First determination of the rate constant for ring-closure of an azahexenoyl radical: 6-aza-7-ethyl-5-hexenoyl

2010 ◽  
Vol 46 (35) ◽  
pp. 6521 ◽  
Author(s):  
Sara H. Kyne ◽  
Ching Yeh Lin ◽  
Ilhyong Ryu ◽  
Michelle L. Coote ◽  
Carl H. Schiesser
Keyword(s):  
Rate Constant ◽  
Ring Closure

Determination of rate constants of redox reactions of second order from current-less potential-time curves by a simplified graphical-numerical method

1983 ◽  
Vol 48 (5) ◽  
pp. 1358-1367 ◽  
Author(s):  
Antonín Tockstein ◽  
František Skopal
Keyword(s):  
Numerical Method ◽  
Explicit Form ◽  
Rate Constant ◽  
Optimization Algorithm ◽  
Rate Constants ◽  
Redox Reactions ◽  
Second Order ◽  
Wide Region ◽  
Recurrent Formula

A method for constructing curves is proposed that are linear in a wide region and from whose slopes it is possible to determine the rate constant, if a parameter, θ, is calculated numerically from a rapidly converging recurrent formula or from its explicit form. The values of rate constants and parameter θ thus simply found are compared with those found by an optimization algorithm on a computer; the deviations do not exceed ±10%.

Regeneration Mechanism Studied by Potential-Time Response to Sinusoidal Current-Time Function

1997 ◽  
Vol 62 (10) ◽  
pp. 1511-1526
Author(s):  
María-Luisa Alcaraz ◽  
Ángela Molina
Keyword(s):  
Kinetic Parameters ◽  
Rate Constant ◽  
Theoretical Study ◽  
Time Function ◽  
Time Response ◽  
Current Time ◽  
Regeneration Mechanism ◽  
Sinusoidal Current ◽  
Regeneration Processes

A theoretical study of the potential-time response to sinusoidal current applied to static and dynamic electrodes for regeneration processes is presented. Methods for determination of the regeneration fraction, rate constant of the chemical reaction and heterogeneous kinetic parameters are proposed.

Direct determination of the rate constant for the reaction CO + N2O → CO2 + N2

1985 ◽  
Vol 122 (5) ◽  
pp. 489-492 ◽  
Author(s):  
Nobuyuki Fujii ◽  
Tomohisa Kakuda ◽  
Takeo Sugiyama ◽  
Hajime Miyama
Keyword(s):  
Rate Constant ◽  
Direct Determination

scholarly journals Mechanism of tubulin–colchicine recognition: a kinetic study of the binding of the colchicine analogues colchicide and isocolchicine

1997 ◽  
Vol 327 (3) ◽  
pp. 685-688 ◽  
Author(s):  
Chantal DUMORTIER ◽  
Qunying YAN ◽  
Susan BANE ◽  
Yves ENGELBORGHS
Keyword(s):  
Rate Constant ◽  
Total Concentration ◽  
Carbonyl Oxygen ◽  
Protein Fluorescence ◽  
Kinetic And Thermodynamic Parameters ◽  
Methoxy Groups ◽  
Displacement Experiments ◽  
Absorbance Changes ◽  
Initial Binding

Colchicide (IDE) is a colchicine (COL) analogue in which the C-10 methoxy group is replaced by a hydrogen atom. Its binding to tubulin is accompanied by a quenching of the protein fluorescence. The fluorescence decrease shows a monoexponential time dependence. The observed rate constant increases in a non-linear way with the total concentration of IDE, allowing the determination of a binding constant for an initial binding site (K1 = 5300±300 M-1) and the rate constant for the subsequent isomerization (k2 = 0.071±0.002 s-1) at 25 °C. The rate constant, k-2, for the reversed isomerization can be determined by displacement experiments. Despite the minor alteration of the C-ring substituent, the kinetic and thermodynamic parameters of binding are substantially different from those of COL itself, for both steps. In isocolchicine (ISO) the carbonyl oxygen atom and the methoxy groups of the C-ring have been interchanged. Its binding to tubulin only results in small fluorescence and absorbance changes. Therefore competition experiments with MTC [2-methoxy-5-(2ʹ,3ʹ,4ʹ-trimethoxyphenyl)-2,4,6-cycloheptatrien-1-one] were performed. ISO competes rapidly and with low affinity with MTC. Fluorimetric titrations of tubulin with MDL (MDL 27048 or trans-1-(2,5 dimethoxyphenyl)-3-[4-(dimethylamino)phenyl]-2-methyl-2-propen-1-one) in the presence and absence of ISO give evidence for the existence of a second, slow-reacting low-affinity site for ISO that is not accessible to MTC or MDL. The relevance of these results for the recognition of COL is analysed.

CuAAC and RuAAC with Alkyne-functionalised Dihydroazulene Photoswitches and Determination of Hammett σ-Constants for Triazoles

2014 ◽  
Vol 67 (3) ◽  
pp. 531 ◽  
Author(s):  
Henriette Lissau ◽  
Søren Lindbæk Broman ◽  
Martyn Jevric ◽  
Anders Ø. Madsen ◽  
Mogens Brøndsted Nielsen
Keyword(s):  
Molecular Electronics ◽  
Ring Closure ◽  
Reference Systems ◽  
Rigid Structure ◽  
Useful Components ◽  
Substituent Constants ◽  
Hammett Σ Constants

Dihydroazulene (DHA)–vinylheptafulvene (VHF) photoswitches have attracted attention as potentially useful components in molecular electronics. The π-conjugated dihydroazulene system is a rigid structure and can be strategically functionalised to place handles for further elaboration. Here we show that alkyne-functionalised dihydroazulenes can be subjected to copper and ruthenium catalysed azide–alkyne cycloadditions (CuAAC and RuAAC) with tolylazide, furnishing 1,4- and 1,5-disubstituted triazoles. The rates of ring-closure of the corresponding vinylheptafulvenes were compared with those of reference systems, which allowed determination of Hammett substituent constants (meta and para) for N-tolyl-substituted 1,2,3-triazoles.

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