Preclusion of nano scale self-assembly in block-selective non-aqueous solvents for rod-coil and coil-rod-coil macromolecular surfactants based on perylene tetracarboxylic diimide

Self-assembly of amphiphilic molecules ranging from simple surfactants to block copolymers in a solvent depends on one part of the molecule (one block in block copolymers) being soluble, and the other not. The aggregation of the insoluble segment in the block-selective solvent leads to the self assembly. In this paper, we describe a system of amphiphilic rod-coil and coil-rod-coil molecules, which do not show self assembly in block-selective non-aqueous solvents. We prepared rod-coil molecules based on hydrophilic propylene oxide/ethylene oxide copolymer (PO-EO copolymer) (Jeffamine®) as the flexible segment and photo-conducting large aromatic perylenediimide (PTCDI) as the rod. PO-EO copolymer was attached either to one side of PTCDI (MJ-PTCDI) or both sides (DJ-PTCDI). The former can be considered an inverse macromolecular surfactant, since the tail is hydrophilic and the head is hydrophobic. The DJ-PTCDI is a pseudo Gemini surfactant. Because of the presence of the chromophore, UV-Vis and fluorescent spectra could be used to study the self assembly of these amphiphilic rod coil polymers in solution. PTCDI forms π-interaction mediated aggregates in aqueous solution and these are H-stacked in MJ-PTCDI and J-stacked in DJ-PTCDI. Variable temperature UV and NMR spectra show that the assembly is stable over a large temperature range in water. The aggregates are also stable up to a pH of 12. However, when a non-aqueous solvent is used, no aggregation occurs. This is attributed to the "solvation" of the π-system of the PTCDI. With the addition of water, such solvation seems to be interrupted and aggregation occurs when water becomes a major component. We find that the mole percentage of the aggregates in acetone/water mixtures increases almost linearly with the concentration of water, providing a route to control the extent of aggregation of the chromophores. Due to the long, waxy PO-EO copolymer, MJ-PTCDI and DJ-PTCDI do not show liquid crystalline behavior or nanorod morphology, which were seen with short side chains. The optical microscopy of the bulk material shows aggregated crystals of PTCDI in the waxy matrix, showing that even in the presence of PO-EO copolymer, the molecular assembly of PTCDI takes place in the bulk. Secondary assembly was seen, in that upon ageing of the aqueous solutions, the drop cast films show that the spherical aggregates one-dimensionally coalesced into long fibers. Although UV-Vis spectra indicated no aggregation in non-aqueous solvents, drop-cast films of these solutions show needle-like aggregates and Lego-like assemblies

Tuning the free volume cavities of polyimide membranes via the construction of pseudo-interpenetrating networks for enhanced gas separation performance

10.1021/ma901251yMacromolecules42187042-7054MAMO

Structures of the fungal dynamin-related protein Vps1 reveal a unique, open helical architecture

Dynamin-related proteins (DRPs) are large multidomain GTPases required for diverse membrane-remodeling events. DRPs self-assemble into helical structures, but how these structures are tailored to their cellular targets remains unclear. We demonstrate that the fungal DRP Vps1 primarily localizes to and functions at the endosomal compartment. We present crystal structures of a Vps1 GTPase–bundle signaling element (BSE) fusion in different nucleotide states to capture GTP hydrolysis intermediates and concomitant conformational changes. Using cryoEM, we determined the structure of full-length GMPPCP-bound Vps1. The Vps1 helix is more open and flexible than that of dynamin. This is due to further opening of the BSEs away from the GTPase domains. A novel interface between adjacent GTPase domains forms in Vps1 instead of the contacts between the BSE and adjacent stalks and GTPase domains as seen in dynamin. Disruption of this interface abolishes Vps1 function in vivo. Hence, Vps1 exhibits a unique helical architecture, highlighting structural flexibilities of DRP self-assembly