SYNTHESIS OF TERPYRIDINE-FUNCTIONALIZED POLY(N-ISOPROPYLACYLAMIDE)S AND THEIR METAL COMPLEXES

SUN Peijian; SHI Xudong; GAN Zhihua

doi:10.3724/SP.J.1105.2010.09467

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SYNTHESIS OF TERPYRIDINE-FUNCTIONALIZED POLY(N-ISOPROPYLACYLAMIDE)S AND THEIR METAL COMPLEXES

Research Article | 更新时间：2021-03-19

- SYNTHESIS OF TERPYRIDINE-FUNCTIONALIZED POLY(N-ISOPROPYLACYLAMIDE)S AND THEIR METAL COMPLEXES
- Acta Polymerica Sinica Issue 4, Pages: 383-389(2010)
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- DOI：10.3724/SP.J.1105.2010.09467
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- Published：20 April 2010，
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SUN Peijian, SHI Xudong, GAN Zhihua. SYNTHESIS OF TERPYRIDINE-FUNCTIONALIZED POLY(N-ISOPROPYLACYLAMIDE)S AND THEIR METAL COMPLEXES. [J]. Acta Polymerica Sinica (4):383-389(2010)
DOI：

SUN Peijian, SHI Xudong, GAN Zhihua. SYNTHESIS OF TERPYRIDINE-FUNCTIONALIZED POLY(N-ISOPROPYLACYLAMIDE)S AND THEIR METAL COMPLEXES. [J]. Acta Polymerica Sinica (4):383-389(2010) DOI： 10.3724/SP.J.1105.2010.09467.

摘要

合成出三吡啶官能化的二硫代酯并以其作为链转移剂进行了异丙基丙烯酰胺(NIPAAm)的可逆加成断裂链转移(RAFT)聚合，得到分子量可控和窄分子量分布的端三吡啶基聚异丙基丙烯酰胺(tpy-PNIPAAm)，聚合反应为对单体浓度的一级动力学关系.Tpy-PNIPAAm在水中既保持了与聚异丙基丙烯酰胺类似的相转变行为，又拥有三吡啶（tpy）的强络合能力.将tpyPNIPAAm与金属核素模型进行络合得到金属配合物，所得金属配合物在水中拥有与PNIPAAm类似的相转变行为，同时tpy-PNIPAAm的金属配合物由于其两亲性，在水中可以形成纳米粒子，由于纳米粒子间的静电排斥作用，这种纳米粒子即使在高于相转变温度时，仍能稳定于水中.

Abstract

A new terpyridine-functionalized dithioester was synthesized as a chain transfer agent in the reversible addition fragmentation chain transfer polymerization (RAFT) of N-isopropylacyamide (NIPAAm).The polymerization showed an first-order kinetics and the molecular weight increased linearly with conversion

indicating that the terpyridine-functionalized dithioester is an efficient chain transfer agent for the RAFT polymerization of NIPAAm.The terpyridine-functionalized poly(N-isopropylacyamide) (tpy-PNIPAAm) not only displays similar phase transition as PNIPAAm

but also have the coordination ability via terpyridine

which were further used to construct macromolecularmetal complex with ferrous ions as model metal ions.The appearance of a strong absorption at 555 nm in UV-Vis spectrum revealed the formation of macromolecular-metal complex

indicating the strong coordination ability of tpy-PNIPAAm to metal.Cloud point method and dynamic light scattering (DLS) were used to characterize the thermosensitivity of tpy-PNIPAAm and macromolecular-metal complex.The results showed that the macromolecularmetal complex could self-assemble into nanoparticles in aqueous solution due to the amphiphilic property The macromolecular-metal complex solution showed a similar phase transition as PNIPAAm.In addition

the nanoparticles of the macromolecular-metal complex in aqueous solution were stable even at temperature above the lower critical solution temperature(LCST) due to electrostatic repulsion.This work indicated the great potentials of tpyPNIPAAm as carriers for the delivery of therapeutic radioisotopes.

关键词

RAFT聚合三吡啶聚异丙基丙烯酰胺温度敏感性核素

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The State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University

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