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81.
The cyclization of the RNA model 2-hydroxypropyl p-nitrophenyl phosphate (HPNPP, 1) promoted by Zn2+ alone and the 1,5,9-triazacyclododecane complex of Zn2+ (Zn2+:[12]aneN3) is studied in ethanol in the presence of 0.5 equiv of -OEt/Zn2+ to investigate the effect of a low polarity/dielectric medium on a metal-catalyzed reaction of biological relevance. Ethanol exerts a medium effect that promotes strong binding of HPNPP to Zn2+, followed by a dimerization to form a catalytically active complex (HPNPP:Zn2+)2 in which the phosphate undergoes cyclization with a rate constant of kcat = 2.9 s(-1) at s(s)pH 7.1. In the presence of the triaza ligand:Zn2+ complex, the change from water to methanol and then to ethanol brings about a mechanism where two molecules of the complex, suggested as EtOH:Zn2+:[12]aneN3 and its basic form, EtO-:Zn2+:[12]aneN3, bind to HPNPP and catalyze its decomposition with a rate constant of kcat of 0.13 s(-1) at s(s)pH 7.1. Overall, the acceleration exhibited in these two situations is 4 x 10(14)-fold and 1.7 x 10(12)-fold relative to the background ethoxide-promoted reactions at the respective s(s)pH values. The implications of these findings are discussed within the context of the idea that enzymatic catalysis is enhanced by a reduced effective dielectric constant within the active site. 相似文献
82.
83.
Carmen Moldovan Carmen Mihailescu Dana Stan Lavinia Ruta Rodica Iosub Raluca Gavrila Munizer Purica Schiopu Vasilica 《Applied Surface Science》2009,255(22):8953-8959
This article presents the characterization of two substrates, silicon and polymer coated with gold, that are functionalized by mixed self-assembled monolayers (SAMs) in order to efficiently immobilize the anti-Escherichia coli O157:H7 polyclonal purified antibody.A biosurface functionalized by SAMs (self-assembled monolayers) technique has been developed. Immobilization of goat anti-E. coli O157:H7 antibody was performed by covalently bonding of thiolate mixed self-assembled monolayers (SAMs) realized on two substrates: polymer coated with gold and silicon coated with gold. The F(ab′)2 fragments of the antibodies have been used for eliminating nonspecific bindings between the Fc portions of antibodies and the Fc receptor on cells. The properties of the monolayers and the biofilm formatted with attached antibody molecules were analyzed at each step using infrared spectroscopy (FTIR-ATR), atomic force microscopy (AFM), scanning electron microscopy (SEM) and cyclic voltammetry (CV). In our study the gold-coated silicon substrates approach yielded the best results.These experimental results revealed the necessity to investigate each stage of the immobilization process taking into account in the same time the factors that influence the chemistry of the surface and the further interactions as well and also provide a solid basis for further studies aiming at elaborating sensitive and specific immunosensor or a microarray for the detection of E. coli O157:H7. 相似文献
84.
I. Benkovský R. Staník M. Polakovičová 《Journal of Radioanalytical and Nuclear Chemistry》2009,280(1):63-68
Quantitative measurement of fission and activation products resulting from neutron irradiation of fissile materials is of interest for applications in environmental monitoring, nuclear waste management, and national security. Based on established separation processes involving co-precipitation, solvent extraction, and ion-exchange and extraction chromatography, we have optimized a proposed sequence of separation steps to allow for the timely quantification of analytes of interest. We have recently evaluated this scheme using an irradiated sample to examine the adequacy of separations for measurement of desired analytes by gamma spectrometry. Here we present the radiochemical separations utilized and the yields and purity obtained. 相似文献
85.
Stan Lipovetsky 《Mathematical and Computer Modelling》2009,49(7-8):1427-1435
Multiple linear regression with special properties of its coefficients parameterized by exponent, logit, and multinomial functions is considered. To obtain always positive coefficients the exponential parameterization is applied. To get coefficients in an assigned range, the logistic parameterization is used. Such coefficients permit us to evaluate the impact of individual predictors in the model. The coefficients obtained by the multinomial–logit parameterization equal the shares of the predictors, which is useful for interpretation of their influence. The considered regression models are constructed by nonlinear optimization techniques, have stable solutions and good quality of fit, have simple structure of the linear aggregates, demonstrate high predictive ability, and suggest a convenient way to identify the main predictors. 相似文献
86.
Neverov AA Lu ZL Maxwell CI Mohamed MF White CJ Tsang JS Brown RS 《Journal of the American Chemical Society》2006,128(50):16398-16405
The catalytic ability of a dinuclear Zn2+ complex of 1,3-bis-N1-(1,5,9-triazacyclododecyl)propane (3) in promoting the cleavage of an RNA model, 2-hydroxypropyl-p-nitrophenyl phosphate (HPNPP, 1), and a DNA model, methyl p-nitrophenyl phosphate (MNPP, 4), was studied in methanol solution in the presence of added CH3O- at 25 degrees C. The di-Zn2+ complex (Zn2 :3), in the presence of 1 equiv of added methoxide, exhibits a second-order rate constant of (2.75 +/- 0.10) x 10(5) M(-1) s(-1) for the reaction with 1 at s(s)pH 9.5, this being 10(8)-fold larger than the k2 value for the CH3O- promoted reaction (kOCH3 = (2.56 +/- 0.16) x 10(-3) M(-1) s(-1)). The complex is also active toward the DNA model 4, exhibiting Michaelis-Menten kinetics with a KM and kmax of 0.37 +/- 0.07 mM and (4.1 +/- 0.3) x 10(-2) s(-1), respectively. Relative to the background reactions at s(s)pH 9.5, Zn2 :3 accelerates cleavage of each phosphate diester by a remarkable factor of 1012-fold. A kinetic scheme common to both substrates is discussed. The study shows that a simple model system comprising a dinuclear Zn2+ complex and a medium effect of the alcohol solvent achieves a catalytic reactivity that approaches enzymatic rates and is well beyond anything seen to date in water for the cleavage of these phosphate diesters. 相似文献
87.
Ecaterina C. Niculescu Cristina Stan Gabriela Tiriba Cristina Truşcǎ 《The European Physical Journal B - Condensed Matter and Complex Systems》2017,90(5):100
The electronic properties and optical characteristics – absorption coefficient, refractive index and group index – in an impurity doped pseudo-harmonic quantum disc subjected to an applied magnetic field are investigated. Numerical calculations are performed using the exact diagonalization technique and the compact density-matrix formalism. It is found that the chosen structure could be switched between a lambda-type and a ladder-type configuration by a proper tailoring of the magnetic field strength. Furthermore, the absorption profile and the associated slow light frequency range can be controlled not only by varying the control field amplitude and its detuning but also by changing the impurity position and the magnetic field strength. 相似文献
88.
Stan Alama Lia Bronsard Xavier Lamy 《Archive for Rational Mechanics and Analysis》2016,222(1):427-450
We consider energy minimizing configurations of a nematic liquid crystal around a spherical colloid particle, in the context of the Landau–de Gennes model. The nematic is assumed to occupy the exterior of a ball Br0, and satisfy homeotropic weak anchoring at the surface of the colloid and approach a uniform uniaxial state as \({|x|\to\infty}\). We study the minimizers in two different limiting regimes: for balls which are small \({r_0\ll L^{\frac12}}\) compared to the characteristic length scale \({L^{\frac 12}}\), and for large balls, \({r_0\gg L^{\frac12}}\). The relationship between the radius and the anchoring strength W is also relevant. For small balls we obtain a limiting quadrupolar configuration, with a “Saturn ring” defect for relatively strong anchoring, corresponding to an exchange of eigenvalues of the Q-tensor. In the limit of very large balls we obtain an axisymmetric minimizer of the Oseen–Frank energy, and a dipole configuration with exactly one point defect is obtained. 相似文献
89.
In this paper we consider the propagation of Rayleigh surface waves in an exponentially graded half-space made of an isotropic Kelvin-Voigt viscoelastic material. Here we take into account the effect of the viscoelastic dissipation energy upon the corresponding wave solutions. As a consequence we introduce the damped in time wave solutions and then we treat the Rayleigh surface wave problem in terms of such solutions. The explicit form of the secular equation is obtained in terms of the wave speed and the viscoelastic inhomogeneous profile. Furthermore, we use numerical methods and computations to solve the secular equation for some special homogeneous materials. The results sustain the idea, existent in literature on the argument, that there is possible to have more than one surface wave for the Rayleigh wave problem. 相似文献
90.