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211.
Amrani A Ma Q Ahmad WS Aizenshtat Z Tang Y 《Chemical communications (Cambridge, England)》2008,(11):1356-1358
(34)S enrichment is shown to occur during sulfurization reactions and for the first time conclusively attributed to an isotope equilibrium effect rather than selective addition of (34)S enriched nucleophiles. 相似文献
212.
213.
Lafon O Lesot P Zimmermann H Poupko R Luz Z 《The journal of physical chemistry. B》2007,111(32):9453-9467
We report 2H and 13C NMR spectra of the crown and saddle isomers of nonamethoxy-tribenzocyclononene (1), dissolved in lyotropic achiral and chiral liquid-crystalline solutions based on poly-gamma-benzyl-glutamate and poly-gamma-benzyl-L-glutamate (PBG and PBLG). The 2H-[1H] measurements include spectra of compound 1 deuterated in the ring methylene and in the aromatic sites as well as of the methyl groups in natural abundance. Carbon-13 spectra were recorded in natural abundance as well as in two isotopomers enriched in the ring methylene and one of the methoxy groups. The crown isomer (c-1) is rigid with C3 symmetry and can be separated into its enantiomers using a chiral high-performance liquid chromatography column. The NMR spectra of racemic c-1 in PBLG solutions exhibit two sets of lines due to the enantiomers. The peaks were identified by comparing the spectra with those of the neat enantiomers. Analysis of the 2H quadrupolar splittings and the 13C residual chemical shift anisotropies shows that the dominant factor determining the chiral discrimination is the difference in the ordering of the two enantiomers in the chiral liquid crystals. The saddle isomer (s-1) is highly flexible, undergoing fast pseudorotation between six conformers. The "frozen" conformers have C1 symmetry and are therefore chiral. Three of these comprise one enantiomer, and the other three the second one. However, the rapidly interconverting species has, on the average, a C3h symmetry and is therefore achiral. The methylene groups in the latter are, however, prostereogenic, and their hydrogen/deuterium-carbon bonds constitute enantiotopic pairs. The 2H NMR spectra of the s-1 methylene-deuterated in PBLG solutions exhibit, in fact, enantio-discrimination with two quadrupolar doublets. This is in contrast to rigid prochiral molecules with a threefold symmetry axis, which normally do not show such discrimination. A detailed analysis of the effect is presented, and it is argued that the discrimination observed for s-1 reflects the different ordering of its enantiomers during the pseudorotation cycle. 相似文献
214.
On shredders and vertex connectivity augmentation 总被引:1,自引:0,他引:1
We consider the following problem: given a k-(node) connected graph G find a smallest set F of new edges so that the graph G+F is (k+1)-connected. The complexity status of this problem is an open question. The problem admits a 2-approximation algorithm. Another algorithm due to Jordán computes an augmenting edge set with at most (k−1)/2 edges over the optimum. CV(G) is a k-separator (k-shredder) of G if |C|=k and the number b(C) of connected components of G−C is at least two (at least three). We will show that the problem is polynomially solvable for graphs that have a k-separator C with b(C)k+1. This leads to a new splitting-off theorem for node connectivity. We also prove that in a k-connected graph G on n nodes the number of k-shredders with at least p components (p3) is less than 2n/(2p−3), and that this bound is asymptotically tight. 相似文献
215.
Luz Z Poupko R Wachtel EJ Zheng H Friedman N Cao X Freedman TB Nafie LA Zimmermann H 《The journal of physical chemistry. A》2007,111(42):10507-10516
The paper concerns the structural and optical isomers of nonamethoxy-tribenzocyclononene (compound 1). In the first part of the paper it is shown that 1 exists in two structural isomers: a rigid crown (c-1) with C3 symmetry and a flexible saddle (s-1) with C1 symmetry. The latter, not previously known, can be prepared from the as-synthesized c-1 by quenching a hot solution (or the melt) followed by HPLC separation. The crown/saddle equilibrium, isomerization kinetics, and associated thermodynamic parameters in various organic solvents are reported. Carbon-13 MAS NMR, X-ray diffraction, and differential scanning calorimetry (DSC) of polycrystalline c-1 and s-1 racemates are also reported. The different melting points of the isomers and their rapid isomerization in the melt result in unconventional DSC thermograms involving multiple endothermic and exothermic transitions. The second part of the paper concerns the chiral properties of 1. Both the saddle and crown isomers are structurally chiral, but due to the fast pseudorotation of s-1 in solution, it cannot be separated into its enantiomers. Those of c-1 were separated by HPLC using a chiral column. Their X-ray structure and melting points differ considerably from those of the racemate. This and their fast racemization in the melt lead to complex DSC thermograms with multiple transitions. Solutions of the neat enantiomers exhibit a relatively small specific optical rotation. In the UV they show circular dichroism for the B1u and B2u transitions, with the latter exhibiting a clear couplet structure. Infrared and vibrational circular dichroism spectra of the enantiomers in solution are reported. Comparison of these spectra with quantum mechanical simulations provides unambiguous identification of the enantiomers. 相似文献
216.
Quach AD Crivat G Tarr MA Rosenzweig Z 《Journal of the American Chemical Society》2011,133(7):2028-2030
The paper describes the development of highly sensitive particle-based fluorescence resonance energy transfer (FRET) probes that do not use molecular fluorophores as donors and acceptors. In these probes, CdSe/ZnS luminescent quantum dots (QDs) were capped with multiple histidine-containing peptides to increase their aqueous solubility while maintaining their high emission quantum yield and spectral properties. The peptide-modified QDs (QD-His) were covalently attached to carboxyl-modified polystyrene (PS) microspheres to form highly emitting PS microspheres (QD-PS). Gold nanoparticles (AuNPs) were then covalently attached to the QD-PS surface to form AuNP-QD-PS composite microspheres that were used as FRET probes. Attachment of AuNPs to QD-PS completely quenched the QD emission through FRET interactions. The emission of QD-PS was restored when the AuNPs were removed from the surface by thiol ligand displacement. The new AuNP-QD-PS FRET platform is simple to prepare and highly stable, and it opens many new possibilities for carrying out FRET assays on microparticle-based platforms and in microarrays. The versatility of these assays could be greatly increased by replacing the linkers between the QDs and AuNPs with ones that selectively respond to specific cleaving agents or enzymes. 相似文献
217.
De Paoli VM De Paoli Lacerda SH Spinu L Ingber B Rosenzweig Z Rosenzweig N 《Langmuir : the ACS journal of surfaces and colloids》2006,22(13):5894-5899
The paper describes the effect of an oscillating magnetic field (OMF) on the morphology and release properties of collagen gels containing magnetic nanoparticles and microparticles and fluorescent drug analogues. Collagen gels were prepared through fibrillogenesis of collagen in the presence of iron oxide magnetic particles averaging 10 nm or 3 mum in diameter and rhodamine-labeled dextran (Dex-R) of molecular weights between 3000-70 000 g/mol. Dextran molecules effectively simulate protein-based drugs, since they have similar molecular weights and dimensions. The paper discusses the effect of an OMF on the release properties of the gels and proposes an empirical model to predict the release rate. It also demonstrates the self-repair capability of collagen gels following the structural damage caused by an OMF. 相似文献
218.
We present a new configuration for superresolution (SR) as well as for field-of-view (FOV) extension in a digital holography concept based on random movement of sparse metallic particles. In the SR configuration, the particles are in proximity to the recorded object, while in the FOV configuration, the particles are in proximity to the hologram plane. The particles' movement encodes the high spatial features in the plane of their movement. This high-resolution information can later be decoded by proper numerical postprocessing that either remedies the resolution limitations in the object plane (or the limited NA of the lens) or extends the FOV in the object plane. 相似文献
219.
The kinetics of gamma-radiation-induced free-radical reactions in carbon tetrachloride solutions of ethanol and n-pentanol were studied in the range of 0.05–0.80M and 25–170°C. The rate constant for the reaction was found as The activation energy is larger by 0.8 kcal/mol than for secondary alcohols, while the A1 factors are about the same. 相似文献
220.