Fluorescent micellar nanoparticles by self-assembly of amphiphilic, nonionic and water self-dispersible polythiophenes with “hairy rod” architecture

An amphiphilic, heterografted polythiophene copolymer containing biocompatible/biodegradable side chains for use as an (electro)active surface in biomedical applications

“…Moreover, as (1)-methylene protons and even (2)methylene protons in poly-3-alkylthiophenes, due to the difference in configuration, present split peaks associated to H-H and H-T dyads, from the intensities of these characteristic peaks the named dyads ratio can be evaluated. 37 Interestingly, in the spectrum of PTh-g-(PEG-r-PCL), in the range 5.05 ppm -5.41 ppm, two separated peaks are present at 5.05 -5.01 ppm and 5.39 -5.41 ppm, that could be attributed to both types of dyads, commented above, in the structural units of the new copolymer. However, due to the statistical distribution of the side chains, as well as the presence of other possibilities for PTh main chain ends, it makes complicate the calculation of such H-H/H-T dyads ratio in the range of 5.05-5.41 ppm.…”

Synthesis and self-assembly of fluorene-vinylene alternating copolymers in “Hairy-Rod” architecture: side chain – mediated tuning of conformation, microstructure and photophysical properties

“…[74] also lower values of the size obtained from aFM can be due to the shrinking during the solvent evaporation, while the higher ones to various phenomena taking place during film formation. [12] referring to the copolymer 11, it should be pointed out that, to the best of our knowledge, this is the first example circular shape with a diameter ranging from 100 to 120 nm and 4-6 nm in height can be observed.…”

“…The shape modification could be triggered by the HOPG hydrophobic surface, while the decrease in size of the new-formed spherical 'core-shell' nanoparticles could be due to the shrinking by evaporation of 'structured water' from the PEG shell. [12] In order to see how the shape and size of supramolecular entities could be modulated, for the copolymer 12, investigations by varying the concentration of dispersions and their films on mica support were also performed ( Figures S13 and S20, Table S3 in the Supporting information). The study revealed that concentration could be a decisive factor influencing the density of the nanoparticles on the support surface as well as their 'shell-shell' interaction during the solvent evaporation.…”

“…[60] It was hypothesized that, in good solvents, the side chains will adopt the most extended conformation, which should prevent the conjugated chain aggregation even in the conditions of spatial constraints imposed by the supramolecular entities formed via Sa. [61] The method used for Sa is the so-called 'direct dissolution method' that was reported as an appropriate approach for both amphihilic [12] and non-amphiphilic [62] rod-coil copolymers. To prove solvent-induced Sa of the reported materials, DLS measurements of the solutions and aFM analysis for the films obtained from these solutions were conducted.…”

“…[11] Both supramolecular shapes of the self-assembled formed entities of rod-coil copolymers as well as their stability can be manipulated by the variation of macromolecular architecture. In this context, conjugated rodcoil copolymers in 'hairy-rod' architecture, best described as 'molecularly reinforced liquids, ' [12] become an exciting research field for the new materials having unexpected properties otherwise impossible to be obtained with the polymers with common topology.…”