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81.
H. D. Beckstead G. A. Neville H. F. Shurvell 《Fresenius' Journal of Analytical Chemistry》1993,345(11):727-732
Summary Five solvates of spironolactone were prepared by crystallization from absolute methanol, acetonitrile, absolute ethanol, ethyl acetate, and benzene, and characterized by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and by FT-Raman spectroscopy. Of these solvates, all were found to be monosolvated except that formed with acetonitrile which gave a spironolactone-acetonitrile (2:1) complex as determined by elemental microanalysis. Distinctive IR and Raman spectral features of the solvates are discussed. Remarkable similarity is seen in the Raman spectra (1800–400 cm–1) of the solvates obtained from methanol, ethanol, and ethyl acetate. The Raman spectrum of the benzene solvate is particularly useful for showing the presence of benzene because of the very intense band near 1000 cm–1 which is unique to the Raman effect.Presented at the 36th Canadian Spectroscopy Conference, 1–3 August 1990, at Brock University, St. Catharines, ON, Canada 相似文献
82.
Protein-protein interactions play an essential role in the assembly of the macromolecular complexes that form functional networks and control cellular behavior. Elucidating principles of molecular recognition governing potentially complex interfaces is a challenging goal for structural and systems biology. Extensive studies of alpha-helical coiled coils have provided fundamental insight into the determinants of one seemingly tractable class of oligomeric protein interfaces. We report here that two different valine-containing mutants of the GCN4 leucine zipper that fold individually as four-stranded coiled coils associate preferentially in mixtures to form an antiparallel, heterotetrameric structure. X-ray crystallographic analysis reveals that the coinciding hydrophobic interfaces of the hetero- and homotetramers differ in detail, thereby controlling their partnering and structural specificity. Equilibrium disulfide exchange and thermal denaturation experiments show that the 50-fold preference for heterospecificity is determined by interfacial van der Waals interactions and hydrophobicity. Parallel studies of two alanine-containing variants confirm the above-mentioned interpretation of the basis and mechanism of this heterospecificity. Our results suggest that coiled-coil recognition is an inherently geometric process in which heterotypic interaction specificity derives from a complementarity of both shape and chemistry. 相似文献
83.
Bhosale SV Bissett MA Forsyth C Langford SJ Neville SM Shapter JG Weeks L Woodward CP 《Organic letters》2008,10(14):2943-2946
A crystallography-instructed strategy to highly ordered layering of porphyrins with different topologies on HOPG is developed based on meso-tetraarylporphyrins bearing 2-ethoxyethanol side chains as "sticky ends". These sticky ends are capable of displaying directive hydrogen bonding motifs with the inherent D4h symmetry of the porphyrins. Solvent effects are shown to have an important role in fabricating the adsorption. Metalation and subsequent axial ligation was a key controlling factor in the topology of the layer, leading to pseudo-2D structures on HOPG. 相似文献
84.
Anion-solvent dependence of bistability in a family of meridional N-donor-ligand-containing iron(II) spin crossover complexes 总被引:1,自引:0,他引:1
Leita BA Neville SM Halder GJ Moubaraki B Kepert CJ Létard JF Murray KS 《Inorganic chemistry》2007,46(21):8784-8795
Five mononuclear spin crossover iron(II) bis-meridional ligand complexes of the general formula [Fe(L)(2)](X)(2).solvent, have been synthesized, where X = BF(4)- or ClO(4)-; L = 2-(1-pyridin-2-ylmethyl-1H-pyrazol-3-yl)-pyrazine (picpzpz) or 2-(3-(2-pyridyl)pyrazol-1-ylmethyl)pyridine) (picpypz); solvent = MeOH or EtOH. The magnetic and structural consequences of systematic variation of meridional ligand, solvent, and anion, including a desolvated species, have been investigated. The complex [Fe(picpzpz)(2)](BF(4))(2).MeOH, 1.MeOH, displays several unique properties including a two-step spin transition with a gradual higher-temperature step ((1)T(1/2) = 197 K) and an abrupt low-temperature step with hysteresis ((2)T(1/2) = 91/98 K) and a metastable intermediate spin state below 70 K with quench-cooling. Removal of the solvent methanol results in the loss of the abrupt step and associated hysteresis (T(1/2) = 150 K). The complexes [Fe(picpzpz)(2)](BF(4))(2).EtOH (1.EtOH), [Fe(picpzpz)(2)](ClO(4))(2).MeOH (2.MeOH), [Fe(picpzpz)(2)](ClO(4))(2).EtOH (2.EtOH), and [Fe(picpypz)(2)](BF(4))(2).MeOH (3.MeOH) all show gradual one-step spin transitions with T(1/2) values in the range 210-250 K. Photomagnetic LIESST measurements on 1.MeOH reveal a near-quantitative excitation of high-spin sites and a unique two-step relaxation process related to the two-step thermal spin transition ((1)T(LIESST) = 49 K and (2)T(LIESST) = 70 K). The structural consequences of the unusual spin transition displayed by 1.MeOH have been investigated by single-crystal X-ray diffraction structural analyses between 25 and 293 K. Detailed characterization of the unit cell parameter evolution vs temperature reflects both the gradual high-temperature step and abrupt low-temperature step, including the thermal hysteresis, observed magnetically. 相似文献
85.
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88.
Smith J Rey G Dickens P Fletcher N Hollenberg L Wolfe J 《The Journal of the Acoustical Society of America》2007,121(1):547-558
Traditional didjeridus have a broad range of bore geometries with many details not immediately apparent to a player, and are therefore suitable for examining the relationship between perceived quality and physical properties. Seven experienced players assessed the overall playing quality of 38 didjeridus that spanned a wide range of quality, pitch, and geometry, as well as 11 plastic cylindrical pipes. The ranking of these instruments was correlated with detailed measurements of their acoustic input impedance spectra. Most significantly, the ranked quality of a didjeridu was found to be negatively correlated with the magnitude of its acoustic input impedance, particularly in the frequency range from 1 to 2 kHz. This is in accord with the fact that maxima in the impedance of the player's vocal tract can inhibit acoustic flow, and consequently sound production, once the magnitude of these impedance maxima becomes comparable with or greater than those of the instrument. This produces the varying spectral peaks or formants in the sound envelope that characterize this instrument. Thus an instrument with low impedance and relatively weak impedance maxima in this frequency range would allow players greater control of the formants in the output sound and thus lead to a higher perceived playing quality. 相似文献
89.
The heat of lysozyme adsorption on mesostructured cellular foam (MCF) silica was measured using flow microcalorimetry (FMC) to investigate the influence of a neutral salt, sodium sulfate. At concentrations up to 0.5 M sodium sulfate, a complex initial exotherm was followed by an endotherm. Protein surface coverage, the magnitudes of the exothermic heat signals and the magnitudes of the net heat of adsorption increased with sodium sulfate concentration. These observations suggest that electrostatic interactions are the principal driving force at low ionic strengths; van der Waals interactions become dominant at higher salt concentrations. Each exotherm could be deconvoluted into two exotherms, indicating multiple modes of lysozyme attachment to the silica surface. The endothermic peak, associated with protein desorption, disappeared at the highest sodium sulfate concentration (1.0 M), indicating irreversible adsorption of the protein on the MCF silica surface. The data are consistent with an adsorption mechanism in which the initial attachment of lysozyme to the surface is followed by a reorientation and formation of a secondary or stronger attachment to the surface. 相似文献
90.