scholarly journals Thiol–disulphide interchange in tubulin: kinetics and the effect on polymerization

2005 ◽  
Vol 389 (2) ◽  
pp. 549-558 ◽  
Author(s):  
P. J. Britto ◽  
Leslie Knipling ◽  
Peter Mcphie ◽  
J. Wolff

All 20 cysteine residues are accessible to disulphide reagents in the tubulin dimer, whereas only four are accessible in taxol-stabilized microtubules. Reaction rates with disulphide reagents are a function of the reagent, are decreased by G nucleotides, and increased with increase in pH and urea. With transient (stop-flow) kinetics, DTNB [5,5′-dithiobis-(2-nitrobenzoic acid)] and 2,2′-dithiodipyridine progress curves cannot be fitted by the sum of exponential terms based only on classes of cysteines. The mixed disulphide products react further to form both intra- and intermonomer disulphide bonds that can be reversed by reducing agents. With MMTS (methyl methanethiosulphonate) or ODNB (n-octyl-dithio-2-nitrobenzoate), virtually no protein–protein disulphide bonds are formed and the ODNB reaction can be given as the sum of three exponential terms with pseudo-first-order rate constants of 0.206, 0.069 and 0.010 s−1 at pH 6.5, suggesting three classes of thiol reactivities. Limited cysteine substitution leads to only small changes in tryptophan or CD spectra, whereas complete substitution leads to loss of the helix content. MMTS-induced loss of SH groups leads to progressive increases in the critical concentration and loss of polymerization competence that can be reversed by assembly promoters such as higher protein concentration, taxol or high ionic strength. Under such conditions, the substituted tubulin forms protofilament-based structures such as microtubules, open tubules, sheets and/or bundles.

1991 ◽  
Vol 24 (6) ◽  
pp. 9-16 ◽  
Author(s):  
P. J. Ossenbruggen ◽  
H. Spanjers ◽  
H. Aspegren ◽  
A. Klapwijk

A series of batch tests were performed to study the competition for oxygen by Nitrosomonas and Nitrobacter in the nitrification of ammonia in activated sludge. Oxygen uptake rate (OUR) and dynamic (compartment) models describing the process are proposed and tested. The OUR model is described by a Monod relationship and the biogradation process by a set of first order nonlinear differential equations with variable coefficients. The results show a mechanistic model and ten reaction rates are sufficient to capture the interactive behavior of the nitrification process. Methods for model specification, calibrating, and testing the model and the design of additional experiments are described.


1985 ◽  
Vol 50 (4) ◽  
pp. 845-853 ◽  
Author(s):  
Miloslav Šorm ◽  
Miloslav Procházka ◽  
Jaroslav Kálal

The course of hydrolysis of an ester, 4-acetoxy-3-nitrobenzoic acid catalyzed with poly(1-methyl-3-allylimidazolium bromide) (IIa), poly[l-methyl-3-(2-propinyl)imidazolium chloride] (IIb) and poly[l-methyl-3-(2-methacryloyloxyethyl)imidazolium bromide] (IIc) in a 28.5% aqueous ethanol was investigated as a function of pH and compared with low-molecular weight models, viz., l-methyl-3-alkylimidazolium bromides (the alkyl group being methyl, propyl, and hexyl, resp). Polymers IIb, IIc possessed a higher activity at pH above 9, while the models were more active at a lower pH with a maximum at pH 7.67. The catalytic activity at the higher pH is attributed to an attack by the OH- group, while at the lower pH it is assigned to a direct attack of water on the substrate. The rate of hydrolysis of 4-acetoxy-3-nitrobenzoic acid is proportional to the catalyst concentration [IIc] and proceeds as a first-order reaction. The hydrolysis depends on the composition of the solvent and was highest at 28.5% (vol.) of ethanol in water. The hydrolysis of a neutral ester, 4-nitrophenyl acetate, was not accelerated by IIc.


2007 ◽  
Vol 55 (10) ◽  
pp. 145-153 ◽  
Author(s):  
T. Ölmez ◽  
I. Kabdaşlı ◽  
O. Tünay

In this study, the effects of the phosphonic acid based sequestering agent EDTMPA used in the textile dye baths on colour and organic matter removal by ozone oxidation was experimentally investigated. Procion Navy HEXL dyestuff that has been commonly used for the reactive dyeing of cellulose fibers was selected as the model component. The organic matter oxidation by ozone was determined to obey the pseudo-first order kinetics as they are treated singly or in combination. COD removal rates obtained from pseudo-first order reaction kinetics showed that oxidation of Navy HEXL alone (0.0947 L/min) was faster than that of EDTMPA (0.0171 L/min) and EDTMPA with dye (0.0155 L/min) at pH 3.0. It was also found that reaction rates of single EDTMPA removal and EDTMPA and dye mixture removal increased as the reaction pH was increased from 3.0 to 10.5.


Author(s):  
Seplapatty Kalimuthu Periyasamy ◽  
H. Satham Hussain ◽  
R. Manikandan

The kinetics of Oxidation of Phenol and aniline by quinolinium Chlorochromate (QCC) in aqueous acetic acid medium leads to the formation of quinone and azobenzene respectively. The reactions are first order with respect to both Phenol and aniline. The reaction is first order with respect to quinolinium chlorochromate (QCC) and is catalyzed by hydrogen ion. The hydrogen-ion dependence has the form: kobs = a+b [H+]. The rate of oxidation decreases with increasing dielectric constant of solvent, indicating the presence of an ion-dipole interaction. The reaction does not induced the polymerization of acrylonitrile. The retardation of the rate by the addition of Mn2+ ions confirms that a two electron transfer process is involved in the reaction. The reaction rates have been determined at different temperatures and the activation parameters have been calculated. From the above observations kinetic results a probable mechanism have been proposed.


1989 ◽  
Vol 37 (1) ◽  
pp. 47-60
Author(s):  
S.E.A.T.M. van der Zee ◽  
W.H. van Riemsdijk ◽  
J.J.M. van Grinsven

The interpolation or extrapolation in time of physicochemical processes from experimental data is often difficult. A theoretically derived time-scaling procedure using an exposure variable of the concentration integrated in time, with at most one adjustable parameter was applied successfully to three systems taken from metallurgical, agricultural and environmental engineering. This scaling rule is potentially useful as a research or management tool for systems that are too complex for mechanistic modelling. (Abstract retrieved from CAB Abstracts by CABI’s permission)


1978 ◽  
Vol 41 (10) ◽  
pp. 774-780 ◽  
Author(s):  
M. P. DOYLE ◽  
E. H. MARTH

Bisulfite reacted with aflatoxin B1 and G1 resulting in their loss of fluorescence. The reaction was first order with rate depending on bisulfite (or the bisulfite and sulfite) concentration(s). Aflatoxin G1 reacted more rapidly with bisulfite than did aflatoxin B1. In the presence of 0.035 M potassium acid phthalate-NaOH buffer (pH 5.5) plus 1.3% (vol/vol) methanol at 25 C, the reaction rate constant for degradation of aflatoxin G1 was 2.23 × 10−2h− and that for aflatoxin B1 was 1.87 × 10−2h− when 50 ml of reaction mixture contained 1.60 g of K2SO3. Besides bisulfite concentrations, temperature influenced reaction rates. The Q10 for the bisulfite-aflatoxin reaction was approximately 2 while activation energies for degrading aflatoxin B1 and aflatoxin G1 were 13.1 and 12.6 kcal/mole, respectively. Data suggest that treating foods with 50 to 500 ppm SO2 probably would not effectively degrade appreciable amounts of aflatoxin. Treating foods with 2000 ppm SO2 or more and increasing the temperature might reduce aflatoxin to an acceptable level.


1956 ◽  
Vol 34 (1) ◽  
pp. 637-653 ◽  
Author(s):  
W. Kalow ◽  
K. Genest ◽  
N. Staron

Benzoylcholine stands out from other known substrates of serum cholinesterase because of its high apparent affinity for this enzyme combined with a rapid rate of destruction. The reaction kinetics of the hydrolysis of benzoylcholine can be studied by ultraviolet spectrophotometry, since the absorbance decreases in proportion to the concentration of substrate. Kinetic data obtained by measuring initial reaction rates, and by analyzing continuous hydrolysis curves, are the same within the range of experimental error. The enzymatic data are compatible with the assumption that in the presence of high substrate concentrations a complex consisting of esterase and two substrate molecules is formed. This complex is hydrolyzed more slowly than the complex containing one molecule of substrate which is formed at low concentrations of benzoylcholine. Alkaline hydrolysis of benzoylcholine follows the kinetics of a first order reaction.


2008 ◽  
Vol 15 (01n02) ◽  
pp. 145-151 ◽  
Author(s):  
MIN LI ◽  
SHOUZHI PU ◽  
CHUNHONG ZHENG ◽  
MINGBIAO LUO ◽  
ZHANGGAO LE

Three new asymmetric photochromic diarylethenes bearing fluorine atoms at the ortho-, meta-, or para-position of one terminal phenyl group were synthesized, and their photochromism and kinetics of the photochromic cyclization/cycloreversion both in different solvents and in PMMA films were investigated. The results showed that the cyclization/cycloreversion process of these compounds were determined to be zeroth/first order reaction, and the reaction rates (k) were obtained from the slope of every line. The substituent position effect on the cycloreversion process of the three compounds was remarkable and the solvent polarity enhanced this effect. The values of reaction rates in PMMA films were quite different from those in solvents indicating that the kinetics processes of the three compounds taking place in PMMA films differs from the same processes occurring in common solvent.


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