Oxidative Catalysis by TAMLs: Obtaining Rate Constants for Non‐Absorbing Targets by UV‐Vis Spectroscopy

ChemPhysChem ◽  
2020 ◽  
Vol 21 (11) ◽  
pp. 1083-1086
Author(s):  
Yogesh Somasundar ◽  
Iris C. Lu ◽  
Matthew R. Mills ◽  
Lisa Y. Qian ◽  
Ximena Olivares ◽  
...  
Keyword(s):  
Rate Constants ◽  
Vis Spectroscopy ◽  
Oxidative Catalysis

scholarly journals Kinetic measurements on the reactivity of hydrogen peroxide and ozone towards small atmospherically relevant aldehydes, ketones and organic acids in aqueous solution

2013 ◽  
Vol 13 (10) ◽  
pp. 25537-25566 ◽  
Author(s):  
L. Schöne ◽  
H. Herrmann
Keyword(s):  
Hydrogen Peroxide ◽  
Rate Constants ◽  
Radical Reaction ◽  
Degradation Process ◽  
Atmospheric Environment ◽  
Radical Reactions ◽  
Kinetic Measurements ◽  
Reaction Rate Constants ◽  
Dual Beam ◽  
Vis Spectroscopy

Abstract. Within the aqueous atmospheric environment free radical reactions are an important degradation process for organic compounds. Nevertheless, non-radical oxidants like hydrogen peroxide and ozone also contribute to the degradation and conversion of this substance group (Tilgner und Herrmann, 2010). In this work kinetic investigations of non-radical reactions were conducted using UV/Vis spectroscopy (dual-beam spectrophotometer and Stopped Flow technique) and a capillary electrophoresis system applying pseudo-first order kinetics of glyoxal, methylglyoxal, glycolaldehyde, glyoxylic, pyruvic and glycolic acids as well as methacrolein (MACR) and methyl vinyl ketone (MVK) towards H2O2 and ozone. The measurements indicate rather small rate constants at room temperature of k2nd < 3 M−1 s−1 (except for the unsaturated compounds exposed to ozone). Compared to radical reaction rate constants the values are about 10 orders of magnitude smaller (kOH· ~ 109 M−1 s−1). However, when considering the much larger non-radical oxidant concentrations compared to radical concentrations in urban cloud droplets, calculated turnovers change the picture to more important H2O2 reactions especially when compared to the nitrate radical. For some reactions also mechanistic suggestions are given.

scholarly journals Kinetic measurements of the reactivity of hydrogen peroxide and ozone towards small atmospherically relevant aldehydes, ketones and organic acids in aqueous solutions

2014 ◽  
Vol 14 (9) ◽  
pp. 4503-4514 ◽  
Author(s):  
L. Schöne ◽  
H. Herrmann
Keyword(s):  
Hydrogen Peroxide ◽  
Rate Constants ◽  
Radical Reaction ◽  
Degradation Process ◽  
Atmospheric Environment ◽  
Radical Reactions ◽  
Kinetic Measurements ◽  
First Order ◽  
Reaction Rate Constants ◽  
Vis Spectroscopy

Abstract. Free radical reactions are an important degradation process for organic compounds within the aqueous atmospheric environment. Nevertheless, non-radical oxidants such as hydrogen peroxide and ozone also contribute to the degradation and conversion of these substances (Tilgner and Herrmann, 2010). In this work, kinetic investigations of non-radical reactions were conducted using UV / Vis spectroscopy (dual-beam spectrophotometer and stopped flow technique) and a capillary electrophoresis system applying pseudo-first order kinetics to reactions of glyoxal, methylglyoxal, glycolaldehyde, glyoxylic, pyruvic and glycolic acid as well as methacrolein (MACR) and methyl vinyl ketone (MVK) with H2O2 and ozone at 298 K. The measurements indicate rather small rate constants at room temperature of k2nd < 3 M−1 s−1 (except for the unsaturated compounds exposed to ozone). Compared to radical reaction rate constants the values are about 10 orders of magnitude smaller (kOH&amp;bullet; ~109 M−1 s−1). However, when considering the much larger non-radical oxidant concentrations compared to radical concentrations in urban cloud droplets, calculated first-order conversion rate constants change the picture towards H2O2 reactions becoming more important, especially when compared to the nitrate radical. For some reactions mechanistic suggestions are also given.

Spectral band wings and rate constants of rotational relaxation as data source on molecular torques

1998 ◽  
Vol 94 (4) ◽  
pp. 627-642 ◽  
Author(s):  
A.P. KOUZOV
Keyword(s):  
Rate Constants ◽  
Spectral Band ◽  
Rotational Relaxation ◽  
Data Source

Modification of optical properties of PC-PBT/Cr2O3 and PC-PBT/CdS nanocomposites by gamma irradiation

2020 ◽  
Vol 92 (2) ◽  
pp. 20402
Author(s):  
Kaoutar Benthami ◽  
Mai ME. Barakat ◽  
Samir A. Nouh
Keyword(s):  
Refractive Index ◽  
Optical Properties ◽  
Band Gap ◽  
Color Difference ◽  
Band Gap Energy ◽  
Polybutylene Terephthalate ◽  
Γ Irradiation ◽  
Gap Energy ◽  
Vis Spectroscopy ◽  
Oxygen Atoms

Nanocomposite (NCP) films of polycarbonate-polybutylene terephthalate (PC-PBT) blend as a host material to Cr2O3 and CdS nanoparticles (NPs) were fabricated by both thermolysis and casting techniques. Samples from the PC-PBT/Cr2O3 and PC-PBT/CdS NCPs were irradiated using different doses (20–110 kGy) of γ radiation. The induced modifications in the optical properties of the γ irradiated NCPs have been studied as a function of γ dose using UV Vis spectroscopy and CIE color difference method. Optical dielectric loss and Tauc's model were used to estimate the optical band gaps of the NCP films and to identify the types of electronic transition. The value of optical band gap energy of PC-PBT/Cr2O3 NCP was reduced from 3.23 to 3.06 upon γ irradiation up to 110 kGy, while it decreased from 4.26 to 4.14 eV for PC-PBT/CdS NCP, indicating the growth of disordered phase in both NCPs. This was accompanied by a rise in the refractive index for both the PC-PBT/Cr2O3 and PC-PBT/CdS NCP films, leading to an enhancement in their isotropic nature. The Cr2O3 NPs were found to be more effective in changing the band gap energy and refractive index due to the presence of excess oxygen atoms that help with the oxygen atoms of the carbonyl group in increasing the chance of covalent bonds formation between the NPs and the PC-PBT blend. Moreover, the color intensity, ΔE has been computed; results show that both the two synthesized NCPs have a response to color alteration by γ irradiation, but the PC-PBT/Cr2O3 has a more response since the values of ΔE achieved a significant color difference >5 which is an acceptable match in commercial reproduction on printing presses. According to the resulting enhancement in the optical characteristics of the developed NCPs, they can be a suitable candidate as activate materials in optoelectronic devices, or shielding sheets for solar cells.

Inhibition in Purified Systems and in Human Plasma of Chimaeric Plasminogen Activators Consisting of the NH2-Terminal Region of Tissue-Type Plasminogen Activator and the COOH-Terminal Region of UrokinaseType Plasminogen Activator

1988 ◽  
Vol 60 (02) ◽  
pp. 247-250 ◽  
Author(s):  
H R Lijnen ◽  
L Nelles ◽  
B Van Hoef ◽  
F De Cock ◽  
D Collen
Keyword(s):  
Plasminogen Activator ◽  
Rate Constants ◽  
Plasminogen Activators ◽  
Second Order ◽  
Tissue Type ◽  
Single Chain ◽  
Chain Molecules ◽  
Order Rate ◽  
Type Plasminogen Activator ◽  
Urokinase Type Plasminogen Activator

SummaryRecombinant chimaeric molecules between tissue-type plasminogen activator (t-PA) and single chain urokinase-type plasminogen activator (scu-PA) or two chain urokinase-type plasminogen activator (tcu-PA) have intact enzymatic properties of scu-PA or tcu-PA towards natural and synthetic substrates (Nelles et al., J Biol Chem 1987; 262: 10855-10862). In the present study, we have compared the reactivity with inhibitors of both the single chain and two chain variants of recombinant u-PA and two recombinant chimaeric molecules between t-PA and scu-PA (t-PA/u-PA-s: amino acids 1-263 of t-PA and 144-411 of u-PA; t-PA/u-PA-e: amino acids 1-274 of t-PA and 138-411 of u-PA). Incubation with human plasma in the absence of a fibrin clot for 3 h at 37° C at equipotent concentrations (50% clot lysis in 2 h), resulted in significant fibrinogen breakdown (to about 40% of the normal value) for all two chain molecules, but not for their single chain counterparts. Preincubation of the plasminogen activators with plasma for 3 h at 37° C, resulted in complete inhibition of the fibrinolytic potency of the two chain molecules but did not alter the potency of the single chain molecules. Inhibition of the two chain molecules occurred with a t½ of approximately 45 min. The two chain variants were inhibited by the synthetic urokinase inhibitor Glu-Gly-Arg-CH2CCl with apparent second-order rate constants of 8,000-10,000 M−1s−1, by purified α2-antiplasmin with second-order rate constants of about 300 M−1s−1, and by plasminogen activator inhibitor-1 (PAI-1) with second-order rate constants of approximately 2 × 107 M−1s−1.It is concluded that the reactivity of single chain and two chain forms of t-PA/u-PA chimaers with inhibitors is very similar to that of the single and two chain forms of intact u-PA.

Effect of Calcium ion on the interaction between Thrombin and Heparin. Thermal Denaturation

1977 ◽  
Vol 38 (03) ◽  
pp. 0677-0684 ◽  
Author(s):  
Raymund Machovich ◽  
Péter Arányi
Keyword(s):  
Calcium Ions ◽  
Rate Constants ◽  
Thermal Denaturation ◽  
Time Course ◽  
Complex Analysis ◽  
Heat Inactivation ◽  
Second Phase ◽  
Denaturation Kinetics ◽  
Enzyme Protection ◽  
Enzyme Denaturation

SummaryHeat inactivation of thrombin at 54° C followed first order kinetics with a rate constant of 1.0 min−1 approximately. Addition of heparin resulted in protection against thermal denaturation and, at the same time, rendered denaturation kinetics more complex. Analysis of the biphasic curve of heat inactivation in the presence of heparin revealed that the rate constants of the second phase changed systematically with heparin concentrations. Namely, at 4.5 × 10−6M, 9 × 10−6M, 1.8 × 10−5M and 3.6 × 10−5M heparin concentrations, the rate constants were 0.27 min−1, 0.17 min−1, 0.11 min−1 and 0.06 min−1, respectively.Sulfate as well as phosphate ions displayed also enzyme protection against heat inactivation, however, the same effect was obtained already at a heparin concentration, lower by three orders of magnitude.The kinetics of enzyme denaturation was not affected by calcium ions, whereas in the presence of heparin the inactivation rate of thrombin changed, i. e. calcium ions abolished the biphasic character of time course of thermal denaturation.Thus, the data suggest that calcium ions contribute to the effect of heparin on thrombin.

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