Chain Mechanism of Radical-Initiated Ligand Exchange in PtCl42-in Aqueous Solution

1996 ◽  
Vol 100 (6) ◽  
pp. 1989-1992 ◽  
Author(s):  
Eberhard Janata ◽  
Arnim Henglein ◽  
Boris Ershov
Author(s):  
Isabelle M. Dixon ◽  
Sylvestre Bonnet ◽  
Fabienne Alary ◽  
Jérôme Cuny

1972 ◽  
Vol 45 (10) ◽  
pp. 3081-3083 ◽  
Author(s):  
Tetsuo Shinohara ◽  
Takato Yamada ◽  
Noriyuki Takebayashi ◽  
Shun-ichi Hiraki ◽  
Akira Ohyoshi

1970 ◽  
Vol 48 (8) ◽  
pp. 1232-1238 ◽  
Author(s):  
C. E. Burchill ◽  
I. S. Ginns

The radiation-induced oxidation of 2-propanol by hydrogen peroxide in neutral deaerated aqueous solution has been investigated. 2-Propanol is oxidized to acetone, and hydrogen peroxide reduced in stoichiometrically equivalent high yields. The yields are independent of hydrogen peroxide concentration in the range 5 × 10−2 to 10−3 M and linearly dependent on alcohol concentration in the range 0.13 to 1.05 M. The reaction yields increased with decreasing dose rate.The results are explained by a chain mechanism in which initiation occurs via H-atom abstraction from 2-propanol to form either (CH3)2ĊOH (1) or CH3 CHOH ĊH2 (2). 1 reacts with H2O2 in a chain propagating reaction[Formula: see text]2 may abstract the α hydrogen from the parent alcohol[Formula: see text]or undergo bimolecular termination. A lower limit of 53 ± 101mole−1 s−1 is estimated for the rate constant for this radical conversion reaction.


1972 ◽  
Vol 50 (11) ◽  
pp. 1751-1756 ◽  
Author(s):  
C. E. Burchill ◽  
G. P. Wollner

The radiation-induced oxidation of 2-propanol to acetone by N2O in alkaline aqueous solution proceeds via a free radical chain mechanism independent of pH above 12.5. The results are explained by abstraction of H from 2-propanol by O− at both the α and β positions (85% α attack). Chain propagation is by reaction of the α radical anion, (CH3)2ĊO−, with N2O with a rate constant of (3.8 ± 0.4) × 104 M−1 s−1 and by reaction of the β radical, ĊH2(CH3)CHOH, with 2-propanol to give the α radical with a rate constant of 430 ± 30 M−1 s−1.The conclusions are supported by the demonstration of kinetic isotope effects for selectively deuterated alcohols.


2000 ◽  
Vol 44 (11) ◽  
pp. 2954-2961 ◽  
Author(s):  
Philippe M. Loiseau ◽  
Patrick Lubert ◽  
Jean-Gerard Wolf

ABSTRACT Twelve new dithiaarsanes were evaluated for their in vitro and in vivo trypanocidal properties in regard to their three parent molecules, 4-amino-phenylarsenoxide, melarsenoxide, and 4-dansylamino-phenylarsenoxide. The most potent dithiaarsane, compound 2b, had a minimum effective concentration of 1.5 nM after 48 h of incubation and at a dose of 0.39 μmol/kg of body weight (0.2 mg/kg) administered subcutaneously cured 100% of mice acutely infected withTrypanosoma brucei brucei CMP. With this model, the chemotherapeutic index of compound 2b was 512, compared to 256 for melarsamine dihydrochloride (Cymelarsan) under the same conditions. With a chronic infection produced by T. brucei brucei GVR, compound 2b cured 100% of mice after treatment at a dose of 25 μmol/kg (12.5 mg/kg) for 4 consecutive days, whereas melarsamine dihydrochloride and potassium melarsonyl (Trimelarsan) cured less than 50% mice at this dose. For both acute and late-stage infections, dithiaarsanes having a melaminophenyl ring exhibited the most-potent trypanocidal activity. Compound 2b is thus one of the most active organoarsenicals described in a mouse trypanosomiasis model. Considering that the main intracellular targets of organoarsenicals are thiol groups, we studied the possibility of ligand exchange between Cymelarsan and several dithiols. In aqueous solution, we observed a rapid exchange of cysteamine from melarsamine with free cysteamine and also with various dithiols always in favor of more stable cyclic derivatives. These ligand exchanges suggest the ability of trivalent organoarsenicals to react with targets such as trypanothione and dihydrolipoic acid. Among several ligands, a 1,3-dimercaptopropane moiety appeared the most suitable for trypanocidal activity.


1992 ◽  
Vol 31 (14) ◽  
pp. 3023-3025 ◽  
Author(s):  
Birthe Broennum ◽  
H. Saaby Johansen ◽  
L. H. Skibsted

2016 ◽  
Vol 16 (6) ◽  
pp. 1603-1613 ◽  
Author(s):  
Chunnuan Ji ◽  
Rongjun Qu ◽  
Qinghua Tang ◽  
Xiguang Liu ◽  
Hou Chen ◽  
...  

A Fe(III)-loaded chelating resin named Fe(III) AO PAN was prepared by immobilizing Fe(III) onto porous amidoximated polyacrylonitrile (AO PAN) obtained by modification of hydroxylamine with polyacrylonitrile (PAN), which was synthesized by suspended emulsion polymerization. The structures of PAN, AO PAN, and Fe(III)-AO PAN were characterized by infrared spectrometry and scanning electron microscopy. The performance of Fe(III)-AO PAN as the ligand exchange adsorbent to remove As(V) from aqueous solution was investigated using static equilibrium and dynamic adsorption experiments. The adsorption experiments showed that Fe(III)-AO PAN had higher adsorption selectivity for As(V) than other ubiquitous anions in nature water body such as Cl−, SO42−, HCO3−, PO43−, and SiO32−. The optimal pH for adsorption of As(V) on Fe(III) AO PAN was 2.0, with the maximum adsorption capacity of 0.55 mg/g. The As(V) adsorbed on Fe(III) AO PAN could be easily eluted with 10 BV of 5% NaCl solution (at pH = 9.0).


Sign in / Sign up

Export Citation Format

Share Document