Quantifying Catalysis at the Origin of Life.

The construction of hypothetical environments to produce organic molecules such as metabolic intermediates or amino acids is the subject of ongoing research into the emergence of life. Experiments specifically focused on an anabolic approach typically rely on a mineral catalyst to facilitate the supply of organics that may have produced prebiotic building blocks for life. Alternatively to a true catalytic system, a mineral could be sacrificially oxidized in the production of organics, necessitating the emergent 'life' to turn to virgin materials for each iteration of metabolic processes. The aim of this perspective is to view the current 'metabolism-first' literature through the lens of materials chemistry to evaluate the need for higher catalytic activity and materials analyses. While many elegant studies have detailed the production of chemical building blocks under geologically plausible and biologically relevant conditions, few appear to do so with sub-stoichiometric amounts of metals or minerals. Moving toward sub-stoichiometric metals with rigorous materials analyses is necessary to demonstrate the viability of an elusive cornerstone of the 'metabolism-first' hypotheses: catalysis. We emphasize that future work should aim to demonstrate decreased catalyst loading, increased productivity, and/or rigorous materials analyses for evidence of true catalysis.

CO2 reduction driven by a pH gradient.

All life on Earth is built of organic molecules, so the primordial sources of reduced carbon remain a major open question in studies of the origin of life. A variant of the alkaline-hydrothermal-vent theory for life's emergence suggests that organics could have been produced by the reduction of CO2 via H2 oxidation, facilitated by geologically sustained pH gradients. The process would be an abiotic analog-and proposed evolutionary predecessor-of the Wood-Ljungdahl acetyl-CoA pathway of modern archaea and bacteria. The first energetic bottleneck of the pathway involves the endergonic reduction of CO2 with H2 to formate (HCOO-), which has proven elusive in mild abiotic settings. Here we show the reduction of CO2 with H2 at room temperature under moderate pressures (1.5 bar), driven by microfluidic pH gradients across inorganic Fe(Ni)S precipitates. Isotopic labeling with 13C confirmed formate production. Separately, deuterium (2H) labeling indicated that electron transfer to CO2 does not occur via direct hydrogenation with H2 but instead, freshly deposited Fe(Ni)S precipitates appear to facilitate electron transfer in an electrochemical-cell mechanism with two distinct half-reactions. Decreasing the pH gradient significantly, removing H2, or eliminating the precipitate yielded no detectable product. Our work demonstrates the feasibility of spatially separated yet electrically coupled geochemical reactions as drivers of otherwise endergonic processes. Beyond corroborating the ability of early-Earth alkaline hydrothermal systems to couple carbon reduction to hydrogen oxidation through biologically relevant mechanisms, these results may also be of significance for industrial and environmental applications, where other redox reactions could be facilitated using similarly mild approaches.

Dry Ice as an Alternative Leavening Agent for Pancakes to Demonstrate Phase Transitions or Chemical Transformations.

A culinary exploration of the role of CO2 in leavening is described. This demonstration substitutes dry ice for chemical leaveners in order to achieve the same pancake fluffiness. Under the universal framework of food and cooking, we developed this activity to bring aspects of phase transitions and chemical transformations to a broad audience.

Convergent Strategy for the Synthesis of Oxa-, Thia-, and Selena[5]helicenes by Acetylene-Activated SNAr Reactions.

A tandem acetylene-activated SNAr-anionic cyclization strategy is presented for the synthesis of chalcogen-containing hetero[5]helicenes. Oxa-, thia-, and selena[5]helicenes are accessed from common ortho-fluoro-ethynylarene precursors, allowing the heteroatoms to be installed at the 1-position or 1- and 12-positions of the hetero[5]helicene inner core surface.

Iron-iron oxide core-shell nanoparticles are active and magnetically recyclable olefin and alkyne hydrogenation catalysts in protic and aqueous media.

We report for the first time the use of iron-iron oxide core-shell nanoparticles for the hydrogenation of olefins and alkynes under mild conditions in ethanol and in an aqueous medium. This catalyst proves robust towards the presence of oxidants, such as oxygen and water, is magnetically recoverable and shows selectivity towards the less activated double bonds.

Fe3O4 nanoparticle-supported copper(I) pybox catalyst: magnetically recoverable catalyst for enantioselective direct-addition of terminal alkynes to imines.

An Fe(3)O(4) nanoparticle-supported copper(I) pybox catalyst, which exhibits excellent reactivity and yields products with good enantioselectivity, was developed. As a proof of concept, six optically active propargyl amines were obtained in excellent yields. The catalyst can be magnetically removed and recycled easily six times without a decrease in activity or enantioselectivity.