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The first synthetic molecular rotor capable of performing repeated 360\u00b0 rotations due to a combination of photo\u2010 and thermally activated processes was reported in 1999. The progress in designing different molecular machines in the intervening years has been remarkable, with several outstanding examples appearing in the last few years. Despite the synthetic accomplishments, there remains confusion regarding the fundamental design principles by which the motions of molecules can be controlled, with significant intellectual tension between mechanical and chemical ways of thinking about and describing molecular machines. A thermodynamically consistent analysis of the kinetics of several molecular rotors and pumps shows that while light driven rotors operate by a power\u2010stroke mechanism, kinetic asymmetry\u2014the relative heights of energy barriers\u2014is the sole determinant of the directionality of catalysis driven machines. Power\u2010strokes\u2014the relative depths of energy wells\u2014play no role whatsoever in determining the sign of the directionality. These results, elaborated using trajectory thermodynamics and the nonequilibrium pump equality, show that kinetic asymmetry governs the response of many non\u2010equilibrium chemical phenomena.<\/jats:p>","DOI":"10.1002\/anie.202306569","type":"journal-article","created":{"date-parts":[[2024,1,18]],"date-time":"2024-01-18T10:11:54Z","timestamp":1705572714000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":43,"title":["Kinetic Asymmetry and Directionality of Nonequilibrium Molecular Systems"],"prefix":"10.1002","volume":"63","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-7472-187X","authenticated-orcid":false,"given":"Raymond Dean","family":"Astumian","sequence":"first","affiliation":[{"name":"Department of Physics and Astronomy The University of Maine  5709 Bennett Hall Orono ME-04469 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2024,1,18]]},"reference":[{"key":"e_1_2_9_1_1","unstructured":"B. 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