Cinétique de la formation de la métalloporphyrine Cu(II)—dérivé tétra éthylènediamino de la protoporphyrine IX (ENP) en milieu aqueux

1979 ◽  
Vol 57 (22) ◽  
pp. 2916-2922 ◽  
Author(s):  
Guy Paquette ◽  
Miklos Zador

The kinetics of formation of the metalloporphyrin Cu(II)–ENP is dependent on the pH due to the protonation of the pyrrol nitrogen atoms and the protonation of the diamino groups of the side chains. The degree of protonation of these side chains also influences the degree of association of the prophyrin and the metalloporphyrin in solution. The order of reaction with respect to the porphyrin is not unity, a consequence of an inhibition by the reaction product; this inhibition operates via the formation of a new species, a mixed complex of porphyrin–metalloporphyrin of low reactivity.The order of reaction with respect to Cu(II) is also not unity, a consequence of the chelation of Cu(II) by the diamino groups of the side chains. The presence of Cu(II) ligands influence both the reaction kinetics and the nature of the final reaction product. [Journal translation]

Author(s):  
V. P. Sklizkova ◽  
L. Z. Vilenchik ◽  
V. V. Kudryavtsev ◽  
T. B. Tennikova ◽  
N. G. Bel'nikevich ◽  
...  

1956 ◽  
Vol 34 (1) ◽  
pp. 1233-1250 ◽  
Author(s):  
G. A. Maclachlan ◽  
E. R. Waygood

A study of the kinetics of the enzymically-catalyzed decarboxylation and oxidation of indoleacetic acid has provided evidence that it is a chain autoxidation initiated and propagated by two enzyme-controlled peroxidations. The following reaction sequence occurs:[Formula: see text]where S—COOH = indoleacetic acid; S∙ = skatole radical; SO2∙ = oxidized skatole radical or indole peroxide; SO2H = final reaction product; ROH = phenolic cofactor, i.e., resorcinol; RO∙ = semiquinol or aryl radical.


1956 ◽  
Vol 34 (6) ◽  
pp. 1233-1250 ◽  
Author(s):  
G. A. Maclachlan ◽  
E. R. Waygood

A study of the kinetics of the enzymically-catalyzed decarboxylation and oxidation of indoleacetic acid has provided evidence that it is a chain autoxidation initiated and propagated by two enzyme-controlled peroxidations. The following reaction sequence occurs:[Formula: see text]where S—COOH = indoleacetic acid; S∙ = skatole radical; SO2∙ = oxidized skatole radical or indole peroxide; SO2H = final reaction product; ROH = phenolic cofactor, i.e., resorcinol; RO∙ = semiquinol or aryl radical.


2002 ◽  
Vol 17 (7) ◽  
pp. 1772-1778 ◽  
Author(s):  
Jau-Ho Jean ◽  
Yu-Ching Fang ◽  
Steve X. Dai ◽  
David L. Wilcox

Crystallization and reaction kinetics of a crystallizable K2O–CaO–SrO–BaO–B2O3–SiO2 glass powder with 17–40 vol% titania powder were investigated. The initially amorphous K2O–CaO–SrO–BaO–B2O3–SiO2 glass powder formed cristobalite (SiO2) and pseudowollastonite [(Ca, Ba, Sr)SiO3] during firing. The above crystalline phases were completely replaced by a crystalline phase of titanite [(Ca, Sr, Ba)TiSiO5] when the amount of added titania was greater than a critical value, e.g., 10 vol%, at 99–1100 °C. A chemical reaction taking place at the interface between titania and the glass was attributed to the above observation. The dissolved titania changed the composition of the glass, and the dissolution kinetics was much faster than the formation of cristobalite and pseudowollastonite. Activation energy analysis showed that the crystallization of titanite [(Ca,Sr,Ba)TiSiO5] was controlled by a reaction-limiting kinetics of formation for the Ti–O bond.


2008 ◽  
Vol 2 (4) ◽  
pp. 263-270
Author(s):  
Ludmila Kosyanchuk ◽  
◽  
Nataly Kozak ◽  
Oksana Antonenko ◽  
Yury Nizelskii ◽  
...  

According to DSC and EPR data kinetics of formation of simultaneous semi-interpenetrating polymer networks based on crosslinked polyurethane and linear polymethylmethacrylate with 50:50 and 70:30 ratio obtained in the presence of 3d-metal chelates depends on type of metal. On the other hand system composition determines polyurethane or polymethylmethacrylate selection during formation of complexes with metal -diketonates.


MRS Advances ◽  
2017 ◽  
Vol 2 (53) ◽  
pp. 3181-3186 ◽  
Author(s):  
Elizabeth A. Pogue ◽  
Melissa Goetter ◽  
Angus Rockett

ABSTRACTDifferential scanning calorimetry experiments on mixed Cu2-xS, ZnS, and SnS2 precursors were conducted to better understand how Cu2ZnSnS4 (CZTS) and Cu2SnS3 form. The onset temperatures of Cu2SnS3 reactions and CZTS suggest that the ZnS phase may mediate Cu2SnS3 formation at lower temperatures before a final CZTS phase forms. We also found no evidence of a stable Cu2ZnSn3S8 phase. The major diffraction peaks associated with Cu2ZnSnS4, and Cu2SnS3 (overlaps with ZnS, as well) began to grow around 380 °C, although the final reaction to form Cu2ZnSnS4 probably did not occur until higher temperatures were reached. An exothermic reaction was observed corresponding to formation of this phase. There was some variability in the onset temperature for reactions to form Cu2SnS3. At least 5 steps are involved in this reaction and several segments of the reaction had relatively reproducible energies.


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