{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,26]],"date-time":"2026-09-26T04:11:49Z","timestamp":1790395909927,"version":"4.1.0"},"reference-count":80,"publisher":"Wiley","issue":"13","license":[{"start":{"date-parts":[[2007,1,16]],"date-time":"2007-01-16T00:00:00Z","timestamp":1168905600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2007,4,27]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>We demonstrate the analytical potential of <jats:sup>2<\/jats:sup>H\u2010{<jats:sup>1<\/jats:sup>H} NMR spectroscopy in weakly ordering, chiral lyotropic liquid crystals made of poly(\u03b3\u2010benzyl\u2010<jats:sc>L<\/jats:sc>\u2010glutamate) (PBLG) dissolved in chloroform or dichloromethane for investigating the intramolecular dynamic processes of four deuterated diaryls (derivatives of 1\u2010(4\u2032\u2010methylphenyl)naphthalene). When the rotation of the aryl groups about the sp<jats:sup>2<\/jats:sup>\uf8ffsp<jats:sup>2<\/jats:sup> bond is sufficiently slow relative to the NMR timescale, the method allows the spectral discrimination of enantiomeric atropisomers or enantiotopic directions in the prochiral derivatives. The effect of the position of substituents on the phenyl group on the conformational dynamics of these compounds has been examined as well as the nature of the organic co\u2010solvent. When coalescence phenomena are observed, simulation of the experimental <jats:sup>2<\/jats:sup>H\u2010{<jats:sup>1<\/jats:sup>H} lineshapes using a formalism tailored for two deuterons undergoing mutual exchange allows the rate constants and the activation parameters for the internal rotation processes to be calculated. Experimental values of \u0394<jats:italic>H<\/jats:italic><jats:sup>\u2260<\/jats:sup> have been compared with data evaluated by molecular modelling calculations and the activation parameters are discussed for the various compounds. It is shown that these polypeptide mesophases have no significant impact on the interconversion dynamics of these compounds. In contrast with the nematic thermotropic phases, Haller's equation cannot be used to predict the evolution of the quadrupolar splittings (\u0394<jats:italic>\u03bd<\/jats:italic><jats:sub>Q<\/jats:sub> values), and hence the order parameters, versus <jats:italic>T<\/jats:italic> in the PBLG mesophases. For these particular lyotropic systems, it is shown that an exponential function of the form \u0394<jats:italic>\u03bd<\/jats:italic><jats:sub>Q<\/jats:sub>[Hz]=<jats:italic>C<\/jats:italic>\u00d7exp\u2009(\u2212<jats:italic>E\/RT<\/jats:italic>[K]) provides excellent agreement between the experimental and expected \u0394<jats:italic>\u03bd<\/jats:italic><jats:sub>Q<\/jats:sub> values. Analysis of the results reported in this work suggests that orientation and chiral discrimination phenomena in these lyotropic solvents could be treated separately because they would involve different interaction mechanisms.<\/jats:p>","DOI":"10.1002\/chem.200601284","type":"journal-article","created":{"date-parts":[[2007,1,16]],"date-time":"2007-01-16T11:15:57Z","timestamp":1168946157000},"page":"3772-3786","source":"Crossref","is-referenced-by-count":30,"title":["Analysis of Intramolecular Dynamic Processes in Enantiomeric Diaryl Atropisomers and Related Derivatives by <sup>2<\/sup>H NMR Spectroscopy in Polypeptide Liquid Crystals"],"prefix":"10.1002","volume":"13","author":[{"given":"Olivier","family":"Lafon","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Philippe","family":"Lesot","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chun\u2010An","family":"Fan","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Henri\u2005B.","family":"Kagan","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2007,4,19]]},"reference":[{"key":"e_1_2_7_1_2","doi-asserted-by":"publisher","DOI":"10.1039\/b001971m"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/9780470147238.ch1"},{"key":"e_1_2_7_3_2","volume-title":"Stereochemistry of Organic Compounds","author":"Eliel A. 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