The role of active centers in the kinetics of new phase formation

1972 ◽  
Vol 13-14 ◽  
pp. 131-134 ◽  
Author(s):  
I. Markov ◽  
D. Kashchiev
Author(s):  
Evgeniy S. Slivchenko ◽  
Vadim N. Isaev ◽  
Alexander P. Samarskiy ◽  
Valerian N. Blinichev

Theoretical and experimental evaluations of crystallization systems solutions stability to overcooling were summarized. The general regulariries of the kinetics of the crystallization process are discussed from the standpoint of the classical theory of the formation and growth of new-phase particles. During the analysis of the process of periodic homogeneous crystallization kinetic diagram, three characteristic periods were revealed: the period of resistance to supercooling, the period of crystal growth, and the period of recrystallization. The nature of the processes determining the duration of the characteristic periods has been established. The applicability of the mathematical apparatus of the new phase formation classical theory for calculating the basic and particular functionals of the crystallization system is substantiated. Relations are given that make it possible to calculate the main and particular functionals of the crystallization system stability for supercooling. The analysis of crystallization system category influence on the magnitude of limit supercooling and periodic homogenous crystallization induction period extreme was made. Parameters of the resistance to supercooling of supersaturated aqueous solutions of inorganic and organic substances certain classes under periodic homogeneous crystallization are presented. Conclusions are drawn regarding the position of the main and particular functionals extrema of the crystallization system. The correctness of the conclusions is confirmed by an analysis of the experimental data on the crystallization kinetics of a number of inorganic and organic substances from aqueous and aqueous-organic solvents. On the example of periodic homogeneous crystallization process of the vitamin B1 thiamin bromide from the water-ethanol solution, a complete series of the crystallization system main and particular functionals extremum positions the are constructed. The regularities of the influence of the organic component concentration in a binary solvent on the stability functionals of the crystallization system are noted.Forcitation:Slivchenko E.S., Samarskiy A.P., Isaev V.N., Blinichev V.N. Stability of supercooling solutions of crystallization systems in classical theory of new phase formation. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2017. V. 60. N 5. P. 88-93.


Holzforschung ◽  
2000 ◽  
Vol 54 (2) ◽  
pp. 165-170 ◽  
Author(s):  
Mikhail Yu. Balakshin ◽  
Chen-Loung Chen ◽  
Josef S. Gratzl ◽  
Adrianna G. Kirkman ◽  
Harald Jakob

Summary Kinetics of the laccase-catalyzed oxidation of veratryl alcohol with dioxygen in the presence of 2,2′-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diamonium salt (ABTS), the mediator, were studied to elucidate the possible reaction mechanism and the role of the mediator in this reaction. The reaction follows a pseudo-first order reaction law. The first order rate constant (κ) is dependent on the Mediator/Substrate (M/S) ratio and has a maximum at M/S molar ratio of 0.15. The kinetic studies show that the mechanism of veratryl alcohol oxidation with dioxygen-laccase-ABTS is rather complex and includes different reaction pathways. The mediator is involved in competitive reactions. It has been suggested that at low mediator concentration, the veratryl alcohol is oxidized via the laccase redox cycle. The mediator acts mostly as a laccase activator at a M/S ratio lower than 0.15. With increasing ABTS concentration with respect to the substrate concentration, ABTS acts increasingly as a cosubstrate competing with the original substrate for active centers of the laccase. This results in inhibition of veratryl alcohol oxidation in the enzyme cycle and increases the role of substrate oxidation by an oxidized mediator.


1993 ◽  
Vol 58 (5) ◽  
pp. 1001-1006 ◽  
Author(s):  
Oľga Vollárová ◽  
Ján Benko

The kinetics of oxidation of [Co(en)2SCH2COO]+ with S2O82- was studied in water-methanol and water-tert-butyl alcohol mixtures. Changes in the reaction activation parameters ∆H≠ and ∆S≠ with varying concentration of the co-solvent depend on the kind of the latter, which points to a significant role of salvation effects. The solvation effect on the reaction is discussed based on a comparison of the transfer functions ∆Ht0, ∆St0 and ∆Gt0 for the initial and transition states with the changes in the activation parameters accompanying changes in the CO-solvent concentration. The transfer enthalpies of the reactant were obtained from calorimetric measurements.


1991 ◽  
Vol 56 (10) ◽  
pp. 1993-2008
Author(s):  
S. Hanafi ◽  
G. M. S. El-Shafei ◽  
B. Abd El-Hamid

The hydration of tricalcium silicate (C3S) with three grain sizes of monoclinic (M) and triclinic (T) modifications and on their thermally activated samples were investigated by exposure to water vapour at 80°C for 60 days. The products were investigated by XRD, TG and N2 adsorption. The smaller the particle size the greater was the hydration for both dried and activated samples from (M). In the activated samples a hydrate with 2θ values of 38.4°, 44.6° and 48.6° could be identified. Hydration increased with particle size for the unactivated (T) samples but after activation the intermediate size exhibited enhanced hydration. Thermal treatment at 950°C of (T) samples increased the surface active centers on the expense of those in the bulk. Changes produced in surface texture upon activation and/or hydration are discussed.


Author(s):  
Aminata Hallimat Cissé ◽  
Sandrine Lioret ◽  
Blandine de Lauzon-Guillain ◽  
Anne Forhan ◽  
Ken K. Ong ◽  
...  

Abstract Background Early adiposity rebound (AR) has been associated with increased risk of overweight or obesity in adulthood. However, little is known about early predictors of age at AR. We aimed to study the role of perinatal factors and genetic susceptibility to obesity in the kinetics of AR. Methods Body mass index (BMI) curves were modelled by using mixed-effects cubic models, and age at AR was estimated for 1415 children of the EDEN mother–child cohort study. A combined obesity risk-allele score was calculated from genotypes for 27 variants identified by genome-wide association studies of adult BMI. Perinatal factors of interest were maternal age at delivery, parental education, parental BMI, gestational weight gain, maternal smoking during pregnancy, and newborn characteristics (sex, prematurity, and birth weight). We used a hierarchical level approach with multivariable linear regression model to investigate the association between these factors, obesity risk-allele score, and age at AR. Results A higher genetic susceptibility to obesity score was associated with an earlier age at AR. At the most distal level of the hierarchical model, maternal and paternal educational levels were positively associated with age at AR. Children born to parents with higher BMI were more likely to exhibit earlier age at AR. In addition, higher gestational weight gain was related to earlier age at AR. For children born small for gestational age, the average age at AR was 88 [±39] days lower than for children born appropriate for gestational age and 91 [±56] days lower than for children born large for gestational age. Conclusion The timing of AR seems to be an early childhood manifestation of the genetic susceptibility to adult obesity. We further identified low birth weight and gestational weight gain as novel predictors of early AR, highlighting the role of the intrauterine environment in the kinetics of adiposity.


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