Supramolecular modification of ABC triblock terpolymers in confinement assembly

The self-assembly of AB diblock copolymers in three-dimensional (3D) soft confinement of nanoemulsions has recently become an attractive bottom up route to prepare colloids with controlled inner morphologies. In that regard, ABC triblock terpolymers show a more complex morphological behavior and could thus give access to extensive libraries of multicompartment microparticles. However, knowledge about their self-assembly in confinement is very limited thus far. Here, we investigated the confinement assembly of polystyrene-block-poly(4-vinylpyridine)-block-poly(tert-butyl methacrylate) (PS-b-P4VP-b-PT or SVT) triblock terpolymers in nanoemulsion droplets. Depending on the block weight fractions, we found spherical microparticles with concentric lamella–sphere (ls) morphology, i.e., PS/PT lamella intercalated with P4VP spheres, or unusual conic microparticles with concentric lamella–cylinder (lc) morphology. We further described how these morphologies can be modified through supramolecular additives, such as hydrogen bond (HB) and halogen bond (XB) donors. We bound donors to the 4VP units and analyzed changes in the morphology depending on the binding strength and the length of the alkyl tail. The interaction with the weaker donors resulted in an increase in volume of the P4VP domains, which depends upon the molar fraction of the added donor. For donors with a high tendency of intermolecular packing, a visible change in the morphology was observed. This ultimately caused a shape change in the microparticle. Knowledge about how to control inner morphologies of multicompartment microparticles could lead to novel carbon supports for catalysis, nanoparticles with unprecedented topologies, and potentially, reversible shape changes by light actuation

Cold gas and young stars in tidally-disturbed ellipticals at z=0

We present an analysis of the neutral hydrogen and stellar populations of elliptical galaxies in the Tal et al. (2009) sample. Our aim is to test their conclusion that the continuing assembly of these galaxies at z~0 is essentially gas-free and not accompanied by significant star formation. In order to do so, we make use of HI data and line-strength indices available in the literature. We look for direct and indirect evidence of the presence of cold gas during the recent assembly of these objects and analyse its relation to galaxy morphological fine structure. We find that >25% of ellipticals contain HI at the level of M(HI)>10^8 M(Sun), and that M(HI) is of the order of a few percent of the total stellar mass. Available data are insufficient to establish whether galaxies with a disturbed stellar morphology are more likely to contain HI. However, HI interferometry reveals very disturbed gas morphology/kinematics in all but one of the detected systems, confirming the continuing assembly of many ellipticals but also showing that this is not necessarily gas-free. We also find that all very disturbed ellipticals have a single-stellar-population-equivalent age <4 Gyr. We interpret this as evidence that ~0.5-5% of their stellar mass is contained in a young population formed during the past ~1 Gyr. Overall, a large fraction of ellipticals seem to have continued their assembly over the past few Gyr in the presence of a mass of cold gas of the order of 10% of the galaxy stellar mass. This material is now observable as neutral hydrogen and young stars.Comment: 5 pages, 1 table, 3 figures. Accepted for publication in MNRAS Letter

Block co-polyMOFs: morphology control of polymer-MOF hybrid materials.

The hybridization of block copolymers and metal-organic frameworks (MOFs) to create novel materials (block co-polyMOFs, BCPMOFs) with controlled morphologies is reported. In this study, block copolymers containing poly(1,4-benzenedicarboxylic acid, H2bdc) and morphology directing poly(ethylene glycol) (PEG) or poly(cyclooctadiene) (poly(COD)) blocks were synthesized for the preparation of BCPMOFs. Block copolymer architecture and weight fractions were found to have a significant impact on the resulting morphology, mediated through the assembly of polymer precursors prior to MOF formation, as determined through dynamic light scattering. Simple modification of block copolymer weight fraction allowed for tuning of particle size and morphology with either faceted and spherical features. Modification of polymer block architecture represents a simple and powerful method to direct morphology in highly crystalline polyMOF materials. Furthermore, the BCPMOFs could be prepared from both Zr4+ and Zn2+ MOFs, yielding hybrid materials with appreciable surface areas and tuneable porosities. The resulting Zn2+ BCPMOF yielded materials with very narrow size distributions and uniform cubic morphologies. The use of topology in BCPMOFs to direct morphology in block copolymer assemblies may open new methodologies to access complex materials far from thermodynamic equilibrium