{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,6]],"date-time":"2026-10-06T21:03:33Z","timestamp":1791320613240,"version":"4.3.1"},"reference-count":47,"publisher":"MDPI AG","issue":"11","license":[{"start":{"date-parts":[[2016,11,21]],"date-time":"2016-11-21T00:00:00Z","timestamp":1479686400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"National Nature Science Foundation of China","award":["51373044, 21576060 and 21574033"],"award-info":[{"award-number":["51373044, 21576060 and 21574033"]}]},{"name":"National Natural Science Foundation of Heilongjiang province, China","award":["LC201404 and E2016019"],"award-info":[{"award-number":["LC201404 and E2016019"]}]},{"name":"Fundamental Research Funds for the Central Universities, China","award":["HEUCFQ1417, HEUCF20161004"],"award-info":[{"award-number":["HEUCFQ1417, HEUCF20161004"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>A phenylacetylene containing the l-valine ethyl ester pendant (PAA-Val) was synthesized and polymerized by an organorhodium catalyst (Rh(nbd)BPh4) to produce the corresponding one-handed helical cis-poly(phenylacetylene) (PPAA-Val). PPAA-Val showed a unique temperature-triggered switchable helix-sense in chloroform, while it was not observed in highly polar solvents, such as N,N\u2032-dimethylformamide (DMF). By heating the solution of PPAA-Val in chloroform, the sign of the CD absorption became reversed, but recovered after cooling the solution to room temperature. Even after six cycles of the heating-cooling treatment, the helix sense of the PPAA-Val\u2019s backbone was still switchable without loss of the CD intensity. The PPAA-Val was then coated on silica gel particles to produce novel chiral stationary phases (CSPs) for high-performance liquid chromatography (HPLC). These novel PPAA-Val based CSPs showed a high chiral recognition ability for racemic mandelonitrile (\u03b1 = 2.18) and racemic trans-N,N\u2032-diphenylcyclohexane-1,2-dicarboxamide (\u03b1 = 2.60). Additionally, the one-handed helical cis-polyene backbone of PPAA-Val was irreversibly destroyed to afford PPAA-Val-H by heating in dimethyl sulfoxide (DMSO) accompanied by the complete disappearance of the Cotton effect. Although PPAA-Val-H had the same l-valine ethyl ester pendants as its cis-isomer PPAA-Val, it showed no chiral recognition. It was concluded that the one-handed helical cis-polyene backbone of PPAA-Val plays an important role in the chiral recognition ability.<\/jats:p>","DOI":"10.3390\/molecules21111583","type":"journal-article","created":{"date-parts":[[2016,11,21]],"date-time":"2016-11-21T11:16:05Z","timestamp":1479726965000},"page":"1583","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":15,"title":["Temperature-Triggered Switchable Helix-Helix Inversion of Poly(phenylacetylene) Bearing l-Valine Ethyl Ester Pendants and Its Chiral Recognition Ability"],"prefix":"10.3390","volume":"21","author":[{"given":"Yanli","family":"Zhou","sequence":"first","affiliation":[{"name":"Polymer Materials Research Center, Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6068-8140","authenticated-orcid":false,"given":"Chunhong","family":"Zhang","sequence":"additional","affiliation":[{"name":"Polymer Materials Research Center, Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yuan","family":"Qiu","sequence":"additional","affiliation":[{"name":"Polymer Materials Research Center, Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2181-747X","authenticated-orcid":false,"given":"Lijia","family":"Liu","sequence":"additional","affiliation":[{"name":"Polymer Materials Research Center, Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Taotao","family":"Yang","sequence":"additional","affiliation":[{"name":"Polymer Materials Research Center, Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hongxing","family":"Dong","sequence":"additional","affiliation":[{"name":"Polymer Materials Research Center, Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5449-9642","authenticated-orcid":false,"given":"Toshifumi","family":"Satoh","sequence":"additional","affiliation":[{"name":"Faculty of Engineering, Hokkaido University, Sapporo 060-8628, Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yoshio","family":"Okamoto","sequence":"additional","affiliation":[{"name":"Polymer Materials Research Center, Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China"},{"name":"Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8601, Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2016,11,21]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"1175","DOI":"10.1021\/ma030501f","article-title":"Design of helical poly(N-propargylamides) that switch the helix sense with thermal stimuli","volume":"37","author":"Tabei","year":"2004","journal-title":"Macromolecules"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"1553","DOI":"10.1021\/ma500147z","article-title":"Chiroptical and thermotropic properties of helical styrenic polymers: Effect of achiral group","volume":"47","author":"Wang","year":"2014","journal-title":"Macromolecules"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"1860","DOI":"10.1126\/science.268.5219.1860","article-title":"A helical polymer with a cooperative response to chiral information","volume":"268","author":"Green","year":"1995","journal-title":"Science"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"3342","DOI":"10.1039\/c2cc00024e","article-title":"Helical polymer brushes with a preferred-handed helix-sense triggered by a terminal optically active group in the pendant","volume":"48","author":"Maeda","year":"2012","journal-title":"Chem. 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