232 research outputs found

    Unlocking Structure-Self-Assembly Relationships in Cationic Azobenzene Photosurfactants.

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    Azobenzene photosurfactants are light-responsive amphiphiles that have garnered significant attention for diverse applications including delivery and sorting systems, phase transfer catalysis, and foam drainage. The azobenzene chromophore changes both its polarity and conformation (trans-cis isomerization) in response to UV light, while the amphiphilic structure drives self-assembly. Detailed understanding of the inherent relationship between the molecular structure, physicochemical behavior, and micellar arrangement of azobenzene photosurfactants is critical to their usefulness. Here, we investigate the key structure-function-assembly relationships in the popular cationic alkylazobenzene trimethylammonium bromide (AzoTAB) family of photosurfactants. We show that subtle changes in the surfactant structure (alkyl tail, spacer length) can lead to large variations in the critical micelle concentration, particularly in response to light, as determined by surface tensiometry and dynamic light scattering. Small-angle neutron scattering studies also reveal the formation of more diverse micellar aggregate structures (ellipsoids, cylinders, spheres) than predicted based on simple packing parameters. The results suggest that whereas the azobenzene core resides in the effective hydrophobic segment in the trans-isomer, it forms part of the effective hydrophilic segment in the cis-isomer because of the dramatic conformational and polarity changes induced by photoisomerization. The extent of this shift in the hydrophobic-hydrophilic balance is determined by the separation between the azobenzene core and the polar head group in the molecular structure. Our findings show that judicious design of the AzoTAB structure enables selective tailoring of the surfactant properties in response to light, such that they can be exploited and controlled in a reliable fashion

    Indexing In Memoriam Assignment

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    Curatorial note from Digital Pedagogy in the Humanities: The origin of humanities computing is usually dated to 1949, when Father Roberto Busa began working with IBM computers to produce a concordance to the works of Saint Thomas Aquinas (Hockey). Of course, concordances and indexes long predate electronic computers and, as Geoffrey Rockwell suggests, are premised upon hermeneutical assumptions of coherence and generative rule-bound procedures (Rockwell 211). The index is thus another example of “digital” or “hands-on” technology that expands beyond the electronic. Rachel Sagner Buurma’s assignment asks students to create an index to Tennyson’s In Memoriam or to use an existing index to create a new edition of the poem, foregrounding how informational technologies like the index create, constrain, or complicate the interpretation of literary works

    Charge-modulated self-assembly and growth of conjugated polyelectrolyte-polyoxometalate hybrid networks.

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    Self-assembly of an anionic polyoxometalate with cationic conjugated polyelectrolytes leads to hybrid supramolecular networks whose dimensionality is controlled by the chain length and steric charge distribution

    Probing the dynamic self-assembly behaviour of photoswitchable wormlike micelles in real-time.

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    Understanding the dynamic self-assembly behaviour of azobenzene photosurfactants (AzoPS) is crucial to advance their use in controlled release applications such as drug delivery and micellar catalysis. Currently, their behaviour in the equilibrium cis- and trans-photostationary states is more widely understood than during the photoisomerisation process itself. Here, we investigate the time-dependent self-assembly of the different photoisomers of a model neutral AzoPS, tetraethylene glycol mono(4',4-octyloxy,octyl-azobenzene) (C8AzoOC8E4) using small-angle neutron scattering (SANS). We show that the incorporation of in situ UV-Vis absorption spectroscopy with SANS allows the scattering profile, and hence micelle shape, to be correlated with the extent of photoisomerisation in real-time. It was observed that C8AzoOC8E4 could switch between wormlike micelles (trans native state) and fractal aggregates (under UV light), with changes in the self-assembled structure arising concurrently with changes in the absorption spectrum. Wormlike micelles could be recovered within 60 seconds of blue light illumination. To the best of our knowledge, this is the first time the degree of AzoPS photoisomerisation has been tracked in situ through combined UV-Vis absorption spectroscopy-SANS measurements. This technique could be widely used to gain mechanistic and kinetic insights into light-dependent processes that are reliant on self-assembly
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