Chiral Autocatalysis and Mirror Symmetry Breaking

Gellman, Andrew J.; Ernst, Karl‐Heinz

doi:10.1007/s10562-018-2380-x

Cited by 33 publications

(48 citation statements)

References 93 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However, enantioselective autocatalysis may also fulfill condition (3) for several different compositions. Autocatalytic reaction networks capable of yielding species/enantiomer selection have been previously reviewed [3,46,47,[56][57][58]. In addition to the networks cited/discussed therein, we must include the recently reported enantioselective hypercycle [50,59], which is highly significant due to its coincidence with the replicators of the nucleic acid and protein domain [60].…”

Section: The Direct Synthesismentioning

confidence: 99%

Chemical Basis of Biological Homochirality during the Abiotic Evolution Stages on Earth

Ribó

Hochberg

2019

Symmetry

View full text Add to dashboard Cite

Spontaneous mirror symmetry breaking (SMSB), a phenomenon leading to non-equilibrium stationary states (NESS) that exhibits biases away from the racemic composition is discussed here in the framework of dissipative reaction networks. Such networks may lead to a metastable racemic non-equilibrium stationary state that transforms into one of two degenerate but stable enantiomeric NESSs. In such a bifurcation scenario, the type of the reaction network, as well the boundary conditions, are similar to those characterizing the currently accepted stages of emergence of replicators and autocatalytic systems. Simple asymmetric inductions by physical chiral forces during previous stages of chemical evolution, for example in astrophysical scenarios, must involve unavoidable racemization processes during the time scales associated with the different stages of chemical evolution. However, residual enantiomeric excesses of such asymmetric inductions suffice to drive the SMSB stochastic distribution of chiral signs into a deterministic distribution. According to these features, we propose that a basic model of the chiral machinery of proto-life would emerge during the formation of proto-cell systems by the convergence of the former enantioselective scenarios.

show abstract

Section: The Direct Synthesismentioning

confidence: 99%

Chemical Basis of Biological Homochirality during the Abiotic Evolution Stages on Earth

Ribó

Hochberg

2019

Symmetry

View full text Add to dashboard Cite

show abstract

“…Experimental results show that the energy difference between catalytic reaction with two enantiomer catalysts is on the order of a few KJ/mol, which translates that enantiospecificity (the ratio of rate coefficients for reactions catalyzed by enantiomers) is~1.5, which after substituting this value into Eq. (6) results that η 1 ≈ 0.2 (Gellman and Ernst 2018). However, it was shown (Wattis and Coveney 2005) that larger values of η 1 are required even when mutual inhibition reaction rate is twice as large as polymerization rate of same chirality polymers (χ…”

Section: Introductionmentioning

confidence: 99%

Chiral Symmetry Breaking in Large Peptide Systems

Konstantinov

Константинова

2020

Orig Life Evol Biosph

View full text Add to dashboard Cite

Chiral symmetry breaking in far from equilibrium systems with large number of amino acids and peptides, like a prebiotic Earth, was considered. It was shown that if organic catalysts were abundant, then effective averaging of enantioselectivity would prohibit any symmetry breaking in such systems. It was further argued that non-linear (catalytic) reactions must be very scarce (called the abundance parameter) and catalysts should work on small groups of similar reactions (called the similarity parameter) in order to chiral symmetry breaking have a chance to occur. Models with 20 amino acids and peptide lengths up to three were considered. It was shown that there are preferred ranges of abundance and similarity parameters where the symmetry breaking can occur in the models with catalytic synthesis / catalytic destruction / both catalytic synthesis and catalytic destruction. It was further shown that models with catalytic synthesis and catalytic destruction statistically result in a substantially higher percentage of the models where the symmetry breaking can occur in comparison to the models with just catalytic synthesis or catalytic destruction. It was also shown that when chiral symmetry breaking occurs, then concentrations of some amino acids, which collectively have some mutually beneficial properties, go up, whereas the concentrations of the ones, which don’t have such properties, go down. An open source code of the whole system was provided to ensure that the results can be checked, repeated, and extended further if needed.

show abstract

“…One of the challenges to optimizing enantioselective processes on chiral surfaces is that it requires a fundamental understanding of the enantiospecific interactions between chiral molecules and chiral surfaces. 14,16,17 The optimization of enantioselective processes on chiral surfaces requires an understanding of the influence of surface structure on surface reaction kinetics. This is complicated by the fact that there are an infinite number of surface orientations that can be exposed by any bulk crystal structure.…”

Section: Introductionmentioning

confidence: 99%

“…This means that, a FCC(hkl) surface is chiral, if h a k a l a h and h Â k Â l a 0. [19][20][21][22] The ideal structures of chiral metal surfaces have low-Miller-index terraces separated by monoatomic kinked step edges as shown for the Cu (3,1,17) surface in the ESI, † Fig. SI 1.…”

Section: Introductionmentioning

confidence: 99%

“…51 TA is an ideal chiral probe for study of enantiospecific surface chemistry because its decomposition mechanism and kinetics are well understood on Cu single crystal surfaces. [52][53][54][55][56][57] After adsorption at 400 K on Cu(110), the saturation coverage has 5/16 TA/Cu atom and with TA singly deprotonated (HO 2 C-CH(OH)CH(OH)CO 2 -Cu). At a lower absolute coverage of 1 4 TA/ Cu atom, the TA is doubly deprotonated copper tartrate (Cu-O 2 CCH(OH)CH(OH)CO 2 -Cu).…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation