Rapid hydrolysis rates of thio- and phosphate esters constrain the origin of metabolism to cool, acidic to neutral environments.

Universal to all life is a reliance on energy carriers such as adenosine triphosphate (ATP) which connect energy-releasing reactions to energy-consuming processes. While ATP is ubiquitously used today, simpler molecules such as thioesters and polyphosphates are hypothesized to be primordial energy carriers. Investigating environmental constraints on the non-enzymatic emergence of metabolism, we find that hydrolysis rates-not hydrolysis energies-differentiate phosphate esters and thioesters.

FeNiS-A Potent Bifunctional Efficient Electrocatalyst for the Overall Electrochemical Water Splitting in Alkaline Electrolyte.

For a carbon-neutral society, the production of hydrogen as a clean fuel through water electrolysis is currently of great interest. Since water electrolysis is a laborious energetic reaction, it requires high energy to maintain efficient and sustainable production of hydrogen. Catalytic electrodes can reduce the required energy and minimize production costs.

Electrochemically induced metal- vs. ligand-based redox changes in mackinawite: identification of a Fe- and polysulfide-containing intermediate.

Under anaerobic conditions, ferrous iron reacts with sulfide producing FeS, which can then undergo a temperature, redox potential, and pH dependent maturation process resulting in the formation of oxidized mineral phases, such as greigite or pyrite. A greater understanding of this maturation process holds promise for the development of iron-sulfide catalysts, which are known to promote diverse chemical reactions, such as H, CO and NO reduction processes. Hampering the full realization of the catalytic potential of FeS, however, is an incomplete knowledge of the molecular and redox processess ocurring between mineral and nanoparticulate phases.

Correction: Simultaneous synthesis of thioesters and iron-sulfur clusters in water: two universal components of energy metabolism.

Correction for 'Simultaneous synthesis of thioesters and iron-sulfur clusters in water: two universal components of energy metabolism' by Sebastian A. Sanden et al., Chem.

Simultaneous synthesis of thioesters and iron-sulfur clusters in water: two universal components of energy metabolism.

Thioesters are important intermediates in both synthetic organic and biosynthetic reaction pathways. Here we show that thioesters can be synthesized in an aqueous reaction between thioacetate and thiols. The reaction can be coupled to a second reaction between sulfide and either ferrous or ferric iron, which drives the reaction forward.