This review discusses recent advances of the self-assembly of amphiphilic block copolymers into novel micellar architectures in dilute solutions. The formation of multi-compartment, disk-like, toroidal and bicontinuous micelles and the macromolecular architectures that give rise to these morphologies are reviewed and discussed.

Internally structured self-assembled nanospheres, cubosomes, are formed from a semi-crystalline block copolymer, poly(ethylene oxide)-block-poly(octadecyl methacrylate) (PEO39-b-PODMA17), in aqueous dispersion. The poly(octadecyl methacrylate) block provides them with a temperature responsive structure and morphology. Using cryo-electron tomography, we show that at room temperature these internally bicontinuous aggregates undergo an unprecedented order-disorder transition of the microphase separated domains that is accompanied by a change in the overall aggregate morphology. This allows switching between spheres with ordered bicontinuous internal structures at temperatures below the transition temperature and more planar oblate spheroids with a disordered microphase-separated state above the transition temperature. The bicontinuous structures offer a number of possibilities for application as templates e.g. for biomimetic mineralisation or polymerization. Furthermore, the unique nature of the thermal transition observed for this system offers up considerable possibilities for their application as temperature-controlled release vessels. Amphiphilic AB and ABA block copolymers have been demonstrated to form a variety of self-assembled aggregate structures in dilute solutions where the solvent preferentially solvates one of the blocks. Temperature responsive nanospheres with bicontinuous internal structures from a semi-crystalline amphiphilic block copolymer1 The most common structures formed by these amphiphilic macromolecules are spherical micelles, cylindrical micelles and vesicles (polymersomes), with the type of aggregate depending principally upon the relative volumes of the different blocks.1 Over the past decade more complex aggregate structures have been observed and targeted for construction. The majority of these aggregates (such as disk-like and toroidal micelles) may be grouped under the description of complex micelles and can be achieved both through manipulating block copolymer structures and through physical means.2 Multicompartment micelles are typically the result of ABC block copolymers, of which one of the blocks is solvophilic and the remaining two are solvophobic but do not mix.3 Hence microphase separated micellar cores result.We recently reported the experimental observation of complex micelles with bicontinuous hydrophilic/hydrophobic internal structures from amphiphilic norbornene-based double-comb diblock copolymers, with peptide and oligo(ethylene oxide) side chain.4 Block copolymer nanoparticles with similar bicontinuous phase separation have also been observed by Wooley et al, 5 and before that were predicted by Fraaije and Sevink. 6 In the present paper we demonstrate the formation of similar complex micelles, with hydrophobic bicontinuous internal morphologies from an amphiphilic semi-crystalline AB(C) comb-like block copolymer. Using cryo-electron tomography, we show that at room temperature these internally structured nanoparticles undergo an unprecedented order-disorder transiti...

The detection of stress in polymeric materials such as plastics, elastomers, composites and coatings is critical in the monitoring of material failure including stress fractures, fatigue and hysteresis. Mechanochromic systems that utilise a change in fluorescent output as a result of the mechanical deformation of a polymer have only been actively investigated relatively recently and whilst the field is still relatively small a considerable number of examples of such systems now exist. This article will discuss the principles behind such systems and review examples in the literature and survey the most common fluorophores used in such systems including phenylene vinylene oligomeric derivatives, polycyclic aromatic compounds, carbazole derivatives and conjugated polymers.

. (2000) Self-assembled structures from an amphiphilic multiblock copolymer containing rigid semiconductor segments. Macromolecules, 33 (22 ABSTRACT: An amphiphilic multiblock copolymer comprising nearly monodisperse poly(ethylene oxide) segments (Mw/Mn ) 1.03) and polydisperse poly(methylphenylsilane) (PMPS) segments (Mw/Mn ) 2.0) forms a variety of well-defined morphologies such as vesicles, micellar rods, and helices upon aggregation in water-based solvent systems, despite this polydisperse character. Since polysilanes show σ-conjugation in the main chain, the optical and electronic properties of the described block copolymer depend on its confomational behavior. It is demonstrated by microscopic and spectroscopic techniques that the conformations of the PMPS backbone can be controlled through manipulation of the aggregation behavior, i.e., by the choice of the solvent composition.