Metallo-supramolecular complexes from mPEG/PDPA diblock copolymers and their self-assembled strip nanosheets

Abstract

Copolymers mPEG(-b-Tpyp)2-b-PDPAx were synthesized. After a hierarchical pattern from the coordination of the copolymers with Ru(ii) ions followed by the self-assembly in water, 2D strip nanosheets were obtained.

On Thiol‐Ene Radical Coupling Reaction when Synthesis of ABCL2Type Heteroarm Star Copolymer Containing PDPA Arm

“…@(-OH) 2 -Br was obtained from the reaction of 1,1,1-tris(hydroxymethyl)propane with 2-bromoisobutyryl bromide (Figure 1R1) and @(-OH) 3 -ene was from the reaction of pentaerythritol with 10-undecenoyl chloride (Figure 1R2). [7] Their 1 H NMR data (Sections S1.2 and S1.3, Figures S1 and S2, Supporting Information) confirmed that they were synthesized successfully. PMPC-SH was synthesized via RAFT polymerization of MPC by using chain transfer agent (CTA) 4-cyano-4-(phenylcarbonothioylthio)pentanoic acid (CPPA) followed by aminolysis of the thiocarbonylthio end group (Figure 1R3).…”

“…Then, one alkenyl and two hydroxyl groups were simultaneously added onto PCL 28 3R9). [7] 1 H NMR spectrum of PCL 28 In Figure 4, the resonance at δ = 4.60 (peak j9'') is assigned to the new À C(=O)OCH 2 À group formed via the esterification. The resonances at δ = 8.71 (t5, t1), 8.63 (t4), 8.14 (t7), 7.95 (t3), 7.87 (t6) and 7.34 (t2) ppm assigned to the Tpyp groups could be observed clearly [7] besides the characteristic those of the PCL and PDPA blocks.…”

“…Therefore, the type of copolymers should have multi-functions and may produce novel self-assembly morphologies and applications. [3,4,6] In our previous work, [7] we synthesized poly(ethylene glycol) methyl ether/poly(2-(diisopropylamino) ethyl methacrylate) (mPEG/ PDPA) block copolymers with two 4-([2,2':6',2''-terpyridine]-4'yl) phenyl (Tpyp) ligand groups at the junction point of the two blocks. Interestingly, after a hierarchical pattern from the coordination of the mPEG/PDPA copolymers with Ru(II) ions followed by the self-assembly in water, 2D strip nanosheets with a monomolecular layer were obtained.…”

“…Herein we report novel amphiphilic ABCL 2 -type heteroarm star copolymers, where A, B and C are poly(ε-caprolactone) (PCL), PDPA and poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) blocks, respectively, and L is Tpyp ligand group. This is because PCL is hydrophobic and biodegradable, [8] PDPA is pH-sensitive [5,7,9] and PMPC is a zwitterionic polyelectrolyte and shows highly biocompatible nature. [10,11] And 2,2':6', 2''-terpyridine (Tpy) is able to form stable Tpy-M-Tpy (M, metal ion) complexes with a wide range of metal ions such as Ni(II), Fe(II), Cu(II), Co(II), Zn(II), Cd(II) and Ru(II), [7,[12][13][14][15] making the metallosupramolecules formed have a well-defined architecture.…”

“…This is because PCL is hydrophobic and biodegradable, [8] PDPA is pH-sensitive [5,7,9] and PMPC is a zwitterionic polyelectrolyte and shows highly biocompatible nature. [10,11] And 2,2':6', 2''-terpyridine (Tpy) is able to form stable Tpy-M-Tpy (M, metal ion) complexes with a wide range of metal ions such as Ni(II), Fe(II), Cu(II), Co(II), Zn(II), Cd(II) and Ru(II), [7,[12][13][14][15] making the metallosupramolecules formed have a well-defined architecture. Thus, the amphiphilic ABCL 2 -type heteroarm star copolymer unit not only possesses properties from PCL, PDPA and PMPC chains but also should be able to coordinate with metal ions to form new supramolecular architecture.…”