Research article

Synthesis of pyridoxine-based eagle-shaped asymmetric star polymers through seATRP

Corresponding Author

Paweł Chmielarz

[email protected]

orcid.org/0000-0002-9101-6264

Faculty of Chemistry, Department of Physical Chemistry, Rzeszów University of Technology, Al. Powstańców Warszawy 6, 35-959 Rzeszów, Poland

Correspondence to: Paweł Chmielarz, Faculty of Chemistry, Department of Physical Chemistry, Rzeszów University of Technology, Al. Powstańców Warszawy 6, 35-959 Rzeszów, Poland.

E-mail: [email protected]

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Paweł Chmielarz,

Corresponding Author

Paweł Chmielarz

[email protected]

orcid.org/0000-0002-9101-6264

Faculty of Chemistry, Department of Physical Chemistry, Rzeszów University of Technology, Al. Powstańców Warszawy 6, 35-959 Rzeszów, Poland

Correspondence to: Paweł Chmielarz, Faculty of Chemistry, Department of Physical Chemistry, Rzeszów University of Technology, Al. Powstańców Warszawy 6, 35-959 Rzeszów, Poland.

E-mail: [email protected]

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First published: 19 April 2017

https://doi.org/10.1002/pat.4062

Citations: 19

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Abstract

The vitamin B₆-based macroinitiator was prepared for the first time by the transesterification reaction of pyridoxine with 2-bromoisobutyryl bromide. A pyridoxine-based star-shaped block copolymer with a hydrophilic pyridoxine core and a dual hydrophilic poly(2-(dimethylamino)ethyl methacrylate)-block-poly(N-isopropylacrylamide) arms was synthesized for the first time via a simplified electrochemically mediated atom transfer radical polymerization, utilizing only 20 ppm of catalyst complex. The rate of the polymerizations was controlled by applying appropriate potential/current values during electrolysis to prevent the possibility of intermolecular coupling of the polymer stars. The asymmetric star polymers showed narrow molecular weight distribution (Đ = 1.09–1.13). ¹H NMR spectral results confirm the formation of star-like block (co)polymers. These new vitamin B₆-based eagle-shaped star (co)polymers may find biomedical and biosensor applications as pH-sensitive and thermo-sensitive drug delivery systems. Copyright © 2017 John Wiley & Sons, Ltd.

Supporting Information

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Supporting Information – Figures showing first-order kinetic plots, GPC traces of polymers, and CV results.

Fig. S1. Cyclic voltammetry results of Cu^IIBr₂/2TPMA alone (black) and in the presence of vitamin-based PN-Br₃ macroinitiator (gray). The arrow indicates the applied potential during electrolysis. Measurement conditions: [DMAEMA]/[PN-Br₃ (per –Br)]/[Cu^IIBr₂/2TPMA] = 125/1/0.0025, [DMAEMA] = 3.0 M, [Cu^IIBr₂/2TPMA] = 0.12 mM, T = 60°C, [TBAP] = 0.2 M, V_tot = 20 ml. Table 1, entries 1 and 2.

Fig. S2. Cyclic voltammetry results of Cu^IIBr₂/2TPMA alone (black) and in the presence of PN-Br₅ (gray). The arrow indicates the applied potential during electrolysis. Measurement conditions: [NIPAM]/[PN-(PDMAEMA-Br)₅ (per –Br)]/[Cu^IIBr₂/2TPMA] = 150/1/0.0030, [NIPAM] = 1.0 M, [Cu^IIBr₂/2TPMA] = 0.02 mM, T = 60°C, [TBAP] = 0.2 M, V_tot = 18 ml. Table 1, entries 3 and 4.

Fig. S3. First-order kinetic plots for preparative electrolysis under constant potential/current conditions. Reaction conditions: [DMAEMA]/[PN-Br₃ (per –Br)]/[Cu^IIBr₂/2TPMA] = 125/1/0.0025, [DMAEMA] = 3.0 M, [Cu^IIBr₂/2TPMA] = 0.12 mM, T = 60°C, [TBAP] = 0.2 M, V_tot = 20 ml. Table 1, entries 1 and 2.

Fig. S4. GPC traces of DMAEMA simplified seATRP in the presence of PN-Br₃ under (a) constant potential electrolysis and (b) constant current electrolysis. GPC traces of NIPAM simplified seATRP in the presence of PN-(PDMAEMA)₃ under (c) constant potential electrolysis and (d) constant current electrolysis.

Fig. S5. First-order kinetic plots for preparative electrolysis under constant potential/current conditions. Reaction conditions: [NIPAM]/[PN-(PDMAEMA-Br)₅ (per –Br)]/[Cu^IIBr₂/2TPMA] = 150/1/0.0030, [NIPAM] = 1.0 M, [Cu^IIBr₂/2TPMA] = 0.02 mM, T = 60°C, [TBAP] = 0.2 M, V_tot = 18 ml. Table 1, entries 3 and 4.

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Volume28, Issue12

December 2017

Pages 1787-1793

Synthesis of pyridoxine-based eagle-shaped asymmetric star polymers through seATRP

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Synthesis of pyridoxine-based eagle-shaped asymmetric star polymers through seATRP

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