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61.
J. N. Spencer Travis F. Ganunis Abrahim I. Zafar Shaym Puppala James L. Ealy Larry J. Fenton Sunita Gupta C. H. Yoder J. E. Mihalick 《Journal of solution chemistry》1992,21(9):1005-1012
Equilibrium constants and enthalpies of hydrogen-bond formation of mcresol to various cyclic (crown) and acyclic polyethers have been determined in benzene solvent. Equilibrium constants indicated no evidence for an operative macrocyclic effect; the relationship between the increasing size of the equilibrium constant and the number of ether oxygens was rationalized with a simple statistical thermodynamic model. Enthalpies of interactions ranged between –19 and –23 kJ-mol–1. In agreement with PCILO calculations, enthalpies of interaction were essentially independent of the number of oxygen atoms in the ether; no significant difference in enthalpies of interaction between cyclic and acyclic ethers was found. 相似文献
62.
63.
D. Zipse N. S. Dalal R. M. Achey J. M. North S. Hill R. S. Edwards 《Applied magnetic resonance》2004,27(1-2):151-163
High-sensitivity, variable-frequency, high-field electron paramagnetic resonance (EPR) measurements and nuclear magnetic resonance (NMR) measurements are reported for theS=10 single-molecule magnet Fe8Br8. We find that theS=10 state is nested with its first excited state, withS=9, located at only 24±2 K above. Also reported are some preliminary81Br NMR measurements of the unpaired electron spin density on the Br? sites. The results provide new insight and benchmarks for improved electronic and magnetic structural calculations and macroscopic tunneling pathways of this class of single-molecule magnets. 相似文献
64.
Accurate measurement of δISO, the isotropic part of the NMR chemical shift tensor, is usually difficult for solids. This study suggests that the technique of magic angle sample spinning (MAS), employing single crystals, might be suitable for this purpose. In our 13C CP(cross polarization)/MAS measurements on squaric acid (H2C4O4), single crystals yielded about five-fold narrower line widths than powder samples. The resolution enhancement thus obtained enabled us to measure δISO for all four carbons of squaric acid, and to show that the average O-H distance can serve as an order parameter for the phase transition at 373 K. Additionally, the 13C δISO data suggest that the transition mechanism involves a significant displacive component, in addition to the known order-disorder behavior, thus demonstrating the high potential of the single crystal MAS-NMR methodology for studying the microscopic mechanism of phase transitions. 相似文献
65.
Some new heterobimetallic tetraxanthates of the type M[Ag(Etxant)2]2 [M = Co(II) or Ni(II), Etxant = ethylxanthate] and their complexes of general formula M[Ag(Etxant)2]2.xL [x = 2 when L= dimethylsulphoxide (DMSO), triphenylphosphine (Pph3), pyridine(py) or 2-aminopyridine (2-ampy); x = 3 when L = 2,2′-bipyridine (bipy)] have been prepared and characterized by elemental analysis, molar conductance, magnetic susceptibility, infrared and electronic spectral studies. Magnetic and electronic spectral studies indicate square planar geometry around Ni(II) and Co(II) in heterobimetallic tetraxanthates and Ni[Ag(Etxant)2]2.2PPh3 and octahedral geometry around the above metal ions in the remaining complexes. 相似文献
66.
Two hydride-based stationary phases (cholesterol and bidentate C18) are evaluated for use in chromatographic analyses with mass spectroscopic detection. The stability of the bonded moieties and the background signal in the effluent from these columns are investigated. Separations of steroids and catecholamines are used to characterize these separation materials. Peak symmetries and efficiencies can provide additional insights into the effectiveness of the two phases. In one case a small column configuration directly connected to the mass spectrometer inlet is also tested. 相似文献
67.
Several diseases, including atherosclerosis, are characterized by inflammation, which is initiated by leukocyte migration to the inflamed lesion. Hence, genes implicated in the early stages of inflammation are potential therapeutic targets to effectively reduce atherogenesis. Algal-derived polysaccharides are one of the most promising sources for pharmaceutical application, although their mechanism of action is still poorly understood. The present study uses a computational method to anticipate the effect of fucoidan and alginate on interactions with adhesion molecules and chemokine, followed by an assessment of the cytotoxicity of the best-predicted bioactive compound for human monocytic THP-1 macrophages by lactate dehydrogenase and crystal violet assay. Moreover, an in vitro pharmacodynamics evaluation was performed. Molecular docking results indicate that fucoidan has a greater affinity for L-and E-selectin, monocyte chemoattractant protein 1 (MCP-1), and intercellular adhesion molecule-1 (ICAM-1) as compared to alginate. Interestingly, there was no fucoidan cytotoxicity on THP-1 macrophages, even at 200 µg/mL for 24 h. The strong interaction between fucoidan and L-selectin in silico explained its ability to inhibit the THP-1 monocytes migration in vitro. MCP-1 and ICAM-1 expression levels in THP-1 macrophages treated with 50 µg/mL fucoidan for 24 h, followed by induction by IFN-γ, were shown to be significantly suppressed as eight- and four-fold changes, respectively, relative to cells treated only with IFN-γ. These results indicate that the electrostatic interaction of fucoidan improves its binding affinity to inflammatory markers in silico and reduces their expression in THP-1 cells in vitro, thus making fucoidan a good candidate to prevent inflammation. 相似文献
68.
The binding of serum albumin and lipoprotein with chlorin p(6) and purpurin 18, two structurally related chlorins, has been studied to understand the role for these proteins as endogenous carriers for these drugs. As a drug carrier a protein may aid in selective delivery of a drug to a tumor region. Binding with serum albumin may result in accumulation of the drug in the stroma of the tumor cell and lead to a reduction of cellular uptake of photosensitizers. However, it is possible that this factor may not be a problem for cellular uptake of chlorin p(6) and purpurin 18 by the tumor tissues, since it binds more efficiently with low-density lipoprotein when it become more lipophilic, indicating that the principal carriers for these molecules are lipoproteins. Since the tumor tissues contain numerous lipoprotein receptors, chlorin p(6) and purpurin 18 could be internalized more efficiently in tumor cells. 相似文献
69.
This work addresses the analytical and numerical investigations of the transmission performance of an optical Single Sideband (SSB) modulation technique generated by a Mach Zehnder Modulator (MZM) with a 90° and 120° hybrid coupler. It takes into account the problem of chromatic dispersion in single mode fibers in Passive Optical Networks (PON), which severely degrades the performance of the system. Considering the transmission length of the fiber, the SSB modulation generated by maintaining a phase shift of π/2 between the two electrodes of the MZM provides better receiver sensitivity. However, the power of higher-order harmonics generated due to the nonlinearity of the MZM is directly proportional to the modulation index, making the SSB look like a quasi-double sideband (DSB) and causing power fading due to chromatic dispersion. To eliminate one of the second-order harmonics, the SSB signal based on an MZM with a 120° hybrid coupler is simulated. An analytical model of conventional SSB using 90° and 120° hybrid couplers is established. The latter suppresses unwanted (upper/lower) first-order and second-order (lower/upper) sidebands. For the analysis, a varying quadrature amplitude modulation (QAM) Orthogonal Frequency Division Multiplexing (OFDM) signal with a data rate of 5 Gb/s is upconverted using both of the SSB techniques and is transmitted over a distance of 75 km in Single Mode Fiber (SMF). The simulation results show that the SSB with 120° hybrid coupler proves to be more immune to chromatic dispersion as compared to the conventional SSB technique. This is in tandem with the theoretical analysis presented in the article. 相似文献
70.
A short and efficient enantioselective synthesis of the HIV protease inhibitor amprenavir 1 (99% ee) as well as a formal synthesis of saquinavir 3 have been achieved in high enantiomeric purity starting from commercially available materials. Our strategy mainly comprises a Co-catalyzed two-stereocentred hydrolytic kinetic resolution (HKR) of racemic 2-(1-azido-2-phenylethyl)oxirane as the chirality inducing step. Also presented is a concise synthesis of (S)-3-hydroxytetrahydrofuran 4, the key structural feature, in high enantiomeric purity (98% ee). 相似文献