Abstract

Biofunctional block copolymers are becoming increasingly attractive materials as active components in biosensors and other nanoscale electronic devices. We have described two different classes of block copolymers with biofuctional properties. Biofunctionality for block copolymers is achieved through functionalization with appropriate biospecific ligands. We have synthesized block copolymers of electroactive poly(3-decylthiophene) and 2-hydroxyethyl methacrylate by atom transfer radical polymerization. The block copolymers were functionalized with the dinitrophenyl (DNP) groups, which are capable of binding to Immunoglobulin E (IgE) on cell surfaces. The block copolymers were shown to be redox active. Additionally, the triblock copolymer of α, ω-bi-biotin (poly(ethylene oxide)-b-poly (styrene)-b-poly(ethylene oxide)) was also synthesized to study their capacity to bind fluorescently tagged avidin. The surface-active property of the poly(ethylene oxide) block improved the availability of the biotin functional groups on the polymer surfaces. Fluorescence microscopy observations confirm the specific binding of biotin with avidin.

Highlights

  • Polymeric materials functionalized with appropriate biospecific ligands have been proved to be effective in targeted drug-delivery and bio-sensing applications, to name a just few examples [1,2].Nano-structured polymeric materials are usually more effective carriers of therapeutic agents, especially in in vivo applications [3]

  • The atom transfer radical polymerization of 2-hydroxyethyl methacrylate (HEMA), was carried out using the bromoester terminated P3DT as macroinitiator in the ratio of 300:2:1:1 (HEMA:P3DT-MI: CuBr:PMDETA) (Scheme 2). 50.3 mg of P3DT functionalized with the bromoester end groups macroinitiator was placed into a 25 mL flask, 156 mg of purified CuBr and 188.6 mg of PMDETA

  • The DNP functionalized block copolymers were processed into thin films by drop-casting from chloroform solution. 1 mg of DNP-PHEMA-b-P3DT was dissolved in 1 mL chloroform

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Summary

Introduction

Polymeric materials functionalized with appropriate biospecific ligands have been proved to be effective in targeted drug-delivery and bio-sensing applications, to name a just few examples [1,2]. Nano-structured polymeric materials are usually more effective carriers of therapeutic agents, especially in in vivo applications [3] Some of these architectures include nanofibers (obtained by self-assembly of the polymers or by electrospinning) [4], nanoparticles (nanospheres or nanorods) [5], nanoplates [6], nanoribbons [7], etc. An example of this is the covalent attachment of a short peptide chain to the polymer, as reported by Baird et al [14] Another approach is the synthesis of polymers containing species capable of specific ligand-receptor interactions. This is essentially conjugating a polymer with a ligand or functional groups that antibodies recognize and adhere to [15]. The functional copolymers were processed into structures decorated with either the biotin or the DNP functional groups

Chemicals and Reagents
Preparation of Difunctional Initiator
Preparation of P3DT with Proton End Group
Preparation of P3DT with Carbonyl End Group
Preparation of P3DT with Hydroxyl End Group
Preparation of Bromoester End Capped P3DT
2.10. ATRP of 2-Hydroxyethyl Methacrylate with P3DT Macroinitiator
2.11. Functionalization of P3DT-b-PHEMA with DNP Groups
2.12. Polymer Processing
2.13. Biofunctional Property Studies
H NMR and 13C NMR spectra were recorded on Bruker AVANCE III 500 MHz and Bruker
Results and Discussion
Functional Polymer-Protein Interactions
Conclusions
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