Modifying the Morphology of Silicon Surfaces by Laser Induced Liquid Assisted Colloidal Lithography

Single, or isolated small arrays of, spherical silica colloidal particles (with refractive index ncolloid = 1.47 and radius R = 350 nm or 1.5 μm) were placed on a silicon substrate and immersed in carbon tetrachloride (nliquid = 1.48) or toluene (nliquid = 1.52). Areas of the sample were then exposed to a single laser pulse (8 ps duration, wavelength λ = 355 nm), and the spatial intensity modulation of the near field in the vicinity of the particles revealed via the resulting patterning of the substrate surface. In this regime, ncolloid < nliquid and the near-field optical intensification is concentrated at and beyond the edge of the particle. Detailed experimental characterization of the irradiated Si surface using atomic force microscopy reveals contrasting topographies. The same optical behavior is observed with both liquids, i.e., the incident laser light diverges on interaction with the colloidal particle, but the resulting interaction with the substrate is liquid dependent. Topographic analysis indicates localized ablation and patterning of the Si substrate when using toluene, whereas the patterning induced under carbon tetrachloride is on a larger scale and extends well below the original substrate surface—hinting at a laser induced photochemical contribution to the surface patterning

“Cross” Supermicelles via the Hierarchical Assembly of Amphiphilic Cylindrical Triblock Comicelles

Self-assembled “cross” architectures are well-known in biological systems (as illustrated by chromosomes, for example); however, comparable synthetic structures are extremely rare. Herein we report an in depth study of the hierarchical assembly of the amphiphilic cylindrical P–H–P triblock comicelles with polar (P) coronal ends and a hydrophobic (H) central periphery in a selective solvent for the terminal segments which allows access to “cross” supermicelles under certain conditions. Well-defined P–H–P triblock comicelles M­(PFS-<i>b</i>-PtBA)-<i>b</i>-M­(PFS-<i>b</i>-PDMS)-<i>b</i>-M­(PFS-<i>b</i>-PtBA) (M = micelle segment, PFS = polyferrocenyldimethylsilane, PtBA = poly­(<i>tert</i>-butyl acrylate), and PDMS = polydimethylsiloxane) were created by the living crystallization-driven self-assembly (CDSA) method. By manipulating two factors in the supermicelles, namely the H segment-solvent interfacial energy (through the central H segment length, <i>L</i>₁) and coronal steric effects (via the PtBA corona chain length in the P segment, <i>L</i>₂ related to the degree of polymerization DP₂) the aggregation of the triblock comicelles could be finely tuned. This allowed a phase-diagram to be constructed that can be extended to other triblock comicelles with different coronas on the central or end segment where “cross” supermicelles were exclusively formed under predicted conditions. Laser scanning confocal microscopy (LSCM) analysis of dye-labeled “cross” supermicelles, and block “cross” supermicelles formed by addition of a different unimer to the arm termini, provided complementary characterization to transmission electron microscopy (TEM) and dynamic light scattering (DLS) and confirmed the existence of these “cross” supermicelles as kinetically stable, micron-size colloidally stable structures in solution

Structural features distinguishing infectious ex vivo mammalian prions from non-infectious fibrillar assemblies generated in vitro

Seeded polymerisation of proteins forming amyloid fibres and their spread in tissues has been implicated in the pathogenesis of multiple neurodegenerative diseases: so called "prion-like" mechanisms. While ex vivo mammalian prions, composed of multichain assemblies of misfolded host-encoded prion protein (PrP), act as lethal infectious agents, PrP amyloid fibrils produced in vitro generally do not. The high-resolution structure of authentic infectious prions and the structural basis of prion strain diversity remain unknown. Here we use cryo-electron microscopy and atomic force microscopy to examine the structure of highly infectious PrP rods isolated from mouse brain in comparison to non-infectious recombinant PrP fibrils generated in vitro. Non-infectious recombinant PrP fibrils are 10 nm wide single fibres, with a double helical repeating substructure displaying small variations in adhesive force interactions across their width. In contrast, infectious PrP rods are 20 nm wide and contain two fibres, each with a double helical repeating substructure, separated by a central gap of 8-10 nm in width. This gap contains an irregularly structured material whose adhesive force properties are strikingly different to that of the fibres, suggestive of a distinct composition. The structure of the infectious PrP rods, which cause lethal neurodegeneration, readily differentiates them from all other protein assemblies so far characterised in other neurodegenerative diseases

De novo designed peptide and protein hairpins self‐assemble into sheets and nanoparticles

AFM, TEM, fluorescence microscopy image files and spectral data published in DOI:10.1002/smll.202100472. Preprint of this is available at bioRxiv DOI:10.1101/2020.08.14.25146

Dimensional control and morphological transformations of supramolecular polymeric nanofibers based on cofacially-stacked planar amphiphilic platinum(II) complexes

Square-planar platinum­(II) complexes often stack cofacially to yield supramolecular fiber-like structures with interesting photophysical properties. However, control over fiber dimensions and the resulting colloidal stability is limited. We report the self-assembly of amphiphilic Pt­(II) complexes with solubilizing ancillary ligands based on polyethylene glycol [PEG_<i>n</i>, where <i>n</i> = 16, 12, 7]. The complex with the longest solubilizing PEG ligand, <b>Pt-PEG</b>_<b>16</b>, self-assembled to form polydisperse one-dimensional (1D) nanofibers (diameters <5 nm). Sonication led to short seeds which, on addition of further molecularly dissolved <b>Pt-PEG</b>_<b>16</b> complex, underwent elongation in a “living supramolecular polymerization” process to yield relatively uniform fibers of length up to <i>ca</i>. 400 nm. The fiber lengths were dependent on the <b>Pt-PEG</b>_<b>16</b> complex to seed mass ratio in a manner analogous to a living covalent polymerization of molecular monomers. Moreover, the fiber lengths were unchanged in solution after 1 week and were therefore “static” with respect to interfiber exchange processes on this time scale. In contrast, similarly formed near-uniform fibers of <b>Pt-PEG</b>_<b>12</b> exhibited dynamic behavior that led to broadening of the length distribution within 48 h. After aging for 4 weeks in solution, <b>Pt-PEG</b>_<b>12</b> fibers partially evolved into 2D platelets. Furthermore, self-assembly of <b>Pt-PEG</b>_<b>7</b> yielded only transient fibers which rapidly evolved into 2D platelets. On addition of further fiber-forming Pt complex (<b>Pt-PEG</b>_<b>16</b>), the platelets formed assemblies <i>via</i> the growth of fibers selectively from their short edges. Our studies demonstrate that when interfiber dynamic exchange is suppressed, dimensional control and hierarchical structure formation are possible for supramolecular polymers through the use of kinetically controlled seeded growth methods