Block polythiophenes

Liu, J., Sheina, E., Kowalewski, T. and McCullough, R. D. (2002) Tuning the electrical conductivity and self-assembly of regioregular polythiophene by block... 

Figure 12.14 Structures of polythiophene pol3uners and building blocks.

Figure 12.14 Stmctures of polythiophene polymers and building blocks.

Another method for the analysis of aptamer-protein complexes involved the use of a positively charged ferrocene-tethered polythiophene, (19), as redox label reporting unit (Fig. 12.19). The antithrombin aptamer was immobilized on an electrode surface, and the electrostatic binding of the redox polymer (19) to the aptamer monolayer resulted in a supramolecular complex that revealed electrical contact between the polymer and the electrode.74 The formation of the aptamer-thrombin complex removed the polymer from the surface and blocked the electrical contact between the polymer label and the electrode. As a result, higher concentrations of thrombin increased the surface coverage of the aptamer-thrombin complex on the electrode, and this decreased the amperometric responses of the sensing device. 

McCullough and coworkers had synthesized block copolymers of poly(3-hexylthiophene) and polystyrene or PMA by ATRP of the vinyl monomer from a polythiophene macroinitiator, which was prepared in several steps... 

After the development of catalyst-transfer condensation polymerization of polythiophene, the block copolymer of polythiophene and PMA could be prepared more easily. As mentioned above, the vinyl-terminated polythiophene was first prepared. The vinyl group was converted to the 2-hydroxyethyl group by hydroboration, followed by esterification with 2-bromopropionyl bromide to give a macroinitiator for ATRP (Scheme 101)... 

Recently, Dai, Su, and coworkers synthesized the block copolymer of polythiophene and polypyridine from the vinyl-terminated polythiophene (Scheme 102) [336]. Meijer and coworkers used an allyl-terminated polythiophene to synthesize a block copolymer of poly(3-hexylthiophene) and polyethylene the ring-opening metathesis polymerization of cyclooctene in the presence of the allyl-terminated polythiophene was followed by hydrogenation (Scheme 103) [337]. 

Stokes, K.K., Henze, K., and McCullough, R.D., New phosphonic acid functionalized, regioregular polythiophenes. Macromolecules 36, 7114—7118, 2003. lovu, M.C. et al., Regioregular poly(3-alkylthiophene) conducting block copolymers, Polymer 46, 8582-8586, 2005. 

In a reversal of the functionalities in the reactants, thienyl halides can be cross-coupled with Grignard reagents under Ni" catalysis (Scheme 130). This method has provided access to 3-(co-haloalkyl)thiophenes which can be used as building blocks for functionalized polythiophenes <90AG(E)419>. 

R. Verduzco, I. Botiz, D. L. Pickel, S. M. Kilbey, K. Hong, E. Dimasi, S. B. Darling, Polythiophene-BZocfc-Polyfluorene and Polythiophene-B/ocfc-Poly(Fluorene-co-Benzothiadiazole) Insights into the Self-Assembly of All-Conjugated Block Copolymers. Macromolecules 2011,44, 530-539. 

T. Antoun, A. Iraqi, L. Kergoat, L. Miozzo, A. Yassar, A Simple Route to Rod-Coil Block Copolymers of Oligo- and Polythiophenes with PMMA and Polystyrene. Macromol. Chem. Phys. 2011,212,1129-1136. 

M. C. lovu, C. R. Craley, M. Jeffries-EL, A. B. Krankowski, R. Zhang, T. Kowalewski, R. D. McCullough, Conducting Regioregular Polythiophene Block Copolymer Nanofibrils Synthesized by Reversible Addition Fragmentation Chain Transfer Polymerization (RAFT) and Nitroxide Mediated Polymerization (NMP). Macromolecules 2007,40,4733-4735. 

---