Synthesis.2-Bromo-3-hexyl-5-iodothiophene (6). NBS (37.38g, 0.21 mol) was added to the solution of 3hexylthiophene (33.66 g, 0.2 mol) in 500 mL of a chloroform-acetic acid mixture (50/50 v/v) in the absence of light, under an argon atmosphere, at temperature 0°C. The mixture was allowed to reach room temperature, and stirred overnight, and hydrolyzed with 500 mL of ice-water, and the aqueous phase extracted with chloroform. The combined extracts were washed with water, 1 M sodium hydroxide solution (50 ml), again with water, dried (MgSO4), and concentrated. The residue was purified by flash chromatography to give 44.45 g (0.18 mol) of monobromide 4 (90% yield). Iodination was performed in a similar manner. To this end, NIS (21.26 g, 95 mmol) was added to 4 (22.25 g, 90 mmol) in 500 mL of a chloroform-acetic acid mixture (50/50 v/v) in the absence of light, under an argon atmosphere, at temperature 0°C. The mixture was allowed to reach room temperature, stirred overnight,
Herein, we present a new approach to synthesize rod−coil block copolymers via consecutive Kumada catalyst-transfer polycondensation (KCTP) and nitroxide-mediated free radical polymerization (NMP) performed from a bifunctional initiator, TIPNO−Ph−Ni(dppp)−Br (TIPNO = 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide; dppp = propane-1,3-diylbis(diphenylphosphane). The utility of the method was exemplified in a preparation of a model block copolymer, poly(3-hexylthiophene)-block-polystyrene (P3HT-b-PS) with a relatively narrow molecular weight distribution of 1.33. Synthesis of the bifunctional initiator was accomplished by a reaction of diethylbipyridylnickel with a readily accessible precursor, TIPNO−Ph−Br, followed by in situ replacement of the bipyridyl ligand onto bidentate phosphorus one.
Silica-supported silver nanoparticles (Ag/SiO2) encapsulated inside the PNIPAM-based microcapsules (MC) were proved to be an efficient and easy-to-handle catalyst. Due to the hydrophilic nature of MCs, they act as microreactors in a mixed organic–aqueous environment. It was demonstrated that the catalytic activity of encapsulated Ag/SiO2 substantially exceeds that of freely dispersed catalyst.
We report on the protein-resistant properties of glass substrates coated with novel copolymers of 2-aminoethyl methacrylate hydrochloride and poly(ethylene glycol) methyl ether methacrylate (AEM-PEG). In comparison to currently available protein-blocking polymer systems, such as poly-l-lysine-poly(ethylene glycol), silane-based poly(ethylene glycol), and poly(ethylene glycol) brushes prepared by surface-initiated polymerization, the proposed AEM-PEG offers the combined advantages of low cost, simplicity of use, and applicability in aqueous solutions. We demonstrate the capability of AEM-PEG to block the surface binding of globular proteins (tubulin), their assemblies (microtubules), and functional motor proteins (kinesin-1). Moreover, we demonstrate the applicability of AEM-PEG for surface patterning of proteins in microfluidic devices.
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