scholarly journals Syncatalytic inactivation of prolyl 4-hydroxylase by anthracyclines

1988 ◽  
Vol 251 (2) ◽  
pp. 365-372 ◽  
Author(s):  
V Günzler ◽  
H M Hanauske-Abel ◽  
R Myllylä ◽  
D D Kaska ◽  
A Hanauske ◽  
...  

The anthracyclines doxorubicin and daunorubicin were found to act as irreversible inhibitors of prolyl 4-hydroxylase. The reaction rate for enzyme from both chick and human origin was first order, the concentration of inhibitor giving 50% inhibition being 60 microM for both compounds after 1 h. The effect was dependent on the presence of iron ions in the reaction mixture. Inactivation could be prevented by addition of high concentrations of ascorbate, but not 2-oxoglutarate, before the inactivation period. The same results were obtained with competitive analogues of these cosubstrates. Lysyl hydroxylase from chick embryos was also susceptible to inactivation. Its activity was decreased by 50% after incubation for 1 h with a 150 microM concentration of the inhibitors. When chick-embryo prolyl 4-hydroxylase was incubated with [14-14C]doxorubicin, both enzyme subunits were radioactively labelled, about 70% of the total radioactivity being found in the alpha-subunit. Since the anthracyclines are known to undergo a redox reaction generating semiquinone radicals with Fe3+ only, the results suggest that the enzyme-bound iron ion is oxidized to a tervalent intermediate in uncoupled reaction cycles. The data also suggest that both enzyme subunits contribute to the catalytic site of prolyl 4-hydroxylase.

2014 ◽  
Vol 28 (2) ◽  
pp. 231-237 ◽  
Author(s):  
Lech W. Szajdak ◽  
Jerzy Lipiec ◽  
Anna Siczek ◽  
Artur Nosalewicz ◽  
Urszula Majewska

Abstract The aim of this study was to verify first-order kinetic reaction rate model performance in predicting of leaching of atrazine and inorganic compounds (K+1, Fe+3, Mg+2, Mn+2, NH4 +, NO3 - and PO4 -3) from tilled and orchard silty loam soils. This model provided an excellent fit to the experimental concentration changes of the compounds vs. time data during leaching. Calculated values of the first-order reaction rate constants for the changes of all chemicals were from 3.8 to 19.0 times higher in orchard than in tilled soil. Higher first-order reaction constants for orchard than tilled soil correspond with both higher total porosity and contribution of biological pores in the former. The first order reaction constants for the leaching of chemical compounds enables prediction of the actual compound concentration and the interactions between compound and soil as affected by management system. The study demonstrates the effectiveness of simultaneous chemical and physical analyses as a tool for the understanding of leaching in variously managed soils.


2019 ◽  
Vol 292 ◽  
pp. 01063
Author(s):  
Lubomír Macků

An alternative method of determining exothermic reactor model parameters which include first order reaction rate constant is described in this paper. The method is based on known in reactor temperature development and is suitable for processes with changing quality of input substances. This method allows us to evaluate the reaction substances composition change and is also capable of the reaction rate constant (parameters of the Arrhenius equation) determination. Method can be used in exothermic batch or semi- batch reactors running processes based on the first order reaction. An example of such process is given here and the problem is shown on its mathematical model with the help of simulations.


1976 ◽  
Vol 29 (2) ◽  
pp. 443 ◽  
Author(s):  
MA Haleem ◽  
MA Hakeem

Kinetic data are reported for the decarboxylation of β-resorcylic acid in resorcinol and catechol for the first time. The reaction is first order. The observation supports the view that the decomposition proceeds through an intermediate complex mechanism. The parameters of the absolute reaction rate equation are calculated.


2015 ◽  
Vol 782 ◽  
pp. 260-299 ◽  
Author(s):  
Preyas N. Shah ◽  
Eric S. G. Shaqfeh

Surfaces that include heterogeneous mass transfer at the microscale are ubiquitous in nature and engineering. Many such media are modelled via an effective surface reaction rate or mass transfer coefficient employing the conventional ansatz of kinetically limited transport at the microscale. However, this assumption is not always valid, particularly when there is strong flow. We are interested in modelling reactive and/or porous surfaces that occur in systems where the effective Damköhler number at the microscale can be $O(1)$ and the local Péclet number may be large. In order to expand the range of the effective mass transfer surface coefficient, we study transport from a uniform bath of species in an unbounded shear flow over a flat surface. This surface has a heterogeneous distribution of first-order surface-reactive circular patches (or pores). To understand the physics at the length scale of the patch size, we first analyse the flux to a single reactive patch. We use both analytic and boundary element simulations for this purpose. The shear flow induces a 3-D concentration wake structure downstream of the patch. When two patches are aligned in the shear direction, the wakes interact to reduce the per patch flux compared with the single-patch case. Having determined the length scale of the interaction between two patches, we study the transport to a periodic and disordered distribution of patches again using analytic and boundary integral techniques. We obtain, up to non-dilute patch area fraction, an effective boundary condition for the transport to the patches that depends on the local mass transfer coefficient (or reaction rate) and shear rate. We demonstrate that this boundary condition replaces the details of the heterogeneous surfaces at a wall-normal effective slip distance also determined for non-dilute patch area fractions. The slip distance again depends on the shear rate, and weakly on the reaction rate, and scales with the patch size. These effective boundary conditions can be used directly in large-scale physics simulations as long as the local shear rate, reaction rate and patch area fraction are known.


2008 ◽  
Vol 5 (3) ◽  
pp. 598-606
Author(s):  
Vandana Sharma ◽  
K. V. Sharma ◽  
V. W. Bhagwat

The kinetics and mechanism of cetyltrimethylammonium bromide catalyzed oxidation of tetraethylene glycol [2,2'-(oxibis(ethylenoxy)diethanol)] byN-chlorosaccharin in aqueous acetic acid medium in presence of perchloric acid have been investigated at 323K. The reaction is first order dependence on Nchlorosaccharin. The reaction rate follows first order kinetics with respect to [tetraethylene glycol] with excess concentration of other reactants. The miceller effect due to cetyltrimethylammonium bromide, a cationic surfactant has been studied. The change in ionic strength shows negligible salt effect. The dielectric effect is found to be positive. Addition of one of the products (saccharin) retards the reaction rate. Activation parameters are calculated from the Arrhenious plot. A possible mechanism consistent with the experimental results has been proposed.


2011 ◽  
Vol 312-315 ◽  
pp. 364-369 ◽  
Author(s):  
Seyed Amir Bahrani ◽  
Catherine Loisel ◽  
Jean Yves Monteau ◽  
Sid Ahmed Rezzoug ◽  
Zoulikha Maache-Rezzoug

Two hydrothermal treatment processes (DV-HMT and DIC treatment) were investigated on standard maize starch for three processing temperatures; 100, 110 and 120°C. The gravimetric change of starch powder during the treatment was analyzed by a simultaneous water diffusion and starch reaction model. The effective diffusivity coefficient (Deff) and reaction rate constant (k) were estimated by minimizing the error between experimental and analytical results. The values of Deff and k clearly increased with temperature. The degree of starch melting was evaluated for the two treatments using the first-order reaction model as a function of processing time. The results suggest that the absorption process is controlled by water–starch reactivity that induces melting phenomenon of starch crystallites, which progresses when temperature increases. The two hydrothermal treatments considerably differ: DIC being more prone to water absorption as demonstrated by the values of Deff and k.


2002 ◽  
Vol 67 (2) ◽  
pp. 103-109 ◽  
Author(s):  
Ljiljana Jelisavac ◽  
Milos Filipovic

A suitable kinetic model for the consumption of stabilizer (diphenylamine) in single base gun propellants was investigated and successfully verified. The model assumes that a reaction of shifting order can be applied for the consumption of diphenylamine in single base gun propellants. It was found that the experimental data were well evaluated by a first-order reaction at high concentrations of diphenylamine in the propellant, but by a zero-order reaction at low concentrations during the final phase of the propellant life time. The mechanism of diphenylamine depletion was discussed with relation to the model and the ageing behavior of the propellants. The kinetic parameters of this model, which permit the calculation of the time up to complete consumption of the diphenylamine, were determined. The results were compared with the kinetic data obtained by a widely accepted model, which combines formally reactions of first and zero order, designated as an "exponential and linear" model. All comparisons gave satisfactory agreement.


1955 ◽  
Vol 8 (3) ◽  
pp. 322 ◽  
Author(s):  
B Breyer ◽  
HH Bauer ◽  
S Hacobian

The equation of the A.C. polarographic current for processes where the frequency of the alternating field is comparable with the rate of the electrode reaction is derived. Relative values of equilibrium rate constants of some first order electrode reactions are evaluated experimentally.


2012 ◽  
Vol 581-582 ◽  
pp. 694-697
Author(s):  
Yong Yao ◽  
De Li Luo ◽  
Zhi Yong Huang ◽  
Jiang Feng Song

In order to evaluate the feasibility of tritium recovery from tritiated water by thermochemical decomposition using ZrNi5, the kinetics of reaction between ZrNi5 and water vapor was studied by thermogravimetric method in the temperature range from 673K to 823K. The result shows that reaction rate increased significantly with the increasing of temperature and H2O concentration; the reaction mechanism for ZrNi5 can be described by the first-order chemical reaction, and the reaction is first order for H2O concentration. The reaction activation energy of ZrNi5 is 55.8kJ/mol calculated from the Arrhenius equation.


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