Spontaneous assembly of redox-active iron-sulfur clusters at low concentrations of cysteine.
Spontaneous assembly of redox-active iron-sulfur clusters at low concentrations of cysteine.
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DOI：
10.1038/s41467-021-26158-2
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发表时间：
2021-10-11
影响因子：
16.6
通讯作者：
Lane N
中科院分区：
文献类型：
--
作者：
Jordan SF;Ioannou I;Rammu H;Halpern A;Bogart LK;Ahn M;Vasiliadou R;Christodoulou J;Maréchal A;Lane N
铁硫(FeS)蛋白是一种古老的、对生命至关重要的蛋白质，它参与电子传递和二氧化碳固定。FeS团簇的结构类似于闪锌矿等FeS矿物的晶胞结构，这种矿物存在于与生命起源有关的热液系统中。然而，从矿物表面到生物簇的益生菌途径尚不清楚。在这里，我们证明了在碱性pH条件下，无机Fe2+/Fe3+和S2−与水中微摩尔浓度的氨基酸半胱氨酸相互作用，自发形成FeS团簇。碳酸氢根离子稳定团簇，甚至在浓度为10 mm时单独促进团簇的形成，可能是通过盐析效应。我们用UV-Vis光谱、57Fe-Mössbauer光谱和1H-核磁共振证明了[4Fe4S]、[2Fe2S]和单核铁团簇的形成与浓度有关。循环伏安测试表明，该簇合物具有氧化还原活性。我们的发现表明，负责生物电子转移和二氧化碳还原的结构可能是在生命起源时由单体自发形成的。铁硫(FeS)蛋白参与电子传递和CO2固定。在这里，作者表明，在氨基酸半胱氨酸的存在下，FeS团簇可以在类似于在Hadean碱性热液喷口预期的条件下自发形成，这表明它们在生命起源时出现的一种可信的机制。
Iron-sulfur (FeS) proteins are ancient and fundamental to life, being involved in electron transfer and CO2 fixation. FeS clusters have structures similar to the unit-cell of FeS minerals such as greigite, found in hydrothermal systems linked with the origin of life. However, the prebiotic pathway from mineral surfaces to biological clusters is unknown. Here we show that FeS clusters form spontaneously through interactions of inorganic Fe2+/Fe3+ and S2− with micromolar concentrations of the amino acid cysteine in water at alkaline pH. Bicarbonate ions stabilize the clusters and even promote cluster formation alone at concentrations >10 mM, probably through salting-out effects. We demonstrate robust, concentration-dependent formation of [4Fe4S], [2Fe2S] and mononuclear iron clusters using UV-Vis spectroscopy, 57Fe-Mössbauer spectroscopy and 1H-NMR. Cyclic voltammetry shows that the clusters are redox-active. Our findings reveal that the structures responsible for biological electron transfer and CO2 reduction could have formed spontaneously from monomers at the origin of life. Iron-sulfur (FeS) proteins are involved in electron transfer and CO2 fixation. Here, the authors show that FeS clusters can form spontaneously in the presence of the amino acid cysteine, in conditions similar those expected in Hadean alkaline hydrothermal vents, suggesting a plausible mechanism of their emergence at the origin of life.
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DOI：
10.3390/life6030033
发表时间：
2016-08-11
期刊：
Life (Basel, Switzerland)
影响因子：
--
作者：
Black RA;Blosser MC
通讯作者：
Blosser MC
DOI：
10.1073/pnas.94.13.6635
发表时间：
1997-06-24
影响因子：
11.1
作者：
Coldren, CD;Hellinga, HW;Caradonna, JP
通讯作者：
Caradonna, JP
影响因子：
1.8
作者：
DAVISON, W;BUFFLE, J;DEVITRE, R
通讯作者：
DEVITRE, R
影响因子：
5.4
作者：
Forzi, L;Koch, J;Hedderich, R
通讯作者：
Hedderich, R
影响因子：
15
作者：
DEPAMPHILIS, BV;AVERILL, BA;HOLM, RH
通讯作者：
HOLM, RH