth, transition and heavy metal cations. It was found that membranes doped with the azoxythiacrown ether (A) show higher affinity towards Pb2+ than Cu2+ (log KCu,Pb
pot = 1.7), whereas membranes with the azothiacrown ether (B) are more selective towards Cu2+ than Pb2+ (log KCu,Pb
pot = -2.4). The discrimination of alkali and alkaline earth cations was found to be greater for B than for A. Electrodes with both ionophores suffered from strong interference by Ag+ and Hg2+. The relation between the carrier structure and electrode properties has been discussed. 相似文献
55.
Richard A. Bartsch Charles L. Cowey Sadik Elshani Mi‐Ja Goo Vincent J. Huber Sheryl N. Ivy Russell J. Johnson Jong Seung Kim Elzbieta Luboch Joseph A. Mcdonough Michael J. Pugia Byungki Son Qiang Zhao 《Journal of heterocyclic chemistry》2001,38(2):311-331
Synthetic routes to forty‐seven dibenzo‐16‐crown‐5 compounds with pendant carboxylic acid groups are reported. When taken together with previously described lariat ether carboxylic acids, these new compounds provide several series with systematic structural variations including changes in the identity and attachment site(s) of one or more lipophilic groups and the length of the spacer that connects the carboxylic acid group to the polyether framework. 相似文献
56.
Vitalij A. Chatyrko Elzbieta Pol 《Proceedings of the American Mathematical Society》2000,128(4):1207-1213
In this note we construct a family of continuum many hereditarily strongly infinite-dimensional Cantor manifolds such that for every two spaces from this family, no open subset of one is embeddable into the other.
57.
58.
Janusz Moskal Krzysztof Nagraba Elzbieta Plonek 《Journal of mass spectrometry : JMS》1977,12(7):439-444
The mass spectra of some 1,3- heterodienes containing the 1-oxa-4-aza-butadiene system have been determined and the characteristic fragmentation pathways are discussed. The pathways suggested are supported by the appropriate metastables, the spectra of model compounds and by deuterium labelling. The 1, 3-heterodienes substituted by the thioarylamide group from ions involving participation of the sulphur atom. 相似文献
59.
Marek Pyda Elzbieta Nowak‐Pyda Jimmy Mays Bernhard Wunderlich 《Journal of Polymer Science.Polymer Physics》2004,42(23):4401-4411
The low‐temperature heat capacity of poly(butylene terephthalate) (PBT) was measured from 5 to 330 K. The experimental heat capacity of solid PBT, below the glass transition, was linked to its approximate group and skeletal vibrational spectrum. The 21 skeletal vibrations were estimated with a general Tarasov equation with the parameters Θ1 = 530 K and Θ2 = Θ3 = 55 K. The calculated and experimental heat capacities of solid PBT agreed within better than ±3% between 5 and 200 K. The newly calculated vibrational heat capacity of the solid from this study and the liquid heat capacity from the ATHAS Data Bank were applied as reference values for a quantitative thermal analysis of the apparent heat capacity of semicrystalline PBT between the glass and melting transitions as obtained by differential scanning calorimetry. From these results, the integral thermodynamic functions (enthalpy, entropy, and Gibbs function) of crystalline and amorphous PBT were calculated. Finally, the changes in the crystallinity with the temperature were analyzed. With the crystallinity, a baseline was constructed that separated the thermodynamic heat capacity from cold crystallization, reorganization, annealing, and melting effects contained in the apparent heat capacity. For semicrystalline PBT samples, the mobile‐amorphous and rigid‐amorphous fractions were estimated to complete the thermal analysis. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4401–4411, 2004 相似文献
60.
Wojciech Duczmal Elzbieta Śliwińska Beata Maciejewska Bogdan Marciniec Hieronim Maciejewski 《Transition Metal Chemistry》1995,20(5):435-439
Summary Trisubstituted silanes, HSiR3-n
X
n
(R = Me or Et, X = Cl, OEt, or Ph; n = 0–3) oxidatively add to the complex [RhCl(cod)(1-hexene)] (cod = cycloocta-1,5-diene) to yield [RhCl(cod)(1-hexene)(H)(SiR3)] [(1)]. Subsequent steps of hydrosilylation follow, i.e. cis-insertion of the alkene (- rearrangement) and then reductive elimination of the product, according to the general Chalk and Harrod scheme. A quantitative correlation between the second order rate constant, k
1, of the oxidative addition (followed spectrophotometrically) at 20°C in benzene solution and the structure of the trisubstituted silane represented by Stereoelectronic parameters , and E' for the SiR3-n
X
n
groups was established. The maximal hydrosilylation rate followed by g.l.c., is strongly retarded by highly electronegative substituents X on silicon and results from the elimination rate of the hydrosilylation product from (1) and the maximal concentration of (1) in solution.Dedicated to Professor K. Rühlmann on the occasion of his 65th birthday. Part XXVII in the series Catalysis of Hydrosilylation; for Part XXVI see Polish J. Appl. Chem., 38, 169 (1994). 相似文献