Facile preparation of well-defined AB> 2 Y-shaped miktoarm star polypeptide copolymer via the combination of ring-opening polymerization and click chemistry

Jingyi Rao, Yanfeng Zhang, Jingyan Zhang, Shiyong Liu

Research output: Contribution to journalArticle

116 Citations (Scopus)

Abstract

Well-defined AB 2 Y-shaped miktoarm star polypeptide copolymer, PZLL-β-(PBLG) 2 , was synthesized via a combination of ring-opening polymerization (ROP) of α-amino acid N-carboxyanhydride (NCA) and click chemistry, where PZLL is poly(ε-benzyloxycarbonyl-L-lysine) and PBLG is poly(y-benzyl-L-glutamate). First, two types of primary-amine-containing initiators, N-aminoethyl 3,5-bis(propargyloxyl)-benzamide and 3-azidopropylamine, were synthesized and employed for the ROP of NCA, leading to the formation of dialkynyl-terminated PZLL and azide-terminated PBLG, dialkynyl-PZLL and PBLG-N 3 , respectively. The subsequent copper(I)-catalyzed cycloaddition reaction between dialkynyl-PZLL and slightly excess PBLG-N 3 led to facile preparation of PZLL-b-(PBLG) 2 Y-shaped miktoarm star polypeptide copolymer. The excess PBLG-N 3 was scavenged off by reacting with alkynyl-functionalized Wang resin. The obtained Y-shaped miktoarm star polypeptide copolymer was characterized by gel permeation chromatograph (GPC), Fourier transform-infrared spectroscopy (FF-IR), and 1 H NMR. Moreover, after the hydrolysis of protecting benzyl and benzyloxycarbonyl groups of PZLL-b-(PBLG) 2 , water-soluble pH-responsive Y-shaped miktoarm star polypeptide copolymer, PLL-b-(PLGA) 2 , was obtained, where PLL is poly(L-lysine) and PLGA is poly(L-glutamic acid). It can self-assemble into PLGA-core micelles at acidic pH and PLL-core micelles at alkaline pH, accompanied with the coil-to-helix transition of PLGA and PLL sequences, respectively. The spontaneous pH-responsive supramolecular assembly of PLL-b-(PLGA) 2 miktoarm star polypeptide copolymer has been investigated via a combination of 1 H NMR, laser light scattering (LLS), transmission electron microscopy (TEM), and circular dichroism (CD) spectroscopy.

Original languageEnglish
Pages (from-to)2586-2593
Number of pages8
JournalBiomacromolecules
Volume9
Issue number10
DOIs
Publication statusPublished - 2008 Oct 1
Externally publishedYes

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Polypeptides
Ring opening polymerization
Phase locked loops
Stars
Copolymers
Peptides
Micelles
Lysine
Glutamic Acid
Nuclear magnetic resonance
Circular dichroism spectroscopy
Azides
Cycloaddition
Permeation
Light scattering
Amines
Fourier transform infrared spectroscopy
Amino acids
Copper
Hydrolysis

ASJC Scopus subject areas

  • Bioengineering
  • Biomaterials
  • Polymers and Plastics
  • Materials Chemistry

Cite this

Facile preparation of well-defined AB> 2 Y-shaped miktoarm star polypeptide copolymer via the combination of ring-opening polymerization and click chemistry . / Rao, Jingyi; Zhang, Yanfeng; Zhang, Jingyan; Liu, Shiyong.

In: Biomacromolecules, Vol. 9, No. 10, 01.10.2008, p. 2586-2593.

Research output: Contribution to journalArticle

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title = "Facile preparation of well-defined AB> 2 Y-shaped miktoarm star polypeptide copolymer via the combination of ring-opening polymerization and click chemistry",
abstract = "Well-defined AB 2 Y-shaped miktoarm star polypeptide copolymer, PZLL-β-(PBLG) 2 , was synthesized via a combination of ring-opening polymerization (ROP) of α-amino acid N-carboxyanhydride (NCA) and click chemistry, where PZLL is poly(ε-benzyloxycarbonyl-L-lysine) and PBLG is poly(y-benzyl-L-glutamate). First, two types of primary-amine-containing initiators, N-aminoethyl 3,5-bis(propargyloxyl)-benzamide and 3-azidopropylamine, were synthesized and employed for the ROP of NCA, leading to the formation of dialkynyl-terminated PZLL and azide-terminated PBLG, dialkynyl-PZLL and PBLG-N 3 , respectively. The subsequent copper(I)-catalyzed cycloaddition reaction between dialkynyl-PZLL and slightly excess PBLG-N 3 led to facile preparation of PZLL-b-(PBLG) 2 Y-shaped miktoarm star polypeptide copolymer. The excess PBLG-N 3 was scavenged off by reacting with alkynyl-functionalized Wang resin. The obtained Y-shaped miktoarm star polypeptide copolymer was characterized by gel permeation chromatograph (GPC), Fourier transform-infrared spectroscopy (FF-IR), and 1 H NMR. Moreover, after the hydrolysis of protecting benzyl and benzyloxycarbonyl groups of PZLL-b-(PBLG) 2 , water-soluble pH-responsive Y-shaped miktoarm star polypeptide copolymer, PLL-b-(PLGA) 2 , was obtained, where PLL is poly(L-lysine) and PLGA is poly(L-glutamic acid). It can self-assemble into PLGA-core micelles at acidic pH and PLL-core micelles at alkaline pH, accompanied with the coil-to-helix transition of PLGA and PLL sequences, respectively. The spontaneous pH-responsive supramolecular assembly of PLL-b-(PLGA) 2 miktoarm star polypeptide copolymer has been investigated via a combination of 1 H NMR, laser light scattering (LLS), transmission electron microscopy (TEM), and circular dichroism (CD) spectroscopy.",
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T1 - Facile preparation of well-defined AB> 2 Y-shaped miktoarm star polypeptide copolymer via the combination of ring-opening polymerization and click chemistry

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AU - Liu, Shiyong

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N2 - Well-defined AB 2 Y-shaped miktoarm star polypeptide copolymer, PZLL-β-(PBLG) 2 , was synthesized via a combination of ring-opening polymerization (ROP) of α-amino acid N-carboxyanhydride (NCA) and click chemistry, where PZLL is poly(ε-benzyloxycarbonyl-L-lysine) and PBLG is poly(y-benzyl-L-glutamate). First, two types of primary-amine-containing initiators, N-aminoethyl 3,5-bis(propargyloxyl)-benzamide and 3-azidopropylamine, were synthesized and employed for the ROP of NCA, leading to the formation of dialkynyl-terminated PZLL and azide-terminated PBLG, dialkynyl-PZLL and PBLG-N 3 , respectively. The subsequent copper(I)-catalyzed cycloaddition reaction between dialkynyl-PZLL and slightly excess PBLG-N 3 led to facile preparation of PZLL-b-(PBLG) 2 Y-shaped miktoarm star polypeptide copolymer. The excess PBLG-N 3 was scavenged off by reacting with alkynyl-functionalized Wang resin. The obtained Y-shaped miktoarm star polypeptide copolymer was characterized by gel permeation chromatograph (GPC), Fourier transform-infrared spectroscopy (FF-IR), and 1 H NMR. Moreover, after the hydrolysis of protecting benzyl and benzyloxycarbonyl groups of PZLL-b-(PBLG) 2 , water-soluble pH-responsive Y-shaped miktoarm star polypeptide copolymer, PLL-b-(PLGA) 2 , was obtained, where PLL is poly(L-lysine) and PLGA is poly(L-glutamic acid). It can self-assemble into PLGA-core micelles at acidic pH and PLL-core micelles at alkaline pH, accompanied with the coil-to-helix transition of PLGA and PLL sequences, respectively. The spontaneous pH-responsive supramolecular assembly of PLL-b-(PLGA) 2 miktoarm star polypeptide copolymer has been investigated via a combination of 1 H NMR, laser light scattering (LLS), transmission electron microscopy (TEM), and circular dichroism (CD) spectroscopy.

AB - Well-defined AB 2 Y-shaped miktoarm star polypeptide copolymer, PZLL-β-(PBLG) 2 , was synthesized via a combination of ring-opening polymerization (ROP) of α-amino acid N-carboxyanhydride (NCA) and click chemistry, where PZLL is poly(ε-benzyloxycarbonyl-L-lysine) and PBLG is poly(y-benzyl-L-glutamate). First, two types of primary-amine-containing initiators, N-aminoethyl 3,5-bis(propargyloxyl)-benzamide and 3-azidopropylamine, were synthesized and employed for the ROP of NCA, leading to the formation of dialkynyl-terminated PZLL and azide-terminated PBLG, dialkynyl-PZLL and PBLG-N 3 , respectively. The subsequent copper(I)-catalyzed cycloaddition reaction between dialkynyl-PZLL and slightly excess PBLG-N 3 led to facile preparation of PZLL-b-(PBLG) 2 Y-shaped miktoarm star polypeptide copolymer. The excess PBLG-N 3 was scavenged off by reacting with alkynyl-functionalized Wang resin. The obtained Y-shaped miktoarm star polypeptide copolymer was characterized by gel permeation chromatograph (GPC), Fourier transform-infrared spectroscopy (FF-IR), and 1 H NMR. Moreover, after the hydrolysis of protecting benzyl and benzyloxycarbonyl groups of PZLL-b-(PBLG) 2 , water-soluble pH-responsive Y-shaped miktoarm star polypeptide copolymer, PLL-b-(PLGA) 2 , was obtained, where PLL is poly(L-lysine) and PLGA is poly(L-glutamic acid). It can self-assemble into PLGA-core micelles at acidic pH and PLL-core micelles at alkaline pH, accompanied with the coil-to-helix transition of PLGA and PLL sequences, respectively. The spontaneous pH-responsive supramolecular assembly of PLL-b-(PLGA) 2 miktoarm star polypeptide copolymer has been investigated via a combination of 1 H NMR, laser light scattering (LLS), transmission electron microscopy (TEM), and circular dichroism (CD) spectroscopy.

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