title: Development of highly-sensitive detection system in19F NMR for bioactive compounds based on the assembly of paramagnetic complexes with fluorinated cubic silsesquioxanes.
abstract: This manuscript reports the detection system with19F NMR probes for bioactive amine compounds at sub-micro molar concentrations. Water-soluble fluorinated polyhedral oligomeric silsesquioxane (POSS) derivatives were prepared, and the paramagnetic Ni-porphyrin (NiPor) with the fluorinated POSS (F-POSS) was adsorbed in the buffer. By adding the series of amine derivatives to the homogeneous dispersion containing the POSS-NiPor complexes, the changes in the signal intensity were evaluated. It was clearly observed from homogeneous dispersions that the signal intensity of19F NMR decreased especially in the presence of ethanediamine and hexylamine. From the dynamic light scattering measurements, it was revealed that the assembly of the F-POSS complexes was dramatically induced by the amine compounds when the signal intensity decreased. According to these data, it is proposed that the signal reduction of19F NMR from the POSS-NiPor complexes could be induced via the strong paramagnetic relaxation enhancement from NiPor in the assembly. Finally, based on the signal reduction by the assembly, we can detect the amine derivatives under 1μM concentration which is similar sensitivity to the conventional fluorescence probes. Our system is valid to monitor the distribution of the bio-active molecules at cellular concentrations.
authors.affiliation: Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan.
authors.forename: Takahiro
authors.initials: T
authors.lastname: Kakuta
authors.affiliation: Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan.
authors.forename: Hayato
authors.initials: H
authors.lastname: Narikiyo
authors.affiliation: Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan.
authors.forename: Jong-Hwan
authors.initials: JH
authors.lastname: Jeon
authors.affiliation: Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan. Electronic address: kazuo123@chujo.synchem.kyoto-u.ac.jp.
authors.forename: Kazuo
authors.initials: K
authors.lastname: Tanaka
authors.affiliation: Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan. Electronic address: chujo@chujo.synchem.kyoto-u.ac.jp.
authors.forename: Yoshiki
authors.initials: Y
authors.lastname: Chujo
mesh_terms: D000588:Amines / Q000032:analysis*; D005461:Fluorine; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D017646:Organosilicon Compounds / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: D000588:Amines; D017646:Organosilicon Compounds; D005461:Fluorine
keywords: (19)F NMR; Fluorinated compound; Molecular probe; Paramagnetic relaxation enhancement; Silsesquioxane