title: Polypeptide-b-Poly(Phenyl Isocyanide) Hybrid Rod-Rod Copolymers: One-Pot Synthesis, Self-Assembly, and Cell Imaging.
abstract: Hybrid rod-rod diblock copolymers, poly(γ-benzyl L-glutamate)-poly(4-cyano-benzoic acid 2-isopropyl-5-methyl-cyclohexyl ester) (PBLG-PPI), with determined chirality are facilely synthesized through sequential copolymerization of γ-benzyl-L-glutamate N-carboxyanhydride (BLG-NCA) and phenyl isocyanide monomers bearing chiral menthyl pendants using a Ni(cod)(bpy) complex as the catalyst in one-pot. Circular dichroism and absorption spectra reveal that each block of the block copolymers possesses a stable helical conformation with controlled helicity in solution due to the induction of chiral pendants. The two diastereomeric polymers self-assemble into helical nanofibrils with opposite handedness due to the different chiral induction of the L- and D-menthyl pendants, confirmed by transmission electron microscopy (TEM). Deprotection of the benzyl groups of the PBLG segment affords biocompatible amphiphilic diblock copolymers, poly(L-glutamic acid)-poly(4-cyano-benzoic acid 2-isopropyl-5-methyl-cyclohexyl ester) (PLGA-PPI), that can self-assemble into well-defined micelles by cosolvent induced aggregation. Very interestingly, a chiral rhodamine chromophores RhB(D) can be selectively encapsulated into the chiral polymeric micelles, which is efficiently internalized into living cells when directly monitored with a confocal microscope. This contribution will be useful for developing novel rod-rod biocompatible hybrid block copolymers with a controlled helicity, and may also provide unique chiral materials for potential bio-medical applications.
authors.affiliation: Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Hefei University of Technology and Anhui Key Laboratory of Advanced Functional Materials and Devices, Hefei, 230009, China.
authors.forename: Sheng-Yu
authors.initials: SY
authors.lastname: Shi
authors.affiliation: Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Hefei University of Technology and Anhui Key Laboratory of Advanced Functional Materials and Devices, Hefei, 230009, China.
authors.forename: Ya-Guang
authors.initials: YG
authors.lastname: He
authors.affiliation: Anhui Provincial Children's Hospital, Hefei, 230000, China.
authors.forename: Wei-Wei
authors.initials: WW
authors.lastname: Chen
authors.affiliation: Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Hefei University of Technology and Anhui Key Laboratory of Advanced Functional Materials and Devices, Hefei, 230009, China.
authors.forename: Na
authors.initials: N
authors.lastname: Liu
authors.affiliation: Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Hefei University of Technology and Anhui Key Laboratory of Advanced Functional Materials and Devices, Hefei, 230009, China.
authors.forename: Yuan-Yuan
authors.initials: YY
authors.lastname: Zhu
authors.affiliation: Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Hefei University of Technology and Anhui Key Laboratory of Advanced Functional Materials and Devices, Hefei, 230009, China.
authors.forename: Yun-Sheng
authors.initials: YS
authors.lastname: Ding
authors.affiliation: Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Hefei University of Technology and Anhui Key Laboratory of Advanced Functional Materials and Devices, Hefei, 230009, China.
authors.forename: Jun
authors.initials: J
authors.lastname: Yin
authors.affiliation: Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Hefei University of Technology and Anhui Key Laboratory of Advanced Functional Materials and Devices, Hefei, 230009, China.
authors.forename: Zong-Quan
authors.initials: ZQ
authors.lastname: Wu
mesh_terms: D000812:Anhydrides / Q000138:chemical synthesis / Q000737:chemistry*; D001672:Biocompatible Materials / Q000737:chemistry; D058948:Cell Tracking; D005971:Glutamates / Q000138:chemical synthesis / Q000737:chemistry*; D006801:Humans; D017879:Isothiocyanates / Q000737:chemistry; D008968:Molecular Conformation; D057054:Molecular Imaging; D010455:Peptides / Q000737:chemistry; D011099:Polyglutamic Acid / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D012996:Solutions / Q000737:chemistry
chemical_list: D000812:Anhydrides; D001672:Biocompatible Materials; D005971:Glutamates; D017879:Isothiocyanates; D010455:Peptides; D012996:Solutions; C568827:gamma-benzylglutamyl-N-carboxy anhydride; C005441:phenylisothiocyanate; C003172:poly-gamma-benzyl-L-glutamate; D011099:Polyglutamic Acid
keywords: cell imaging; chirality; helix; poly(phenyl isocyanide); self-assembly