Functional nanostructures by NiCCo-PISA of helical poly(aryl isocyanide) copolymers

Abstract

Herein, we present a straightforward and versatile methodology to achieve functional polymeric nano-objects that contain helical cores. Nickel-catalysed coordination polymerisation-induced self-assembly (NiCCo-PISA) of helical poly(aryl isocyanide) amphiphilic diblock copolymers was...

Precise control over supramolecular nanostructuresviamanipulation of H-bonding in π-amphiphiles

“…Significant emission in water confirms that NDI-amphiphiles in all the nanostructures' (cylindrical micelles/nanoribbons/nanotubes) maleimide moiety remain in a hydrophobic microenvironment and are shielded from water. It is known that the emission wavelength and the intensity of the DTM moiety are closely related to the microenvironment 67,68 and the different values of blue-shifted spectra for the NDI 1/2/3 assembly indicate the degree of hydrophobicity of the maleimide microenvironment; this varies (NDI-1 having the most hydrophobic core while NDI-3 has the least hydrophobic core) as a consequence of H-bonding. Intermolecular H-bonding in aqueous medium was confirmed by a solvent dependent FT-IR study (Fig.…”

Stimuli-responsive and core cross-linked micelles developed by NiCCo-PISA of helical poly(aryl isocyanide)s

“…Building on the NiCCo-PISA-derived functionalisable micelles presented in our earlier works, 86,87 the synthesis of stimulusresponsive nanostructures through a PPM methodology was envisioned. Namely, a functionalisable poly(PEG-ester aryl isocyanide) 20 -block-poly(menthyl-ester aryl isocyanide 15 -co-pentafluorophenyl-ester aryl isocyanide 15 ), i.e.…”

“…These polyisocyanides were synthesised in earlier studies, which contain complete characterisation data for the polymers. 86,87 Basic characterisation data, including molecular weight and dispersity, is summarized here (Table 1).…”

“…45,[88][89][90][91][92][93] Conditions from a previous report were used for the cross-linking experiments. 86 The NiCCo-PISA suspension of non-functionalised D50% NPs was reacted with 0.6 equivalents of each of the diamine cross-linkers for three days in DMSO at 50 °C. These PPM reactions were repeated using non-functional particles D0% (i.e.…”

“…[79][80][81][82][83][84][85] Herein, we report the development of core-functionalised poly(aryl isocyanide) nanostructures synthesised by nickel-catalysed coordination polymerisation-induced self-assembly (NiCCo-PISA). Subsequent post-polymerisation modification (PPM) of pentafluorophenyl (PFP) activated ester units 43,86 using a variety of primary diamines, enabled cross-linking of the core of the derived micelles. The latter cross-linking step provided stability and/or stimuli-responsive properties to the final nanostructures.…”