“Prebiotic soup” often features in discussions of origins of life research, both as a theoretical concept when discussing abiological pathways to modern biochemical building blocks and, more recently, as a feedstock in prebiotic chemistry experiments focused on discovering emergent, systems-level processes such as polymerization, encapsulation, and evolution. However, until now, little systematic analysis has gone into the design of well-justified prebiotic mixtures, which are needed to facilitate experimental replicability and comparison among researchers. This paper explores principles that should be considered in choosing chemical mixtures for prebiotic chemistry experiments by reviewing the natural environmental conditions that might have created such mixtures and then suggests reasonable guidelines for designing recipes. We discuss both “assembled” mixtures, which are made by mixing reagent grade chemicals, and “synthesized” mixtures, which are generated directly from diversity-generating primary prebiotic syntheses. We discuss different practical concerns including how to navigate the tremendous uncertainty in the chemistry of the early Earth and how to balance the desire for using prebiotically realistic mixtures with experimental tractability and replicability. Examples of two assembled mixtures, one based on materials likely delivered by carbonaceous meteorites and one based on spark discharge synthesis, are presented to illustrate these challenges. We explore alternative procedures for making synthesized mixtures using recursive chemical reaction systems whose outputs attempt to mimic atmospheric and geochemical synthesis. Other experimental conditions such as pH and ionic strength are also considered. We argue that developing a handful of standardized prebiotic recipes may facilitate coordination among researchers and enable the identification of the most promising mechanisms by which complex prebiotic mixtures were “tamed” during the origin of life to give rise to key living processes such as self-propagation, information processing, and adaptive evolution. We end by advocating for the development of a public prebiotic chemistry database containing experimental methods (including soup recipes), results, and analytical pipelines for analyzing complex prebiotic mixtures.
more »
« less
Nitrile regio-synthesis by Ni centers on a siliceous surface: implications in prebiotic chemistry
By means of quantum chemistry (PBE0/def2-TZVPP; DLPNO-CCSD(T)/cc-pVTZ) and small, but reliable models of Polyhedral Oligomeric Silsesquioxanes (POSS), an array of astrochemically-relevant catalysis products, related to prebiotic and origin of life chemistry, has been theoretically explored. In this work, the heterogeneous phase hydrocyanation reaction of an unsaturated CC bond (propene) catalyzed by a Ni center complexed to a silica surface is analyzed. Of the two possible regioisomers, the branched iso-propyl-cyanide is thermodynamically and kinetically preferred over the linear n -propyl-cyanide ( T = 200 K). The formation of nitriles based on a regioselective process has profound implications on prebiotic and origin of life chemistry, as well as deep connections to terrestrial surface chemistry and geochemistry.
more »
« less
- Award ID(s):
- 1846408
- PAR ID:
- 10431074
- Date Published:
- Journal Name:
- Chemical Communications
- Volume:
- 58
- Issue:
- 82
- ISSN:
- 1359-7345
- Page Range / eLocation ID:
- 11579 to 11582
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Urea is a key molecule in the search for the origin of life and a basic chemical produced in large quantities by industry. Its formation from ammonia and carbon dioxide requires either high pressures and temperatures or, under milder conditions, catalysts or additional reagents. In this study, we observed the spontaneous formation of urea under ambient conditions from ammonia and carbon dioxide in the surface layer of aqueous droplets. Single, optically trapped droplets were probed by using Raman bands as markers. We found the surface layer to act like a microscopic flow reactor, with chemical gradients providing access to unconventional reaction pathways. This observation revealed a general mechanistic scheme for distinctive droplet chemistry. Interfacial chemistry is a possible nonenergetic route for urea formation under prebiotic conditions.more » « less
-
The discovery of over 200 gas-phase chemical compounds in interstellar space has led to the speculation that this non-terrestrial synthesis may play a role in the origin of life. These identifications were possible because of laboratory spectroscopy, which provides the molecular “fingerprints” for astronomical observations. Interstellar chemistry produces a wide range of small, organic molecules in dense clouds, such as NH2COCH3, CH3OCH3, CH3COOCH3, and CH2(OH)CHO. Carbon is also carried in fullerenes C60 and C70, which can preserve C-C bonds from circumstellar environments for future synthesis. Elusive phosphorus is now found in molecular clouds, the sites of star formation, in the molecules PO and PN. Such clouds can collapse into solar systems, although the chemical/physical processing of the emerging planetary disk is uncertain. The presence of molecule-rich interstellar starting material, as well as the link to planetary bodies such as meteorites and comets, suggests astrochemical processes set a prebiotic foundation.more » « less
-
Abstract MXenes, two‐dimensional (2D) transition metal carbides and/or nitrides, possess surface termination groups such as hydroxyl, oxygen, and fluorine, which are available for surface functionalization. Their surface chemistry is critical in many applications. This article reports amine functionalization of Ti3C2TxMXene surface with [3‐(2‐aminoethylamino)‐propyl]trimethoxysilane (AEAPTMS). Characterization techniques such as X‐ray photoelectron spectroscopy verify the success of the surface functionalization and confirm that the silane coupling agent bonds to Ti3C2Txsurface both physically and chemically. The functionalization changes the MXene surface charge from −35 to +25 mV at neutral pH, which allows for in situ preparation of self‐assembled films. Further, surface charge measurements of the functionalized MXene at different pH values show that the functionalized MXene has an isoelectric point at a pH around 10.7, and the highest reported positive surface charge of +62 mV at a pH of 2.58. Furthermore, the existence of a mixture of different orientations of AEAPTMS and the simultaneous presence of protonated and free amine groups on the surface of Ti3C2Txare demonstrated. The availability of free amine groups on the surface potentially permits the fabrication of crosslinked electrically conductive MXene/epoxy composites, dye adsorbents, high‐performance membranes, and drug carriers. Surface modifications of this type are applicable to many other MXenes.more » « less
-
null (Ed.)In the search for life beyond Earth, distinguishing the living from the non-living is paramount. However, this distinction is often elusive, as the origin of life is likely a stepwise evolutionary process, not a singular event. Regardless of the favored origin of life model, an inherent “grayness” blurs the theorized threshold defining life. Here, we explore the ambiguities between the biotic and the abiotic at the origin of life. The role of grayness extends into later transitions as well. By recognizing the limitations posed by grayness, life detection researchers will be better able to develop methods sensitive to prebiotic chemical systems and life with alternative biochemistries.more » « less
An official website of the United States government

