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Extended Set (extended + set)
Selected AbstractsIdentification of the effective distribution function for determination of the distributed activation energy models using the maximum likelihood method: Isothermal thermogravimetric dataINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 1 2009Bojan Jankovi The new procedure for identification of the effective distribution function for determination of the distributed activation energy models, which is based on use the maximum likelihood method (MLM), was established. The five different continuous probability functions (exponential, logistic, normal, gamma, and Weibull probability functions (the extended set of distributions)) were used for searching the best reactivity model for two heterogeneous processes: (a) the isothermal reduction process of nickel oxide under hydrogen atmosphere and (b) the isothermal degradation process of bisphenol-A polycarbonate (Lexan) under nitrogen atmosphere. The MLM showed that for both processes, the most suitable reactivity model represents the Weibull distribution model. It was concluded that the values of Arrhenius parameters (ln A and Ea), evaluated from the Weibull distribution model, represent the effective kinetic values for both considered processes. This procedure enables identification the suitable distribution model for considered process only from the experimental data (based on the shapes of obtained integral kinetic curves), and this fact represents the advantage of established analysis. The established mathematical procedure, which is based on the MLM, can be applied as the preliminary analysis for evaluating the distribution of activation energies for complex heterogeneous processes. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 41: 27,44, 2009 [source] Tumors Associated With Oncogenic Osteomalacia Express Genes Important in Bone and Mineral MetabolismJOURNAL OF BONE AND MINERAL RESEARCH, Issue 6 2002Suzanne M. Jan De Beur Abstract Oncogenic osteomalacia (OOM) is associated with primitive mesenchymal tumors that secrete phosphaturic factors resulting in low serum concentrations of phosphate and calcitriol, phosphaturia, and defective bone mineralization. To identify overexpressed genes in these tumors, we compared gene expression profiles of tumors resected from patients with OOM and histologically similar control tumors using serial analysis of gene expression (SAGE). Three hundred and sixty-four genes were expressed at least twofold greater in OOM tumors compared with control tumors. A subset of 67 highly expressed genes underwent validation with an extended set of OOM and control tumors using array analysis or reverse-transcription polymerase chain reaction (RT-PCR). Ten of these validated genes were consistently overexpressed in all OOM tumors relative to control tumors. Strikingly, genes with roles in bone matrix formation, mineral ion transport, and bone mineralization were highly expressed in the OOM tumors. [source] Association Between Birth Control Pills and Voice QualityTHE LARYNGOSCOPE, Issue 6 2004Ofer Amir PhD Abstract Objectives/Hypothesis: The objective was to extend our knowledge of the effect of birth control pills on voice quality in women based on various acoustic measures. Study Design: A longitudinal comparative study of 14 healthy young women over a 36- to 45-day period. Methods: Voices of seven women who used birth control pills and seven women who did not were recorded repeatedly approximately 20 times. Voice samples were analyzed acoustically, using an extended set of frequency perturbation parameters (jitter, relative average perturbation, pitch period perturbation quotient), amplitude perturbation parameters (shimmer, amplitude average perturbation quotient), and noise indices (noise-to-harmonics ratio, voice turbulence index). Results: Voice quality and stability were found to be better among the women who used birth control pills. Lower values were found for all acoustic measures with the exception of voice turbulence index. Results also provided preliminary indication for vocal changes associated with the days preceding ovulation. Conclusion: In contrast to the traditional view of oral contraceptives as a risk factor for voice quality, and in keeping with the authors' previous work, the data in the present study showed that not only did oral contraceptives have no adverse effect on voice quality but, in effect, most acoustic measures showed improved voice quality among women who used the birth control pill. The differences in the noise indices between groups may also shed light on the nature of the effect of sex hormones on vocal fold activity. It was suggested that hormonal fluctuations may have more of an effect on vocal fold regulation of vibration than on glottal adduction. [source] Kinetic, Thermodynamic, and Mechanistic Patterns for Free (Unbound) Cytochrome c at Au/SAM Junctions: Impact of Electronic Coupling, Hydrostatic Pressure, and Stabilizing/Denaturing AdditivesCHEMISTRY - A EUROPEAN JOURNAL, Issue 27 2006Dimitri E. Khoshtariya Prof. Dr. Abstract Combined kinetic (electrochemical) and thermodynamic (calorimetric) investigations were performed for an unbound (intact native-like) cytochrome c (CytC) freely diffusing to and from gold electrodes modified by hydroxyl-terminated self-assembled monolayer films (SAMs), under a unique broad range of experimental conditions. Our approach included: 1) fine-tuning of the charge-transfer (CT) distance by using the extended set of Au-deposited hydroxyl-terminated alkanethiol SAMs [-S-(CH2)n -OH] of variable thickness (n=2, 3, 4, 6, 11); 2) application of a high-pressure (up to 150,MPa) kinetic strategy toward the representative Au/SAM/CytC assemblies (n=3, 4, 6); 3) complementary electrochemical and microcalorimetric studies on the impact of some stabilizing and denaturing additives. We report for the first time a mechanistic changeover detected for "free" CytC by three independent kinetic methods, manifested through 1) the abrupt change in the dependence of the shape of the electron exchange standard rate constant (ko) versus the SAM thickness (resulting in a variation of estimated actual CT range within ca. 15 to 25 Å including ca. 11 Å of an "effective" heme-to-,-hydroxyl distance). The corresponding values of the electronic coupling matrix element vary within the range from ca. 3 to 0.02 cm,1; 2) the change in activation volume from +6.7 (n=3), to ,0 (n=4), and ,5.5 (n=6) cm3,mol,1 (disclosing at n=3 a direct pressure effect on the protein's internal viscosity); 3) a "full" Kramers-type viscosity dependence for ko at n=2 and 3 (demonstrating control of an intraglobular friction through the external dynamic properties), and its gradual transformation to the viscosity independent (nonadiabatic) regime at n=6 and 11. Multilateral cross-testing of "free" CytC in a native-like, glucose-stabilized and urea-destabilized (molten-globule-like) states revealed novel intrinsic links between local/global structural and functional characteristics. Importantly, our results on the high-pressure and solution-viscosity effects, together with matching literature data, strongly support the concept of "dynamic slaving", which implies that fluctuations involving "small" solution components control the proteins' intrinsic dynamics and function in a highly cooperative manner as far as CT processes under adiabatic conditions are concerned. [source] | |||||||||||||