scholarly journals Porphyrin in prebiotic catalysis: Ascertaining a route for the emergence of early metalloporphyrins

2021 ◽  
Author(s):  
Shikha Dagar ◽  
Susovan Sarkar ◽  
Sudha Rajamani

Metal ions are known to catalyze certain prebiotic reactions. However, the transition from metal ions to extant metalloenzymes remains unclear. Porphyrins are found ubiquitously in the catalytic core of many ancient metalloenzymes. In this study, we evaluated the influence of porphyrin-based organic scaffold, on the catalysis, emergence and putative molecular evolution of prebiotic metalloporphyrins. We studied the effect of porphyrins on the transition metal ion-mediated oxidation of hydroquinone (HQ). We report a change in the catalytic activity of the metal ions in the presence of porphyrin. This was observed to be facilitated by the coordination between metal ions and porphyrins or by formation of non-coordinated complexes. The metal-porphyrin complexes also oxidized NADH, underscoring its versatility at oxidizing more than one substrate. Our study highlights the selective advantage that some of the metal ions would have had in the presence of porphyrin, underscoring their role in shaping the evolution of protometalloenzymes.

1981 ◽  
Vol 46 (10) ◽  
pp. 2354-2363 ◽  
Author(s):  
Svatomír Kmošták ◽  
Karel Setínek

The catalytic activity of sulphonated macroporous styrene-divinylbenzene copolymers, the exchange capacity of which was neutralized from 30, 50 and 80% by Fe(III) ions and from 30% by Na ions and that of Wofatit Y-37 ion exchanger neutralized from 10% of its total exchange capacity by several transition metal ions and by sodium has been studied in isomerisation of cyclohexene and dehydration of 1-propanol in the gas phase at 130 °C. It was demonstrated that in both reactions transition metal ions exhibit additional effect to the expected neutralization of the polymer acid groups. In the case of cyclohexene isomerization, this effect depends on the degree of crosslinking of polymer mass of the catalyst. Such dependence has not been, however, observed in dehydration of 1-propanol. The type of transition metal ions did not exhibit any significant effect on the catalytic activity of the polymer catalysts studied.


1988 ◽  
Vol 58 (4) ◽  
pp. 198-210 ◽  
Author(s):  
James W. Rucker ◽  
David M. Cates

Peracetic acid can be catalyzed to bleach cotton fibers at temperatures as low as 30°C by incorporating 2,2î-bipyridine in the bleach solution. Treatment of the fibers with HCl prior to bleaching reduces bleaching effectiveness by removing trace transition metal ions from the fibers. Sorption of individual ions (Cr+3 Mn+2, Fe+2, Fe+3 Co+2, Ni+2, Cu+2, and Zn+2) by HCl treated cotton fibers prior to bleaching indicates that the ferrous ion produces the greatest catalytic effect, and it is only effective when the metal ion is in the fiber as opposed to in solution. Ferrous ions in the fibers sorb 2,2î-bipyridine from solution to form the tris-2,2î-bipyridine ferrous ion complex that is associated with the fibers, and it is the trischelate associated with the fibers that catalyzes bleaching. The effects of pH, temperature, and concentrations of 2,2î-bipyridine, sodium lauryl sulfate, and transition metal ions (in the fibers and in solution) on bleaching effectiveness and peracetic acid decomposition have been studied, and a bleaching mechanism is proposed.


2013 ◽  
Vol 45 (11) ◽  
pp. 721-733 ◽  
Author(s):  
F. Aneesa ◽  
K. C. Rajanna ◽  
M. Venkateswarlu ◽  
K. Rajendar Reddy ◽  
Y. Arun Kumar

1982 ◽  
Vol 35 (7) ◽  
pp. 1335 ◽  
Author(s):  
M Chatterjee ◽  
D Ganguli

The exchange behaviour of some divalent transition metal ions M2+ (Zn2+, Cu2+, Ni2+, Co2+, Mn2+) in a zeolite NaX (SiO2/Al2O3 2.75) was studied at intermediate stages before equilibrium. The equivalent counter ion supply in the solution, given by the equivalent ratio of the two counter ions 2M2+/Na+, was found to be critical in determining the saturation level of exchange. The series of relative abilities of exchange was very similar to the well known selectivity series at equilibrium. It is suggested that water exchange of the metal ions in solution could be one of the factors controlling the relative ease of ion exchange.


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