Assembly of [FenSn(SR)4]2- (n = 2, 4) in aqueous media from iron salts, thiols, and sulfur, sulfide, or thiosulfate plus rhodanese

Bonomi, F.; Werth, Mark T.; Kurtz, Donald M.

doi:10.1021/ic00219a026

Cited by 80 publications

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“…[ (Bonomi et al, 1985;Stevens and Kurtz, 1985). This was the beginning of the organic take-over from a mineral based prebiotic chemistry (Milner-White and Russell, 2005).…”

Section: The Hydrothermal Moundmentioning

confidence: 99%

Geodynamic and metabolic cycles in the Hadean

2005

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Abstract. High-degree melting of hot dry Hadean mantle at ocean ridges and plumes resulted in a crust about 30 km thick, overlain in places by extensive and thick mafic volcanic plateaus. Continental crust, by contrast, was relatively thin and mostly submarine. At constructive and destructive plate boundaries, and above the many mantle plumes, acidic hydrothermal springs at ∼400 • C contributed Fe and other transition elements as well as P and H 2 to the deep ocean made acidulous by dissolved CO 2 and minor HCl derived from volcanoes. Away from ocean ridges, submarine hydrothermal fluids were cool (≤100 • C), alkaline (pH ∼10), highly reduced and also H 2 -rich. Reaction of solvents in this fluid with those in ocean water was catalyzed in a hydrothermal mound, a natural self-restoring flow reactor and fractionation column developed above the alkaline spring. The mound consisted of brucite, Mg-rich clays, ephemeral carbonates, Fe-Ni sulfide and green rust. Acetate and glycine were the main products, some of which were eluted to the ocean. The rest, along with other organic byproducts were retained and concentrated within Fe-Ni sulfide compartments. These compartments, comprising the natural hydrothermal reactor, consisted partly of greigite (Fe 5 NiS 8 ). It was from reactions between organic modules confined within these inorganic compartments that the first prokaryotic organism evolved. These acetogenic precursors to the bacteria diversified and migrated down the mound and into the ocean floor to inaugurate the "deep biosphere". Once there they were protected from cataclysmic heating events caused by large meteoritic impacts. Geodynamic forces led to the eventual obduction of the deep biosphere into the photic zone where, initially protected by a thin veneer of sediment, the use of solar energy was mastered and photosynthesis emerged. The further evolution to oxygenic photosynthesis was effected as catalytic [Mn,Ca] -bearing molecules that otherwise wouldCorrespondence to: N. T. Arndt (arndt@ujf-grenoble.fr) have been interred in minerals such as ranciéite and hollandite in shallow marine manganiferous sediments, were sequestered and invaginated within the cyanobacterial precursor where, energized by light, they could oxidize water. Thus, a chemical sedimentary environment was required both for the emergence of chemosynthesis and of oxygenic photosynthesis, the two innovations that did most to change the nature of our planet.

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“…[ (Bonomi et al, 1985;Stevens and Kurtz, 1985). This was the beginning of the organic take-over from a mineral based prebiotic chemistry (Milner-White and Russell, 2005).…”

Section: The Hydrothermal Moundmentioning

confidence: 99%

Geodynamic and metabolic cycles in the Hadean

2005

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“…This could be a consequence either of an incomplete removal of iron from the protein or of the reduction of ferric iron to the ferrous form by the large excess of dithiol present in those experiments, to give the colorless Fe(II)/DHL-COOH complex. This reduction is known to occur easily, in particular under fairly alkaline conditions such as those used in the present experiments [8]. When DHL-CONH2 replaced the corresponding acid in the presence of the necessary detergent, no variation in the reaction rate was observed over iron concentrations ranging from 0.09 mM to 0.56 mM.…”

Section: Iron Removal Us U Function Of the Concentrution Ojjerritinmentioning

confidence: 54%

“…Sephadex G-25 fine, under identical conditions, gave a very poor separation. As a control we chromatographed a buffered solution of synthetically made [Fe2(DHL-C00-)3]3- [8], which was eluted from the G-25 column in the void volume, and gave an apparent M , of about 14000 on AcA 54. Since the expected M , of the ferric iron/DHL-COOH complex is about 700 [8], this chromatographic behaviour appears to indicate an aggregation of the molecules of the complex itself in the experimental conditions used.…”

Section: Gel Permeation Chromatography Of Jerritin Reacted With Dithiolsmentioning

confidence: 99%

“…As a control we chromatographed a buffered solution of synthetically made [Fe2(DHL-C00-)3]3- [8], which was eluted from the G-25 column in the void volume, and gave an apparent M , of about 14000 on AcA 54. Since the expected M , of the ferric iron/DHL-COOH complex is about 700 [8], this chromatographic behaviour appears to indicate an aggregation of the molecules of the complex itself in the experimental conditions used. Another possible explanation for the poor permeation of the highly hydrophilic pores of the Sephadex matrixes by the molecules of the complex could rely on its amphipathic nature.…”

Section: Gel Permeation Chromatography Of Jerritin Reacted With Dithiolsmentioning

confidence: 99%

“…In the course of other studies we noticed the ease of formation and the stability of complexes of iron(1II) with the physiological dithiols DL-dihydrolipoate and uL-dihydrolipoamidc [8,91. The size of these two compounds, their amphiphilic nature, thcir rcducing properties and their natural occurrence in mammalian tissues, where they are formed from the corresponding oxidized compounds, led us to an in vitro investigation of the reaction between them and horse spleen ferritin, which gave very encouraging preliminary results [I 01.…”

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confidence: 91%

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Removal of ferritin‐bound iron by DL‐dihydrolipoate and DL‐dihydrolipoamide

Bonomi

Pagani

1986

European Journal of Biochemistry

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The naturally occurring dithiols DL-dihydrolipoate and DL-dihydrolipoamide were tested for their ability in the removal of ferritin-bound iron. Both compounds remove the iron stored inside the protein by complexing it in the ferric form. The iron can be reduced to the ferrous form by excess dithiol, but this is not necessary for complete removal. Reaction is complete in few hours and, at molar ratios of chelator to metal higher than 10, more than 60% of the ferritin-bound iron was removed. The amount of iron stored in the ferritin molecule does not affect the rate and the yield of the removal reaction.The iron-removing ability of DL-dihydrolipoate was found to be identical to that of an equimolar solution of sodium dithionite, and to be pH-dependent.Results are discussed in terms of the molecular architecture of ferritin and of the chelators, and their possible physiological relevance is pointed out.Iron storage and mobilisation in mammalian cells have drawn the attention of many investigators from different fields. Ferritin plays a central role in iron metabolism, so that studies of this protein have been particularly intensive. Highly detailed structural information about this molecule is available [l], its response to metabolic and pathological changes in the iron concentration has been extensively studied [2, 31 and a large number of compounds have been tested for their ability in the removal of the iron stored inside the ferritin protein shell [4 -61. Removal of ferritin-bound iron is a prominent topic from the point of view of either biochemists and clinicians, since it relates to the metabolic fate of iron and to the treatment of the iron overload, which is consequent to, among others, the heavy transfusional therapy of some blood diseases. The most widely used chelators are of bacterial origin, are fairly expensive and require parentheral administration [7].In the course of other studies we noticed the ease of formation and the stability of complexes of iron(1II) with the physiological dithiols DL-dihydrolipoate and uL-dihydrolipoamidc [8, 91. The size of these two compounds, their amphiphilic nature, thcir rcducing properties and their natural occurrence in mammalian tissues, where they are formed from the corresponding oxidized compounds, led us to an in vitro investigation of the reaction between them and horse spleen ferritin, which gave very encouraging preliminary results [I 01.In the present paper we wish to report a more extensive investigation of this subject.C'orrc,spondc~ic.nc~~ lu

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Functional Display of Active Bovine Adrenodoxin on the Surface of E. coli by Chemical Incorporation of the [2Fe–2S] Cluster

2001

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The display of heterologous proteins on the surface of living cells bears promising options for a wide variety of biotechnological applications. Up to now, however, cellular surface display was merely restricted to simple polypeptide chains. Here we present for the first time the efficient display of a protein (bovine adrenodoxin) that contains an inorganic, prosthetic group in its active form on the surface of Escherichia coli. For this purpose apo-adrenodoxin was transported to the cell surface and anchored within the outer membrane by the autotransporter pathway. Incorporation of the iron-sulfur cluster was achieved by a single-vial, one-step titration under anaerobic conditions. The biological function of surface-displayed holo-adrenodoxin could be established through adrenodoxin-dependent steroid conversion by two different cytochrome P450 enzymes and the number of functional molecules on the cell surface could be determined to be more than 10(5) per cell. Neither the expression of adrenodoxin nor the incorporation of the chemical iron-sulfur cluster reduced the viability of the bacterial cells.

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Assembly of [FenSn(SR)4]2- (n = 2, 4) in aqueous media from iron salts, thiols, and sulfur, sulfide, or thiosulfate plus rhodanese

Cited by 80 publications

References 0 publications

Geodynamic and metabolic cycles in the Hadean

Geodynamic and metabolic cycles in the Hadean

Removal of ferritin‐bound iron by DL‐dihydrolipoate and DL‐dihydrolipoamide

Functional Display of Active Bovine Adrenodoxin on the Surface of E. coli by Chemical Incorporation of the [2Fe–2S] Cluster

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