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41.
Malham R Johnstone S Bingham RJ Barratt E Phillips SE Laughton CA Homans SW 《Journal of the American Chemical Society》2005,127(48):17061-17067
The contributions of solute-solute dispersion interactions to binding thermodynamics have generally been thought to be small, due to the surmised equality between solute-solvent dispersion interactions prior to the interaction versus solute-solute dispersion interactions following the interaction. The thermodynamics of binding of primary alcohols to the major urinary protein (MUP-I) indicate that this general assumption is not justified. The enthalpy of binding becomes more favorable with increasing chain length, whereas the entropy of binding becomes less favorable, both parameters showing a linear dependence. Despite the hydrophobicity of the interacting species, these data show that binding is not dominated by the classical hydrophobic effect, but can be attributed to favorable ligand-protein dispersion interactions. 相似文献
42.
Elizabeth Nunes Fernandes Mariele Nair de Campos Moura Jos Luis F. Costa Lima Boaventura F. Reis 《Microchemical Journal》2004,77(2):107-112
An automatic flow procedure for the determination of glycerol in wines by employing a flow system based on multicommutation and enzymatic reaction is described. Glycerol dehydrogenase was immobilized on aminopropyl glass beads and packed into a column that was coupled to the flow system. The NADH produced by the enzymatic reaction was monitored by spectrophotometry at 340 nm and its radiation absorption presented a relationship with glycerol concentration. The system manifold comprised a set of three-way solenoid valves controlled by a microcomputer, which was furnished with electronic interfaces and runs a software that was designed to carry out on-line sample dilution, reagent addition, and data acquisition. The procedure allows the determination of glycerol in wine samples without any prior pretreatment. The procedure presented as profitable features a linear response range between 2.0 and 10.0 g l−1 glycerol (R=0.998), a detection limit of 0.006 g l−1 glycerol, a relative standard deviation of 1.8% (n=14) for a typical wine sample presenting 5.3 g l−1 glycerol, a sampling throughput of 33 determinations per hour, and a NAD+ consumption of 0.8 mg per determination. The results were compared with those obtained using a reference method and no significant difference at 90% confidence level was observed. 相似文献
43.
Robin J. Marles James B. Hudson Elizabeth A. Graham Chantal Soucy-Breau Peter Morand R. Lilia Compadre Cesar M. Compadre G. H. Neil Towers J. Thor Arnason 《Photochemistry and photobiology》1992,56(4):479-487
The photoactivated antiviral and cytotoxic activities of the naturally occurring thiophene, alpha-terthienyl (1), and 15 synthetic analogues were evaluated against murine cytomegalovirus and Sindbis virus, and murine mastocytoma cells. After irradiation with near UV light, alpha-terthienyl and most of its analogues had significant toxicity, with minimum inhibitory concentrations in the range of 0.02-40 microM. In the absence of near UV irradiation, only one analogue had antiviral activity and five were cytotoxic. The most active analogues were those containing carboxylic acid, hydroxyl, or cyano substituents. Quantitative structure-activity relationship analysis of thiophene phototoxicity suggested that the rate of singlet oxygen production is the primary determinant of antiviral and cytotoxic activities. For phototoxicity against murine cytomegalovirus, a significant role for hydrophobicity was also demonstrated. Tricyclic thiophenes show significant potential for photochemotherapy of viral infections and cancer, and further evaluation in animal models is recommended. 相似文献
44.
This paper presents the synthesis and characterization of pyridine-substituted artificial oligopeptides with an aminoethylglycine backbone of varying length, which are designed to act as scaffolds for the self-assembly of multimetallic structures. The identities and purities of the oligopeptides are confirmed with mass spectrometry, (1)H NMR, HPLC, and pH titrations. The acid dissociation constants for the oligopeptides were determined and were found to decrease with increasing pyridine units. Titrations of the oligopeptides with Cu(II) and Pt(II) complexes containing the tridentate ligands 2,2':6',2'-terpyridine and pyridine 2,6-dicarboxylic acid were monitored using UV-visible absorption spectroscopy and showed stoichiometric binding based on the number of pyridines on the peptide strand. Metal titrations performed using an analogous oligopeptide with methyl substituents (in place of the pyridine ligands) showed very weak or no binding. In the case of the oligopeptides containing bound Pt(terpyridine)(2+) complexes, cyclic voltammetry reveals two sequential one-electron reductions at formal potentials that do not vary as a function of oligopeptide length. The measured diffusion coefficients were measured with chronoamperometry and were found to decrease with increasing oliopeptide length. 相似文献
45.
We show that, for any Jordan domain J in R2, harmonic measureis supported by a Borel set of packing dimension 1. We alsoobtain incomplete analogs to the results of Makarov, which connectthe almost everywhere behavior of the derivative near the boundaryfor the conformal mapping function from the unit disk J withthe Hausdorff measure properties of sets supporting the harmonicmeasure. 相似文献
46.
In this paper we study symmetry reductions and exact solutions of the shallow water wave (SWW) equation $$u_{xxxt} + \alpha u_x u_{xt} + \beta u_t u_{xx} - u_{xt} - u_{xx} = 0,$$ whereα andβ are arbitrary, nonzero, constants, which is derivable using the so-called Boussinesq approximation. Two special cases of this equation, or the equivalent nonlocal equation obtained by settingu x =U, have been discussed in the literature. The caseα=2β was discussed by Ablowitz, Kaup, Newell and Segur (Stud. Appl. Math.,53 (1974), 249), who showed that this case was solvable by inverse scattering through a second-order linear problem. This case and the caseα=β were studied by Hirota and Satsuma (J. Phys. Soc. Japan,40 (1976), 611) using Hirota's bi-linear technique. Further, the caseα=β is solvable by inverse scattering through a third-order linear problem. In this paper, a catalogue of symmetry reductions is obtained using the classical Lie method and the nonclassical method due to Bluman and Cole (J. Math. Mech,18 (1969), 1025). The classical Lie method yields symmetry reductions of (1) expressible in terms of the first, third and fifth Painlevé transcendents and Weierstrass elliptic functions. The nonclassical method yields a plethora of exact solutions of (1) withα=β which possess a rich variety of qualitative behaviours. These solutions all like a two-soliton solution fort < 0 but differ radically fort > 0 and may be viewed as a nonlinear superposition of two solitons, one travelling to the left with arbitrary speed and the other to the right with equal and opposite speed. These families of solutions have important implications with regard to the numerical analysis of SWW and suggests that solving (1) numerically could pose some fundamental difficulties. In particular, one would not be able to distinguish the solutions in an initial-value problem since an exponentially small change in the initial conditions can result in completely different qualitative behaviours. We compare the two-soliton solutions obtained using the nonclassical method to those obtained using the singular manifold method and Hirota's bi-linear method. Further, we show that there is an analogous nonlinear superposition of solutions for two (2+1)dimensional generalisations of the SWW Equation (1) withα=β. This yields solutions expressible as the sum of two solutions of the Korteweg-de Vries equation. 相似文献
47.
Carlos Gutierrez Marco-Antonio Teixeira 《Bulletin of the Brazilian Mathematical Society》1995,26(1):57-66
Let >0 andX be aC
1 vector field on the plane such that: (i) for allq2, Det(DX(q))>0; and (ii) for allp2, with p, Trace(D(X(p))<0. IfX has a singularity and
2 Trace(DX)dxdy is less than 0 (resp. greater or equal than 0), then the point at infinity of the Riemann sphere 2{} is a repellor (resp. an attractor) ofX. 相似文献
48.
49.
Alverson G Baker WF Ballocchi G Benson R Berg D Blusk S Bromberg C Brown D Carey D Chand T Chandlee C Choudhary BC Chung WH de Barbaro L DeSoi W Dlugosz W Dunlea J Easo S Engels E Faissler W Fanourakis G Ferbel T Garelick D Ginther G Glass G Glaubman M Gutierrez P Hartman K Huston J Johnstone C Kapoor V Kourbanis L Lanaro A Lirakis C Lobkowicz F Lukens P Mani S Maul A Mansour J Miller R Nelson CA Oh BY Orris D Pothier E Prebys E Rajaram BM Roser R Ruddick K Shepard P Shivpuri RK Sinanidis A 《Physical review D: Particles and fields》1993,48(1):5-28
50.
David G. Whitten Mohammad S. Farahat Elizabeth R. Gaillard 《Photochemistry and photobiology》1997,65(1):23-32
Abstract— Characterization of short-lived intermediates in homogeneous and microheterogeneous systems has been carried out using time-resolved spectroscopic techniques. The data obtained from these techniques have been analyzed in a relatively unconventional manner to elucidate complex transient behavior for two reactive systems. The highly nonexponential fluorescence decay for a series of fraws-stilbene-derivatized amphiphiles that readily form bilayer systems in aqueous media has been analyzed using a distribution of lifetimes analysis (DLA). The utility of DLA for quantitative studies was first determined by simulation of artificial decay data. Despite some limitations in DLA, qualitative conclusions as to the nature of the fluorescing species may be drawn when supplementary information such as steady-state spectroscopic data are also considered. The results indicate that the observed fluorescence originates from different types of excited-state species that consist of two or more trans-stilbene units; one of the emissions is attributed to the excited state of a ground-state aggregate while the other is assigned to an excimer that may arise from a 'defect'in the bilayer. The nonexponential nature of the decays is attributed to distributions of environments experienced by the fluorescing species. Electron transfer (ET) reactions between several excited pinacols and carbon tetrachloride in solution have been found to yield products with quantum yields that are higher than unity in the presence of oxygen, suggesting a chain mechanism for product formation. In these systems both the donor and the acceptor undergo bond fragmentation following the initial ET step. The individual steps involved in the proposed mechanism for these systems have been investigated in part using different steady-state and time-resolved laser spectroscopic techniques. However, it was also necessary to utilize pulse radiolysis in order to confirm the involvement of certain radical intermediates that were not observable by the usual flash photolysis techniques. 相似文献