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

Research output

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
Publication statusPublished - 1 Apr 2019

Fingerprint

Ring opening polymerization
quinoline
Zinc
polymerization
zinc
Nanospheres
Polyethylene glycols
rings
copolymers
synthesis
Copolymers
Polydispersity
initiators
particle size distribution
Drug delivery
shelves
Sulfhydryl Compounds
thiols
Particle size analysis
toxicity

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

AN - SCOPUS:85063333313

VL - 372

SP - 362

EP - 369

JO - Journal of Catalysis

JF - Journal of Catalysis

SN - 0021-9517

ER -