Matches in SemOpenAlex for { <https://semopenalex.org/work/W4313455053> ?p ?o ?g. }
- W4313455053 endingPage "1754" @default.
- W4313455053 startingPage "1734" @default.
- W4313455053 abstract "Experimental reports about observation of spontaneous mirror symmetry breaking and chiral amplification in stereoselective Mannich and aldol reactions, run under fully achiral initial conditions, have drawn a lot of attention, fuelled partly by the role these reactions could have played in chemical evolution as a cause for still puzzling observed homochirality of biomolecules, often considered a prerequisite for the origin of life. We have now revisited this still unresolved problem, using DFT computation of all combinatorially possible transition states and numerical solution of complete set of resulting coupled kinetic rate equations to model the aldol reaction rigorously from the first principles and without making any a priori assumptions. Spontaneous mirror symmetry breaking in this autocatalytic, reversible, closed and homogenous system is explained by a supercritical pitchfork bifurcation, occurring in concentrations of enantiomers due to time-delayed kinetic instability of racemic composition of reaction mixture, when reactants are initially provided in non-stoichiometric quantities. Same process, taking place under similar conditions in primordial soup of chemicals, might conceivably explain origin of biological homochirality of sugar molecules on early earth billions of years ago. Our results suggest that seemingly innocuous chemical reactions could exhibit unexpected and counter-intuitive emergent behaviour, when initial conditions are appropriately chosen. Chiral amplification in self-catalyzed aldol reaction occurs during approach of thermodynamic equilibrium in accord with principle of microscopic reversibility and second law of thermodynamics." @default.
- W4313455053 created "2023-01-06" @default.
- W4313455053 creator A5063930311 @default.
- W4313455053 date "2023-01-01" @default.
- W4313455053 modified "2023-09-27" @default.
- W4313455053 title "Spontaneous emergence of enantioenriched chiral aldol reaction products from Achiral precursors in solution and origin of biological homochirality of sugars: a first-principles study" @default.
- W4313455053 cites W1133972832 @default.
- W4313455053 cites W126915739 @default.
- W4313455053 cites W1458390031 @default.
- W4313455053 cites W180974030 @default.
- W4313455053 cites W1830333769 @default.
- W4313455053 cites W1938657618 @default.
- W4313455053 cites W1967935039 @default.
- W4313455053 cites W1974030786 @default.
- W4313455053 cites W1980657276 @default.
- W4313455053 cites W1980661496 @default.
- W4313455053 cites W1981473471 @default.
- W4313455053 cites W1983589072 @default.
- W4313455053 cites W1999816960 @default.
- W4313455053 cites W2001396724 @default.
- W4313455053 cites W2003501808 @default.
- W4313455053 cites W2007151621 @default.
- W4313455053 cites W2012621789 @default.
- W4313455053 cites W2016414726 @default.
- W4313455053 cites W2018847257 @default.
- W4313455053 cites W2024034443 @default.
- W4313455053 cites W2026033901 @default.
- W4313455053 cites W2026655238 @default.
- W4313455053 cites W2030102144 @default.
- W4313455053 cites W2030991498 @default.
- W4313455053 cites W2031596719 @default.
- W4313455053 cites W2034707078 @default.
- W4313455053 cites W2036543135 @default.
- W4313455053 cites W2037795808 @default.
- W4313455053 cites W2039369009 @default.
- W4313455053 cites W2042880407 @default.
- W4313455053 cites W2046451925 @default.
- W4313455053 cites W2046891991 @default.
- W4313455053 cites W2049456149 @default.
- W4313455053 cites W2049967797 @default.
- W4313455053 cites W2055270014 @default.
- W4313455053 cites W2055393482 @default.
- W4313455053 cites W2057208203 @default.
- W4313455053 cites W2062378595 @default.
- W4313455053 cites W2066606644 @default.
- W4313455053 cites W2074781111 @default.
- W4313455053 cites W2078033380 @default.
- W4313455053 cites W2082255480 @default.
- W4313455053 cites W2085268679 @default.
- W4313455053 cites W2086742287 @default.
- W4313455053 cites W2091214342 @default.
- W4313455053 cites W2094879703 @default.
- W4313455053 cites W2094997337 @default.
- W4313455053 cites W2095382289 @default.
- W4313455053 cites W2098142145 @default.
- W4313455053 cites W2099542709 @default.
- W4313455053 cites W2104976075 @default.
- W4313455053 cites W2106344185 @default.
- W4313455053 cites W2108229334 @default.
- W4313455053 cites W2114597423 @default.
- W4313455053 cites W2120693706 @default.
- W4313455053 cites W2122284068 @default.
- W4313455053 cites W2129633896 @default.
- W4313455053 cites W2129642562 @default.
- W4313455053 cites W2145355283 @default.
- W4313455053 cites W2148809791 @default.
- W4313455053 cites W2149166648 @default.
- W4313455053 cites W2150196878 @default.
- W4313455053 cites W2158686686 @default.
- W4313455053 cites W2159132799 @default.
- W4313455053 cites W2168358964 @default.
- W4313455053 cites W2168898569 @default.
- W4313455053 cites W2293468725 @default.
- W4313455053 cites W2333229651 @default.
- W4313455053 cites W2334005130 @default.
- W4313455053 cites W2409684087 @default.
- W4313455053 cites W2513049044 @default.
- W4313455053 cites W2520922898 @default.
- W4313455053 cites W2575255273 @default.
- W4313455053 cites W2602093712 @default.
- W4313455053 cites W2606356817 @default.
- W4313455053 cites W2612513854 @default.
- W4313455053 cites W2752811770 @default.
- W4313455053 cites W2765491844 @default.
- W4313455053 cites W2790922269 @default.
- W4313455053 cites W2885896728 @default.
- W4313455053 cites W2897918831 @default.
- W4313455053 cites W2920863558 @default.
- W4313455053 cites W2921646214 @default.
- W4313455053 cites W2979524262 @default.
- W4313455053 cites W3000068290 @default.
- W4313455053 cites W3033722918 @default.
- W4313455053 cites W3037559536 @default.
- W4313455053 cites W3097841722 @default.
- W4313455053 cites W3099371444 @default.
- W4313455053 cites W3131099722 @default.
- W4313455053 cites W3135069445 @default.
- W4313455053 cites W3156150680 @default.