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111.
Eduljee, G.H. and McDermott, C., 1984. Estimating the maximum coordination number for spheres of different sizes. Fluid Phase Equilibria, 18: 103–108.The maximum coordination number is determined from a physical model in which the coordinatng spheres are packed on the surface of the central sphere to form a series of triangles. The efficiency of packing is given by a parameter α, which is 60° for the closest possible packing and greater than 60° for looser packing. The model is applied to computer-simulated coordination number data using the principles of spherical trigonometry to obtain a value of α that provides the best match. The results compare favourably with those of empirical fitting equations. 相似文献
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Vandali AE Sucher C Tsang DJ McKay CM Chew JW McDermott HJ 《The Journal of the Acoustical Society of America》2005,117(5):3126-3138
Pitch ranking of sung vowel stimuli, separated in fundamental frequency (F0) by half an octave, was measured with a group of eleven Nucleus 24 cochlear implant recipients using different sound coding strategies. In three consecutive studies, either two or three different sound coding strategies were compared to the Advanced Combinational Encoder (ACE) strategy. These strategies included Continuous Interleaved Sampling (CIS), Peak Derived Timing (PDT), Modulation Depth Enhancement (MDE), F0 Synchronized ACE (FOSync), and Multi-channel Envelope Modulation (MEM), the last four being experimental strategies. While pitch ranking results on average were poor compared to those expected for most normal hearing listeners, significantly higher scores were obtained using the MEM, MDE, and FOSync strategies compared to ACE. These strategies enhanced coding of temporal F0 cues by providing deeper modulation cues to F0 coincidentally in time across all activated electrodes. In the final study, speech recognition tests were also conducted using ACE, CIS, MDE, and MEM. Similar results among all strategies were obtained for word tests in quiet and between ACE and MEM for sentence tests in noise. These findings demonstrate that strategies such as MEM may aid perception of pitch and still adequately code segmental speech features as per existing coding strategies. 相似文献
114.
In structural studies of cytochrome P450 enzymes, substrates have been seen to bind in a variety of modes; it is important to identify those with the closest resemblance to the configurations adopted during selective oxidation. We attempt here to identify conditions in which the catalytic binding mode of cytochrome P450 BM-3 saturated with N-palmitoylglycine is highly populated. When the substrate binds directly atop the heme, primed for oxidation, displacement of the water ligand is necessary, and thereby the ferric heme is generally converted from low-spin to high-spin. Using both optical spectroscopy and solid-state nuclear magnetic resonance, studying both the full-length enzyme and the isolated heme domain, we show that a high population of the high-spin form is seen at room temperature and above, but not at reduced temperatures. In contrast, the reduced state exhibits high spin throughout the temperature range. The isotropic chemical shift of deuterons in the substrate bound to the oxidized and reduced forms of the enzyme was temperature-dependent, consistent with the presence of a nearby paramagnetic center, but temperature-independent for the diamagnetic CO-bound form, and for the free form of the compound. The reduced (ferrous heme) species shows Curie law dependence of the2H substrate chemical shift with respect to temperature from ?54 to +35 °C, but the oxidized (ferric heme) species showed a pronounced non-Curie dependence in both the2H and the13C shift of the substrate’s methyl group, with the effect of the paramagnetic heme at low temperatures being much reduced. These data are consistent with a mixture of at least two binding modes in rapid equilibrium wherein the heme is high-spin at room temperature but low-spin at cryogenic temperatures. 相似文献
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Biomimetic arrays of oriented helical ZnO nanorods and columns 总被引:5,自引:0,他引:5
Tian ZR Voigt JA Liu J McKenzie B McDermott MJ 《Journal of the American Chemical Society》2002,124(44):12954-12955
Extended helical or chiral nanostructures are usually associated with biomolecules but are mostly absent in synthetic materials. Here we report the first synthesis of unusual oriented and extended helical nanostructures in synthetic ceramics. Large arrays of oriented helical ZnO nanorods and columns are formed using simple citrate ions to control the growth habits of the ZnO crystal. This novel mechanism could lead to new approaches to control the orientation, the surface area, and the defect structure of synthetic materials that are critical for practical applications. The morphology generated in the helical ZnO nanostructure shows remarkable resemblance to the growth morphology of nacreous calcium carbonate and thus may shed new light on morphology and orientation control of biominerals. 相似文献
118.
Marulanda D Tasayco ML McDermott A Cataldi M Arriaran V Polenova T 《Journal of the American Chemical Society》2004,126(50):16608-16620
De novo site-specific backbone and side-chain resonance assignments are presented for U-15N(1-73)/U-13C,15N(74-108) reassembly of Escherichia coli thioredoxin by fragment complementation, determined using solid-state magic angle spinning NMR spectroscopy at 17.6 T. Backbone dihedral angles and secondary structure predicted from the statistical analysis of 13C and 15N chemical shifts are in general agreement with solution values for the intact full-length thioredoxin, confirming that the secondary structure is retained in the reassembled complex prepared as a poly(ethylene glycol) precipitate. The differential labeling of complementary thioredoxin fragments introduced in this work is expected to be beneficial for high-resolution structural studies of protein interfaces formed by protein assemblies by solid-state NMR spectroscopy. 相似文献
119.
Site-specific assignments for the solid-state NMR spectra of uniformly 13C,15N-enriched ubiquitin are described. The assignments are derived from three three-dimensional 15N-13C-13C correlation spectra collected at 400 MHz on microcrystalline material. A few residues (the loop near Threonine 9 and the C-terminal fragment) were missing and correspond to regions previously reported to be mobile on the basis of X-ray crystallography and solution NMR studies. A few additional sites exhibit shifts that differ from previously reported solution NMR assignments. Nonetheless, these de novo assignments indicate close agreement between the chemical shifts observed in solution and those in microcrystalline or precipitated solids. The methods utilized are likely to be generally applicable for other noncrystalline, nonsoluble proteins. 相似文献
120.
Geoffrey P. McDermott Elspeth K. Bowen Michaela M. Cooke Xavier A. Conlan Neil W. Barnett Paul S. Francis 《Analytica chimica acta》2009,634(2):222-12741
Previous studies have suggested that tris(4,7-diphenyl-1,10-phenanthrolinedisulfonate)ruthenium(II) (Ru(BPS)34−) has great potential as a chemiluminescence reagent in acidic aqueous solution. We have evaluated four different samples of this reagent (two commercially available and two synthesised in our laboratory) in comparison with tris(2,2′-bipyridine)ruthenium(II) (Ru(bipy)32+) and tris(1,10-phenanthroline)ruthenium(II) (Ru(phen)32+), using a range of structurally diverse analytes. In general, Ru(BPS)34− produced more intense chemiluminescence, but the oxidised Ru(BPS)33− species is less stable in aqueous solution than Ru(bipy)33+ and produced a greater blank signal than Ru(bipy)33+ or Ru(phen)33+, which had a detrimental effect on sensitivity. Although the complex is often depicted with the sulfonate groups of the BPS ligand in the para position on the phenyl rings, NMR characterisation revealed that the commercially available BPS material used in this study was predominantly the meta isomer. 相似文献