02340nas a2200169   4500008004100000022001400041245014000055210006900195260000900264300001600273490000700289520168600296100001901982700002602001700001702027856012602044       2025                        eng d  a2041-652000aThe critical helping hand of water: theory shows the way to obtain elusive, granular information about kinetic asymmetry driven systems0 acritical helping hand of water theory shows the way to obtain el  cAUG   a14940-149550 v163 a<p>
	Kinetic asymmetry is crucial in chemical systems where the selective synthesis of one product over another, or the acceleration of specific reaction(s) is necessary. However, obtaining precise information with current experimental methods about the behavior of such systems as a function of time, substrate concentration and other relevant factors, is not possible. Computational chemistry provides a powerful means to address this problem. The current study unveils a two-pronged computational approach: (i) full quantum chemical studies with density functional theory (DFT), followed by (ii) stochastic simulations with a validated Gillespie algorithm (GA) (using representative model systems where necessary), to study the behavior of a kinetic asymmetry driven unidirectional molecular motor (1-phenylpyrrole2,2 `-dicarboxylic acid) (Nature, 2022, 604 (7904), 80-85). Our approach allows us to understand what is really taking place in the system, underlining the crucial role played by water molecules in facilitating the rotation of the motor. It is seen that water lubricates the motion by increasing the rotation rate constant of the final step by, remarkably, more than ten orders of magnitude! These insights further serve to explain the efficient rotation of the very recently reported gel-embedded molecular motor (Nature, 2025, 637 (8046), 594-600), providing an upper limit for the allowed rotation barrier in such systems, and thus also casts light into the functioning of bio-molecular motors. The current work therefore provides a template for carefully and properly studying a wide variety of important, kinetic asymmetry driven systems in the future.</p>
1 aBajpai, Priyam1 aThulasiram, Shrivatsa1 aVanka, Kumar  uhttps://library.ncl.res.in/content/critical-helping-hand-water-theory-shows-way-obtain-elusive-granular-information-about