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Ramanarayanan Krishnamurthy

Publications and source records attributed to Ramanarayanan Krishnamurthy.

17 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2024

Experimentally Modeling the Emergence of Prebiotically Plausible Phospholipid Vesicles

The prebiotic emergence of protocells is an important part of any origins of life scenario. Although fatty-acid-based vesicles are well studied, how they transitioned to phospholipid vesicles is uncertain. Herein, we show that cyclic-phospholipids formed from fatty acids and glycerol could have played a role by generating a heterogeneous library of vesicles with diverse morphologies and tolerance to a range of metal ions, temperature, and pH. The cyclic phosphate moiety facilitates the natural emergence of vesicles composed of diacyl-phospholipids to become part of the chemical evolutionary process. Competing emergent properties of the various systems (facilitated by additives) could have led to an early preference of the sn-1,2-acyl-substitution on the glycerol backbone coincidental with extant biology. Thus, cyclic-phospholipids could have played a significant role not only in early prebiotic protocellular chemistry but also in facilitating the chemical evolution of protocells from the structurally simple to the functionally more complex.

Sunil Pulletikurti↗
NASA NTRS2022

A Plausible Prebiotic Path to Nucleosides: Ribosides and Related Aldosides Generated from Ribulose, Fructose, and Similar Abiotic Precursors

The prebiotic origins of ribose, nucleosides, and eventually RNA are enduring questions whose answers are central to the RNA world hypothesis. The abiotic synthesis of sugars was first demonstrated over a century ago, but no known prebiotic reaction produces ribose (an aldose sugar) selectively and in good yield. In contrast, ribulose, and fructose (ketose sugars) and other monosaccharides are formed in high yield by several robust abiotic reactions. It is reported here that ketose sugars - both ketopentoses and ketohexoes - serve as precursors for the formation of ribosides and other aldosides, as demonstrated by glycoside-forming reactions involving barbituric acid, a plausibly prebiotic nucleobase. Moreover, a one-pot reaction of glyceraldehyde and barbituric acid was discovered which under mild conditions, and without special minerals or other catalysts, results in the formation of glycosides. These results reveal that an exclusive or high-yielding generation of free ribose was not required for its incorporation into processes that provided the foundations for life.

Tyler P. Roche↗
NASA NTRS2020

A Sensitive Quantitative Analysis of Abiotically Synthesized Short Homopeptides using Ultraperformance Liquid Chromatography and Time-of-Flight Mass Spectrometry

In the origins of life field understanding the abiotic polymerization of simple organic monomers (e.g., amino acids) into larger biomolecules (e.g., oligopeptides), remains a seminal challenge. Recently, preliminary observations showed a limited set of peptides formed in the presence of the plausible prebiotic phosphorylating agent, diamidophosphate (DAP), highlighting the need for an analytical tool to critically evaluate the ability of DAP to induce oligomerization of simple organics under aqueous conditions. However, performing accurate and precise, targeted analyses of short oligopeptides remains a distinct challenge in the analytical chemistry field. Here, we developed a new technique to detect and quantitate amino acids and their homopeptides in a single run using ultraperformance liquid chromatography-fluorescence detection/time of flight mass spectrometry. Over an 8-minute retention time window, 18 target analytes were identified and quantitated, 16 of which were chromatographically separated at, or near baseline resolution. Compound identity was confirmed by accurate mass analysis using a 10 ppm mass tolerance window. This method featured limits of detection < 5 nM (< 1 fmol on column) and limits of quantitation (LOQs) <15 nM (< 3 fmol on column). The LODs and LOQs were upwards of ∼28x and ∼788x lower, respectively, than previous methods for the same analytes, highlighting the quantifiable advantages of this new method. Both detectors provided good quantitative linearity (R(exp 2) > 0.985) for all analytes spanning concentration ranges ∼3 - 4 orders of magnitude. We performed a series of laboratory experiments to investigate DAP-mediated oligomerization of amino acids and peptides and analyzed experimental products with the new method. DAP readily polymerized amino acids and peptides under a range of simulated environmental conditions. This research underscores the potential of DAP to have generated oligopeptides on the primordial Earth, enhancing prebiotic chemical diversity and complexity at or near the origin of life.

Prebiotic Chemistry and Analytical Chemistry↗