TY - JOUR

T1 - Formation of Chiral and Supercoiled Structures in Photoinduced Formose Reaction in the de novo Model

AU - Stovbun, S. V.

AU - Zanin, A. M.

AU - Skoblin, A. A.

AU - Tregubova, M. A.

AU - Tverdislov, V. A.

AU - Taran, O. P.

AU - Parmon, V. N.

N1 - Publisher Copyright: © 2019, Pleiades Publishing, Ltd.

PY - 2019/5/1

Y1 - 2019/5/1

N2 - Abstract: In a de novo physicochemical modeling, the synthesis of biologically important sugars and other chiral compounds without any chemical initiators is demonstrated for the first time by photolysis of a concentrated formaldehyde solution and subsequent condensation of the product; chiral condensed phase detected; the splitting of enantiomers in terms of chirality sign at the moment of condensation is determined; hierarchical (three-level) helical structure of the optically active anisometric phase (strings) is detected, in which the strings of a larger diameter consists of helically plaited strings of a smaller diameter; it was found that the direction of twisting of the strings when they are helically plaited from the strings of the previous hierarchical level is determined by their supramolecular chirality (the sign of an excess of the left or right helical supramolecular submicroscopic structures); it was shown that structure formation in systems similar to prebiological may occur through the mechanism of supercoiling already in an aqueous solution of sugars with molecular weights μ of ~102 Da, that is, much earlier than linear chiral macromolecules are formed. The results are obtained under conditions that correspond to modern ideas about the form and vector of prebiological evolution, and therefore may be of fundamental importance for molecular biology.

AB - Abstract: In a de novo physicochemical modeling, the synthesis of biologically important sugars and other chiral compounds without any chemical initiators is demonstrated for the first time by photolysis of a concentrated formaldehyde solution and subsequent condensation of the product; chiral condensed phase detected; the splitting of enantiomers in terms of chirality sign at the moment of condensation is determined; hierarchical (three-level) helical structure of the optically active anisometric phase (strings) is detected, in which the strings of a larger diameter consists of helically plaited strings of a smaller diameter; it was found that the direction of twisting of the strings when they are helically plaited from the strings of the previous hierarchical level is determined by their supramolecular chirality (the sign of an excess of the left or right helical supramolecular submicroscopic structures); it was shown that structure formation in systems similar to prebiological may occur through the mechanism of supercoiling already in an aqueous solution of sugars with molecular weights μ of ~102 Da, that is, much earlier than linear chiral macromolecules are formed. The results are obtained under conditions that correspond to modern ideas about the form and vector of prebiological evolution, and therefore may be of fundamental importance for molecular biology.

KW - chirality

KW - evolution

KW - formaldehyde

KW - formose reaction

KW - self-organization

KW - supercoiling

KW - STRINGS

KW - MECHANISM

KW - FORMALDEHYDE

UR - http://www.scopus.com/inward/record.url?scp=85070763170&partnerID=8YFLogxK

U2 - 10.1134/S1990793119020222

DO - 10.1134/S1990793119020222

M3 - Article

AN - SCOPUS:85070763170

VL - 13

SP - 486

EP - 501

JO - Russian Journal of Physical Chemistry B

JF - Russian Journal of Physical Chemistry B

SN - 1990-7931

IS - 3

ER -