Effect of Hydrodynamic Forces on<i>meso</i>‐(4‐Sulfonatophenyl)‐Substituted Porphyrin J‐Aggregate Nanoparticles: Elasticity, Plasticity and Breaking

Balaban, Teodor Silviu; Campos, J. Lourdes; Cespedes, Sergio; Crusats, Joaquim; Escudero, Carlos; Kamma-Lorger, Christina S.; Llorens, Joan; Malfois, Marc; Mitchell, Geoffrey R.; Tojeira, Ana; Ribó, Josep M.

doi:10.1002/chem.201600874

Cited by 36 publications

(63 citation statements)

References 76 publications

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“…2c) reveals that the printed stripes are formed by small, rod-like nano-aggregates, whose length spans from 100 nm up to 400 nm with an aspect ratio ranging between 1:4 and 1:5. Our findings are in agreement with several structural investigations on these J-aggregates, which have been characterized as hollow nanotubes eventually collapsing in bilayered nanoribbons due to solvent evaporation15.…”

Section: Discussionsupporting

confidence: 92%

Spatial control of chirality in supramolecular aggregates

Castriciano

Gentili

Romeo

et al. 2017

Sci Rep

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Chirality is one of the most intriguing properties of matter related to a molecule’s lack of mirror symmetry. The transmission of chirality from the molecular level up to the macroscopic scale has major implications in life sciences but it is also relevant for many chemical applications ranging from catalysis to spintronic. These technological applications require an accurate control of morphology, homogeneity and chiral handedness of thin films and nanostructures. We demonstrate a simple approach to specifically transfer chirality to the model supramolecular system of J aggregates of the protonated form of tetrakis(4-sulfonatophenyl)-porphyrin by utilizing a soft lithography technique. This approach successfully allows the fabrication of an ordered distribution of sub-micrometric structures in precise and controllable positions with programmed chirality, providing a fundamental breakthrough toward the exploitation of chiral supramolecular aggregates in technological applications, such as sensors, non-linear optics and spintronic.

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Section: Discussionsupporting

confidence: 92%

Spatial control of chirality in supramolecular aggregates

Castriciano

Gentili

Romeo

et al. 2017

Sci Rep

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“…A concentration increase to the mM range yields a viscosity increase and gel‐like solutions constituted by bundles of nanotubes. These concentrated solutions show, as measured in a rotating plate viscometer, irreversible changes of the viscosity value . The first change corresponds to the dispersion of the bundles to single nanotubes, but at very high shear forces fragmentation of the nanotubes occurs.…”

Section: Hydrodynamic Effectsmentioning

confidence: 94%

“…Notice that in order to find correlations between structure and properties the goal is to obtain solutions with unique nanoparticle type. In this respect, the capillary injection of a concentrated solution of H 4 TPPS 4 , free of metallic counter cations, into acidified water, also free of metallic countercations, yields suspensions where practically all J‐aggregates are monolayered hollow nanotubes . This would mean a selective growth of the basic sheet of Figure b closing to monolayered nanotubes.…”

Section: Hydrodynamic Effectsmentioning

confidence: 99%

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Hydrodynamic Effects in Soft‐matter Self‐assembly: The Case of J‐Aggregates of Amphiphilic Porphyrins

Ribó

Arteaga

Canillas

et al. 2017

The Chemical Record

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Chiral J-aggregates of achiral amphiphilic porphyrins (4-sulfonatophenyl and aryl meso-substituted porphyrins) show several effects under the hydrodynamic forces of common stirring. These effects can be classified as pure mechanic (e. g. elasticity, plasticity and breaking of the self-assembly non-covalent bonding) and chemically selective as detected in the formation/growth of the nanoparticles. Diastereoselective, enantioselective and, depending on the sign of chiral shear forces, even enantiospecific selections have been described. Some types of these effects have been reported in other type of J-aggregates. Reversible and irreversible structural effects have been studied by atomic force imaging. The determination of the optical polarization properties (linear and circular) of their solutions is best done using Mueller matrix polarimetry methods.

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“…From these examples it becomes clear that porphyrins are highly interesting molecules for a generation of supramolecular architectures. However, their complex assembly behaviour can give rise to a variety of self‐assembled architectures from the same molecular structure . Furthermore, small changes in the molecular architecture or coordinated metal frequently result in the formation of different types of aggregates .…”

Section: Introductionmentioning

confidence: 99%

Directing the Self‐Assembly Behaviour of Porphyrin‐Based Supramolecular Systems

Weegen

Teunissen

Meijer

2017

Chemistry A European J

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The self-assembly behaviour of a library of tetra-amidated porphyrin molecules decorated with a variety of solubilizing wedges is investigated as dilute solutions in methylcyclohexane. Small changes in the solubilising wedge of the porphyrins resulted in different aggregated states, as evidenced by CD and UV/Vis absorption spectroscopy. The porphyrins form co-facially stacked H-aggregates, slip-stacked J-aggregates or a mixture of both. Detailed thermodynamic and kinetic analysis showed that in all cases the formation of J-aggregates proceeds via an isodesmic mechanism whereas H-aggregates are formed via a cooperative mechanism. It is shown that these aggregates assemble in a parallel pathway, in which both compete for the monomer, compared to a sequential pathway, in which one of the aggregates interconverts into the other. Interestingly, kinetic analysis of porphyrins that only form H-aggregates in thermodynamic equilibrium revealed that the competing pathway towards J-aggregates is operational in these systems as well. Our findings show that the balance between H- and J-aggregates depends on remarkably small changes in the architecture of the solubilising wedges.

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Effect of Hydrodynamic Forces onmeso‐(4‐Sulfonatophenyl)‐Substituted Porphyrin J‐Aggregate Nanoparticles: Elasticity, Plasticity and Breaking

Cited by 36 publications

References 76 publications

Spatial control of chirality in supramolecular aggregates

Spatial control of chirality in supramolecular aggregates

Hydrodynamic Effects in Soft‐matter Self‐assembly: The Case of J‐Aggregates of Amphiphilic Porphyrins

Directing the Self‐Assembly Behaviour of Porphyrin‐Based Supramolecular Systems

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