title: Emergent Molecular Recognition through Self-Assembly: Unexpected Selectivity for Hyaluronic Acid among Glycosaminoglycans.
abstract: Oligophenylenevinylene (OPV)-based fluorescent (FL) chemosensors exhibiting linear FL responses toward polyanions were designed. Their application to FL sensing of glycosaminoglycans (heparin: HEP, chondroitin 4-sulfate: ChS, and hyaluronic acid: HA) revealed that the charge density encoded as the unit structure directs the mode of OPV self-assembly: H-type aggregate for HEP with 16-times FL increase and J-type aggregate for HA with 93-times FL increase, thus unexpectedly achieving the preferential selectivity for HA in contrast to the conventional HEP selective systems. We have found that the integral magnitude of three factors consisting of binding mechanism, self-assembly, and FL response can amplify the structural information on the target input into the characteristic FL output. This emergent property has been used for a novel molecular recognition system that realizes unconventional FL sensing of HA, potentially applicable to the clinical diagnosis of cancer-related diseases.
authors.affiliation: Institute for Advanced Study, Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka, 819-0395, Japan. tnoguchi@mail.cstm.kyushu-u.ac.jp.|Nanotechnology Laboratory, Institute of Systems, Information Technologies and Nanotechnologies (ISIT), 4-1 Kyudai-Shinmachi, Nishi-ku, Fukuoka, 819-0388, Japan. tnoguchi@mail.cstm.kyushu-u.ac.jp.
authors.forename: Takao
authors.initials: T
authors.lastname: Noguchi
authors.affiliation: Institute for Advanced Study, Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka, 819-0395, Japan.
authors.forename: Bappaditya
authors.initials: B
authors.lastname: Roy
authors.affiliation: Nanotechnology Laboratory, Institute of Systems, Information Technologies and Nanotechnologies (ISIT), 4-1 Kyudai-Shinmachi, Nishi-ku, Fukuoka, 819-0388, Japan.
authors.forename: Daisuke
authors.initials: D
authors.lastname: Yoshihara
authors.affiliation: Nanotechnology Laboratory, Institute of Systems, Information Technologies and Nanotechnologies (ISIT), 4-1 Kyudai-Shinmachi, Nishi-ku, Fukuoka, 819-0388, Japan.
authors.forename: Junji
authors.initials: J
authors.lastname: Sakamoto
authors.affiliation: Nanotechnology Laboratory, Institute of Systems, Information Technologies and Nanotechnologies (ISIT), 4-1 Kyudai-Shinmachi, Nishi-ku, Fukuoka, 819-0388, Japan.
authors.forename: Tatsuhiro
authors.initials: T
authors.lastname: Yamamoto
authors.affiliation: Institute for Advanced Study, Kyushu University, 744 Moto-oka, Nishi-ku, Fukuoka, 819-0395, Japan. shinkai_center@mail.cstm.kyushu-u.ac.jp.|Nanotechnology Laboratory, Institute of Systems, Information Technologies and Nanotechnologies (ISIT), 4-1 Kyudai-Shinmachi, Nishi-ku, Fukuoka, 819-0388, Japan. shinkai_center@mail.cstm.kyushu-u.ac.jp.|Department of Nanoscience, Faculty of Engineering, Sojo University, 4-22-1 Ikeda, Kumamoto, 860-0082, Japan. shinkai_center@mail.cstm.kyushu-u.ac.jp.
authors.forename: Seiji
authors.initials: S
authors.lastname: Shinkai
mesh_terms: D002809:Chondroitin Sulfates / Q000737:chemistry; D005456:Fluorescent Dyes / Q000737:chemistry*; D006025:Glycosaminoglycans / Q000737:chemistry*; D006493:Heparin / Q000737:chemistry; D006820:Hyaluronic Acid / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D013050:Spectrometry, Fluorescence
chemical_list: D005456:Fluorescent Dyes; D006025:Glycosaminoglycans; D006820:Hyaluronic Acid; D006493:Heparin; D002809:Chondroitin Sulfates
keywords: emergent properties; fluorescent probes; molecular recognition; self-assembly; supramolecular chemistry