Biocompatible zinc(II) 8-(dihydroimidazolyl)quinoline complex and its catalytic application for synthesis of poly(L,L-lactide)

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Abstract

A 1:1 reaction of 8-(dihydroimidazolyl)quinoline (abbreviated as L) with MCl 2 ·2H 2 O (M = Co II , Ni II , Cu II , Zn II ) conducted in EtOAc (for Zn II and Cu II ) or MeOH (Ni II and Co II ) at 50 °C for 10 min provided the respective air- and shelf-stable [MCl 2 L] complexes (94–96%). The catalytic activity of these well-defined species was evaluated in L-lactide ring-opening polymerization (ROP) that was conducted in the presence of 2-hydroxyethylmethacrylate (HEMA) as a nucleophilic initiator. The biocompatible zinc(II) complex was found to be more catalytically active in ROP compared to the other three complexes as well as SnOct 2 , a common reference catalyst. The zinc(II)-catalyzed ROP also gives the macromolecular product with the lowest polydispersity index (1.2). The applicability of the HEMA-terminated PLA, prepared in the presence of the [ZnCl 2 L] complex, was demonstrated when PLA was converted into amphiphilic copolymer PLA-PEG via the thiol-ene click reaction. The PLA-PEG copolymer was shown to form nanospheres (calculated mean diameter 95 ± 10 nm) characterized by low particle size distribution. This – along with anticipated lower toxicity of [ZnCl 2 L] traces in the polymer – makes these nanospheres potentially applicable as vehicles for intravenous drug delivery.

Original languageEnglish
Pages (from-to)362-369
Number of pages8
JournalJournal of Catalysis
Volume372
DOIs
StatePublished - 1 Apr 2019

Keywords

  • Homogeneous catalysis
  • Lactide
  • Metal complexes
  • Quinoline
  • Ring-opening polymerization
  • MECHANISM
  • COPOLYMERS
  • RAC-LACTIDE
  • NANOPARTICLES
  • ROP
  • EPSILON-CAPROLACTONE
  • SURFACE
  • CHEMISTRY
  • RING-OPENING POLYMERIZATION
  • INITIATORS

Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry

Cite this

@article{7e2d88191f0b4a8b9100e277ed909be9,
title = "Biocompatible zinc(II) 8-(dihydroimidazolyl)quinoline complex and its catalytic application for synthesis of poly(L,L-lactide)",
abstract = "A 1:1 reaction of 8-(dihydroimidazolyl)quinoline (abbreviated as L) with MCl 2 ·2H 2 O (M = Co II , Ni II , Cu II , Zn II ) conducted in EtOAc (for Zn II and Cu II ) or MeOH (Ni II and Co II ) at 50 °C for 10 min provided the respective air- and shelf-stable [MCl 2 L] complexes (94–96{\%}). The catalytic activity of these well-defined species was evaluated in L-lactide ring-opening polymerization (ROP) that was conducted in the presence of 2-hydroxyethylmethacrylate (HEMA) as a nucleophilic initiator. The biocompatible zinc(II) complex was found to be more catalytically active in ROP compared to the other three complexes as well as SnOct 2 , a common reference catalyst. The zinc(II)-catalyzed ROP also gives the macromolecular product with the lowest polydispersity index (1.2). The applicability of the HEMA-terminated PLA, prepared in the presence of the [ZnCl 2 L] complex, was demonstrated when PLA was converted into amphiphilic copolymer PLA-PEG via the thiol-ene click reaction. The PLA-PEG copolymer was shown to form nanospheres (calculated mean diameter 95 ± 10 nm) characterized by low particle size distribution. This – along with anticipated lower toxicity of [ZnCl 2 L] traces in the polymer – makes these nanospheres potentially applicable as vehicles for intravenous drug delivery.",
keywords = "Homogeneous catalysis, Lactide, Metal complexes, Quinoline, Ring-opening polymerization, MECHANISM, COPOLYMERS, RAC-LACTIDE, NANOPARTICLES, ROP, EPSILON-CAPROLACTONE, SURFACE, CHEMISTRY, RING-OPENING POLYMERIZATION, INITIATORS",
author = "Bolotin, {Dmitrii S.} and Viktor Korzhikov-Vlakh and Ekaterina Sinitsyna and Yunusova, {Sevilya N.} and Suslonov, {Vitalii V.} and Anton Shetnev and Angelina Osipyan and Mikhail Krasavin and Kukushkin, {Vadim Yu}",
year = "2019",
month = "4",
day = "1",
doi = "10.1016/j.jcat.2019.03.002",
language = "English",
volume = "372",
pages = "362--369",
journal = "Journal of Catalysis",
issn = "0021-9517",
publisher = "Elsevier",

}

TY - JOUR

T1 - Biocompatible zinc(II) 8-(dihydroimidazolyl)quinoline complex and its catalytic application for synthesis of poly(L,L-lactide)

AU - Bolotin, Dmitrii S.

AU - Korzhikov-Vlakh, Viktor

AU - Sinitsyna, Ekaterina

AU - Yunusova, Sevilya N.

AU - Suslonov, Vitalii V.

AU - Shetnev, Anton

AU - Osipyan, Angelina

AU - Krasavin, Mikhail

AU - Kukushkin, Vadim Yu

PY - 2019/4/1

Y1 - 2019/4/1

N2 - A 1:1 reaction of 8-(dihydroimidazolyl)quinoline (abbreviated as L) with MCl 2 ·2H 2 O (M = Co II , Ni II , Cu II , Zn II ) conducted in EtOAc (for Zn II and Cu II ) or MeOH (Ni II and Co II ) at 50 °C for 10 min provided the respective air- and shelf-stable [MCl 2 L] complexes (94–96%). The catalytic activity of these well-defined species was evaluated in L-lactide ring-opening polymerization (ROP) that was conducted in the presence of 2-hydroxyethylmethacrylate (HEMA) as a nucleophilic initiator. The biocompatible zinc(II) complex was found to be more catalytically active in ROP compared to the other three complexes as well as SnOct 2 , a common reference catalyst. The zinc(II)-catalyzed ROP also gives the macromolecular product with the lowest polydispersity index (1.2). The applicability of the HEMA-terminated PLA, prepared in the presence of the [ZnCl 2 L] complex, was demonstrated when PLA was converted into amphiphilic copolymer PLA-PEG via the thiol-ene click reaction. The PLA-PEG copolymer was shown to form nanospheres (calculated mean diameter 95 ± 10 nm) characterized by low particle size distribution. This – along with anticipated lower toxicity of [ZnCl 2 L] traces in the polymer – makes these nanospheres potentially applicable as vehicles for intravenous drug delivery.

AB - A 1:1 reaction of 8-(dihydroimidazolyl)quinoline (abbreviated as L) with MCl 2 ·2H 2 O (M = Co II , Ni II , Cu II , Zn II ) conducted in EtOAc (for Zn II and Cu II ) or MeOH (Ni II and Co II ) at 50 °C for 10 min provided the respective air- and shelf-stable [MCl 2 L] complexes (94–96%). The catalytic activity of these well-defined species was evaluated in L-lactide ring-opening polymerization (ROP) that was conducted in the presence of 2-hydroxyethylmethacrylate (HEMA) as a nucleophilic initiator. The biocompatible zinc(II) complex was found to be more catalytically active in ROP compared to the other three complexes as well as SnOct 2 , a common reference catalyst. The zinc(II)-catalyzed ROP also gives the macromolecular product with the lowest polydispersity index (1.2). The applicability of the HEMA-terminated PLA, prepared in the presence of the [ZnCl 2 L] complex, was demonstrated when PLA was converted into amphiphilic copolymer PLA-PEG via the thiol-ene click reaction. The PLA-PEG copolymer was shown to form nanospheres (calculated mean diameter 95 ± 10 nm) characterized by low particle size distribution. This – along with anticipated lower toxicity of [ZnCl 2 L] traces in the polymer – makes these nanospheres potentially applicable as vehicles for intravenous drug delivery.

KW - Homogeneous catalysis

KW - Lactide

KW - Metal complexes

KW - Quinoline

KW - Ring-opening polymerization

KW - MECHANISM

KW - COPOLYMERS

KW - RAC-LACTIDE

KW - NANOPARTICLES

KW - ROP

KW - EPSILON-CAPROLACTONE

KW - SURFACE

KW - CHEMISTRY

KW - RING-OPENING POLYMERIZATION

KW - INITIATORS

UR - http://www.scopus.com/inward/record.url?scp=85063333313&partnerID=8YFLogxK

U2 - 10.1016/j.jcat.2019.03.002

DO - 10.1016/j.jcat.2019.03.002

M3 - Article

VL - 372

SP - 362

EP - 369

JO - Journal of Catalysis

JF - Journal of Catalysis

SN - 0021-9517

ER -