The title porphyrin shows non ideal cmc with formation of J-aggregates, due to the formation of intermolecularly stabilized zwitterions, which at high concentration also results in H-aggregates.
Homoassociates of the achiral title porphyrins in acid solutions show spontaneous symmetry breaking, which can be detected by circular dichroism (CD). The CD spectra are due to differential scattering and differential absorption contributions, the relative significance of which is related to the shape and size of the homoassociate. When an earlier model, designed for the association of these diprotonated porphyrins (J aggregates with the geometry of stepped sheets of intramolecularstabilised zwitterions), was applied to an exciton-coupling point-dipole approximation, the folding of the onedimensional homoassociates explained the CD signals detected. An effect of the vortex direction, caused by stirring or rotary evaporation, upon the exciton chirality sign was detected. In the case of H 2 TPPS 3 , the number of experiments performed gave a statistical significance to this effect. This vortex effect can be attributed to enhancement of the chirality fluctuations that originate in the diffusion-limited aggregation to highmolecular-weight homoassociates. In this sense, the phenomenon could be general for supramolecular systems that are obtained under kinetic control, and its detection would be possible when inherent chiral chromophores were being generated in the association process. H , B J and Q bands of all compounds and experiments. Example of the evolution of a metastable solution.
Different phoretic driving mechanisms have been proposed for the transport of solid or liquid microscopic inclusions in integrated chemical processes. It is now shown that a substrate that was chemically modified with photosensitive self-assembled monolayers enables the direct control of the assembly and transport of large ensembles of micrometer-sized particles and drops that were dispersed in a thin layer of anisotropic fluid. This strategy separates particle driving, which was realized by AC electrophoresis, and steering, which was achieved by elastic modulation of the nematic host fluid. Inclusions respond individually or in collective modes following arbitrary reconfigurable paths that were imprinted by irradiation with UV or blue light. Relying solely on generic material properties, the proposed procedure is versatile enough for the development of applications that involve either inanimate or living materials.
Different phoretic driving mechanisms have been proposed for the transport of solid or liquid microscopic inclusions in integrated chemical processes. It is now shown that a substrate that was chemically modified with photosensitive self‐assembled monolayers enables the direct control of the assembly and transport of large ensembles of micrometer‐sized particles and drops that were dispersed in a thin layer of anisotropic fluid. This strategy separates particle driving, which was realized by AC electrophoresis, and steering, which was achieved by elastic modulation of the nematic host fluid. Inclusions respond individually or in collective modes following arbitrary reconfigurable paths that were imprinted by irradiation with UV or blue light. Relying solely on generic material properties, the proposed procedure is versatile enough for the development of applications that involve either inanimate or living materials.
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