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81.
Density functional modelling of silicate and aluminosilicate dimerisation solution chemistry 总被引:1,自引:0,他引:1
White CE Provis JL Kearley GJ Riley DP van Deventer JS 《Dalton transactions (Cambridge, England : 2003)》2011,40(6):1348-1355
Common throughout sol-gel chemistry, including zeolite synthesis, aluminosilicate glass formation and geopolymerisation, is the process of inorganic oxide polymerisation and deprotonation. In this investigation, some of the fundamental reactions occurring during zeolite synthesis and geopolymerisation at high pH are investigated using density functional theory (DFT), and are compared with: (i) existing values reported in the literature, and (ii) new and previously published DFT-derived data for similar silicate reactions at near-neutral pH. From the results it is seen that the energetics of deprotonation and dimerisation reactions depend greatly on the pH value, and these results correlate well with existing experimental values and trends. Hence, this investigation exemplifies that an accurate replication of the solution environment is crucial for obtaining useful theoretical results for species dissolved in non-ideal environments. 相似文献
82.
The characterization and determination of peptides is of great importance in the pharmaceutical industry as is the ability to rapidly perform targeted determinations of bioactive peptides in complex matrices. The purpose of the presented work is to assess the feasibility of packed column supercritical fluid chromatography (SFC) for the separation of two-pairs of water soluble peptides of identical mass, composition and charge that differ only in amino acid sequence. Upon evaluating a variety of conditions, trifluoroacetic acid (HTFA) in conjunction with methanol as the modifier proved to be, in general, the most successful mobile phase additive for elution of the two isomeric peptide pairs from all nitrogenous stationary phases. In contrast, water and ammonium acetate gave distorted peak shapes and therefore proved to be less satisfactory as neutral additives. The basic additive, iso-propylamine (IPAm), coupled with HA-Pyridine yielded the highest resolution factor for the complete study. Aminopropyl and HA-Pyridine columns with 5 μm particle size and 60 Å pore size were found to be best for resolution of each peptide pair. Bare silica and phenyl-hexyl stationary phases did not afford any separation. The primary roles of the carbon dioxide and methanol modifier are believed to provide (a) stationary phase solvation and (b) peptide solubility and transport; while, HTFA is postulated to fully protonate each peptide and form ion pairs between its conjugate base and cationic peptide analyte. The separation process, therefore, is best viewed as ion pair supercritical fluid chromatography (IP-SFC). For the case where IPAm gave good resolution on the HA-Pyridine column, the peptides are probably in the neutral state. 相似文献
83.
Simmons CJ Stratemeier H Hitchman MA Reinen D Masters VM Riley MJ 《Inorganic chemistry》2011,50(11):4900-4916
The crystal structures of trans-diaquabis(methoxyacetato)copper(II) and the isostructural nickel(II) complex have been determined over a wide temperature range. In conjunction with the reported behavior of the g-values, the structural data suggest that the copper(II) compound exhibits a thermal equilibrium between three structural forms, two having orthorhombically distorted, tetragonally elongated geometries but with the long and intermediate bonds to different atoms, and the third with a tetragonally compressed geometry. This is apparently the first reported example of a copper(II) complex undergoing an equilibrium between tetragonally elongated and compressed forms. The optical spectrum of single crystals of the copper(II) compound is used to obtain metal-ligand bonding parameters which yield the g-values of the compressed form of the complex and hence the proportions of the complex in each structural form at every temperature. When combined with estimates of the Jahn-Teller distortions of the different forms, the latter produce excellent agreement with the observed temperature dependence of the bond lengths. The behavior of an infrared combination band is consistent with such a thermal equilibrium, as is the temperature dependence of the thermal ellipsoid parameters and the XAFS. The potential surfaces of the different forms of the copper(II) complex have been calculated by a model based upon Jahn-Teller coupling. It is suggested that cooperative effects may cause the development of the population of tetragonally compressed complexes, and the crystal packing is consistent with this hypothesis, though the present model may oversimplify the diversity of structural forms present at high temperature. 相似文献
84.
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86.
A rapid single-reagent spectrofluorimetric assay for salicylate in human blood plasma is reported. The method is based on ternary complex formation with terbium and EDTA in alkaline solution; it requires only 10 μl of plasma, and protein precipitation is not necessary. Within-assay relative standard deviations were better than 2.5%, and correlation with the Trinder method was excellent. The procedure is particularly suited for emergency use in cases of suspected aspirin poisoning. 相似文献
87.
Koichi Omori Ashutosh Kacker Linda M. Carroll William D. Riley Stanley M. Blaugrund 《Journal of voice》1996,10(3):228-235
This paper presents a parameter for objectively evaluating singing voice quality. Power spectrum of vowel sound / a / was analyzed by Fast Fourier Transform. The greatest harmonics peak between 2 and 4 kHz and the greatest harmonics peak between 0 and 2 kHz were identified. Power ratio of these peaks, termed singing power ratio (SPR), was calculated in 37 singers and 20 nonsingers. SPR of sung / a / in singers was significantly greater than in nonsingers. In singers, SPR of sung / a / was significantly greater than that of spoken / a /. By digital signal processing, power spectrum of sung / a / was varied, and the processed sounds were perceptually analyzed. SPR had a significant relationship with perceptual scores of “ringing” quality. SPR provides an important quantitative measurement for evaluating singing voice quality for all voice types, including soprano. 相似文献
88.
89.
Noakes C. J.; King J. R.; Riley D. S. 《The Quarterly Journal of Mechanics and Applied Mathematics》2006,59(2):163-190
Analysis of thin-film rimming and coating flows is extendedto create a more general model, which can be identified as anew distinguished limit that has the work of certain previousstudies as specific limiting cases. Specifically, three-dimensionalflows under the influence of gravity are considered in whichthe Reynolds number is large enough to necessitate considerationof both inertial and centrifugal effects, along with those ofviscous, gravitational and surface-tension forces. Reductionof dimensionality is shown to be attainable within a systematic(multiple-timescale) asymptotic framework that encompasses allthese effects, leading to a two-dimensional formulation thatnot only is more general than many of the existing ones butalso represents a rational approximation in the sense that,in particular, the sizes of the dimensionless physical parametersto which it corresponds, together with the orders of magnitudeof the errors resulting from the reduction, can be preciselycharacterized. 相似文献
90.
Norman Riley 《Zeitschrift für Angewandte Mathematik und Physik (ZAMP)》1978,29(3):439-449
Summary The steady streaming velocity induced by the circular motion of a cylinder of elliptic cross-section in a viscous fluid is considered. The amplitude of this circular motion is supposed small compared with a typical diameter of the cylinder, which maintains a fixed orientation throughout the motion. Outside the Stokes shear-wave layer Reynolds stresses contribute to the induced steady streaming. The outer flow is calculated in the case of large streaming Reynolds numbers for two particular cylinders.
Zusammenfassung Es wird die stationäre Strömung untersucht, die durch die kreisförmige Bewegung eines Zylinders mit elliptischem Querschnitt in einer zähen Flüssigkeit induziert wird. Die Amplitude dieser Kreisbewegung wird als klein angenommen gegenüber den Halbachsen der Ellipse, deren Orientierung während der Bewegung unverändert bleibt. Ausserhalb der Stokes-Schicht tragen die Reynolds-Spannungen zur Induzierten stationären Strömung bei. Die äussere Strömung wird im Falle von grossen Reynolds-Zahlen der Strömung für zwei besondere Zylinder berechnet.相似文献