Сhiral and Racemic Fields Concept for Understanding of the Homochirality Origin, Asymmetric Catalysis, Chiral Superstructure Formation from Achiral Molecules, and B-Z DNA Conformational Transition

Павлов, В. А.; Shushenachev, Yaroslav V.; Zlotin, S. G.

doi:10.3390/sym11050649

Cited by 9 publications

(3 citation statements)

References 321 publications

(508 reference statements)

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“…Chirality, or handedness, is a fundamental physical attribute, which spans the length scales ranging from the elementary particles to the asymmetry of galaxies. , The way that chirality in chemistry, or molecular handedness, arose in a primitive terrestrial environment and how it can be triggered, amplified, and transferred by chemists, are challenging problems with clear scientific and technological potentials for science and society . Chirality constitutes a unifying feature of the living world and is a prime driving force for molecular selection and genetic evolution. , …”

Section: Introductionmentioning

confidence: 99%

Spontaneous Deracemizations

et al. 2021

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Spontaneous deracemizations is a challenging, multidisciplinary subject in current chirality research. In the absence of any chiral inductors, an achiral substance or a racemic composition is driven into an enantioenriched or even homochiral state through a selective energy input, e.g., chemical potential, photoirradiation, mechanical grinding, ultrasound waves, thermal gradients, etc. The most prominent examples of such transformations are the Soai reaction and the Viedma deracemization. In this review, we track the most recent developments in this topic and recall that many other deracemizations have been reported for solutions from mesophases to conglomerate crystallizations. A compiled set of simply available achiral organic, inorganic, organometallic, and MOF compounds, yielding conglomerate crystals, should give the impetus to realize new experiments on spontaneous deracemizations. Taking into account thermodynamic constraints, modeling efforts have shown that structural features alone are not sufficient to describe spontaneous deracemizations. As a guideline of this review, particular attention is paid to the physicochemical origin and symmetry requirements of such processes.

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Section: Introductionmentioning

confidence: 99%

Spontaneous Deracemizations

et al. 2021

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“…Interestingly, despite the detection of over 20 prochiral molecules in the ISM, we were surprised to note that the significance of prochirality in interstellar chemistry has been severely understated in the literature. In fact, to the extent we exhaustively searched, the phrases “prochiral”/”prochirality”/”prochiral molecule” themselves barely appear not more than ∼a dozen times in the literature of astrochemistry and interstellar chemistry. − Even therein, the aforementioned phrases appeared casually in scattered contexts, and the chemistry associated with prochirality was not discussed at all. One reason could perhaps be that, until recently no chiral molecule was detected in the ISM.…”

Section: Introductionmentioning

confidence: 99%

Possible Role of Metal-Ions in the Chemistry of Prochirality and the Origin of Chirality in the Interstellar Medium

Thripati

Gautam

Ramabhadran

2023

ACS Earth Space Chem.

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Propylene oxide (c-C 3 H 6 O) is the first chiral molecule detected in the interstellar medium (ISM). Its recent detection has opened up newer avenues to be explored in interstellar chemistry. On earth, metal-ions play a preeminent role in the chemistry of chirality and prochirality. Taking a cue from this idea, we computationally investigate the possible role of metal-ions in (a) the origin of chirality in the ISM and (b) advancing interstellar prochiral chemistry; noting that prochirality is a severely understudied concept in astrochemistry. The gas-phase reactions of ethylene, and propylene with OOH radical to lead to the formation of ethylene oxide and propylene oxide respectively were noted to be excellent model reactions, and have been chosen to examine the role of the metal-ions. The interstellar metal-ions being studied (viz. Al + , Mg + , and Mg 2+ ) are considered in three different forms�as bare metal-ions, or as hydrated metal-ions bound to one molecule of water, and as part of a neutral molecule. Carefully calibrated electronic structure calculations (CCSD(T) and DFT) were used to obtain the relevant saddle points (minimum energy structures and transition states). One key conclusion from this work is that, metal-ions, regardless of what form they are in, lead to the barrierless formation of the epoxides, thereby facilitating the generation of interstellar chirality. The key chemical, and astrochemical facets involved in the chemistry of metal-ions in the circumstellar envelope of IRC+10216 are also discussed herein in detail. This work further recommends the detection of four molecules in the ISM, namely, aziridine, methyl aziridine, 2-amino-3-hydroxy propane, and 2-hydroxy-3-amino propane. Lastly, a foremost point to emerge out of this study and related contemporary works probing the chemistry of metal-ions in the ISM is that metal-ions may act as the glue connecting interstellar gas-phase chemistry with the surface chemistry occurring on ice-grains, and could aid in the unravelling of complex and new aspects in astrochemistry.

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“…Bonner et al have first demonstrated asymmetric adsorption of alanine on crystal faces of quartz [11], but it was not considered as an effective process for regional or global racemate resolution because dand l-quartz occur in equal proportions on a global scale [29][30][31]. However, sizeable volumes of homochiral quartz were reported from hydrothermal veins [32], and from graphic granite [33].…”

Section: Introductionmentioning

confidence: 99%

Racemate Resolution of Alanine and Leucine on Homochiral Quartz, and Its Alteration by Strong Radiation Damage

Garcia

Meinert

Finger

et al. 2021

Life

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Homochiral proteins orchestrate biological functions throughout all domains of life, but the origin of the uniform l-stereochemistry of amino acids remains unknown. Here, we describe enantioselective adsorption experiments of racemic alanine and leucine onto homochiral d- and l-quartz as a possible mechanism for the abiotic emergence of biological homochirality. Substantial racemate resolution with enantiomeric excesses of up to 55% are demonstrated to potentially occur in interstitial pores, along grain boundaries or small fractures in local quartz-bearing environments. Our previous hypothesis on the enhanced enantioselectivity due to uranium-induced fission tracks could not be validated. Such capillary tubes in the near-surface structure of quartz have been proposed to increase the overall chromatographic separation of enantiomers, but no systematic positive correlation of accumulated radiation damage and enantioselective adsorption was observed in this study. In general, the natural l-quartz showed stronger enantioselective adsorption affinities than synthetic d-quartz without any significant trend in amino acid selectivity. Moreover, the l-enantiomer of both investigated amino acids alanine and leucine was preferably adsorbed regardless of the handedness of the enantiomorphic quartz sand. This lack of mirror symmetry breaking is probably due to the different crystal habitus of the synthetic z-bar of d-quartz and the natural mountain crystals of l-quartz used in our experiments.

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Сhiral and Racemic Fields Concept for Understanding of the Homochirality Origin, Asymmetric Catalysis, Chiral Superstructure Formation from Achiral Molecules, and B-Z DNA Conformational Transition

Cited by 9 publications

References 321 publications

Spontaneous Deracemizations

Spontaneous Deracemizations

Possible Role of Metal-Ions in the Chemistry of Prochirality and the Origin of Chirality in the Interstellar Medium

Racemate Resolution of Alanine and Leucine on Homochiral Quartz, and Its Alteration by Strong Radiation Damage

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