Aggregation Properties of the Chromonic Liquid Crystal Benzopurpurin 4B

McKitterick, Christopher B.; Erb‐Satullo, Nathaniel L.; LaRacuente, Nicholas D.; Dickinson, Alexandra J.; Collings, Peter J.

doi:10.1021/jp910136p

Cited by 35 publications

(50 citation statements)

References 26 publications

(61 reference statements)

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“…It is well known that organic dyes in aqueous solution tend to form stacks at high concentration, 42,57−60 and BPP has been reported to form aggregates as long as several micrometers. 42 As per our previous work on the Sunset Yellow dye, 61 we calculated the free energy to separate two BPP molecules in water using metadynamics simulations. 54 The computed binding free energy is −31.5 or −35.5 kJ/mol ( Figure S1), depending on the choice of collective variable, which is similar to the value for Sunset Yellow (−28 kJ/mol 61 ) The Journal of Physical Chemistry C Article and an experimental estimate (∼−26 kJ/mol 42 ).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…37−40 Computational work has also been used to understand the interaction of organic molecules with calcium carbonate. Benzopurpurine 4B (BPP, Figure 1b) is a commonly used textile dye 41,42 and structurally closely related to Congo Red, which has previously been studied with in-situ dynamic AFM on the calcite (10.4) cleavage plane. 27 Congo Red has been shown to drastically restructure the calcite (10.4) surface, indicative of a strong molecule−surface interaction perhaps mediated through the negatively charged sulfonate (SO 3 − ) groups.…”

Section: ■ Introductionmentioning

confidence: 99%

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Where Is the Most Hydrophobic Region? Benzopurpurine Self-Assembly at the Calcite–Water Interface

et al. 2017

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Control of molecular self-assembly at solid− liquid interfaces is challenging due to the complex interplay between molecule−molecule, molecule−surface, molecule− solvent, surface−solvent, and solvent−solvent interactions. Here, we use in-situ dynamic atomic force microscopy to study the self-assembly of Benzopurpurine 4B into oblong islands with a highly ordered inner structure yet incommensurate with the underlying calcite (10.4) surface. Molecular dynamics and free energy calculations provide insights by showing that Benzopurpurine 4B molecules do not anchor to the surface directly but instead assemble on top of the second hydration layer. This seemingly peculiar behavior was then rationalized by considering that hydrophobic molecules placed atop the second water layer cause the least distortion to the existing hydration structure. Further experiments for the adsorption of Benzopurpurine 4B on other minerals indicate that the specific interfacial water structure on calcite is decisive for rationalizing the self-assembly of Benzopurpurine 4B in this system.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Where Is the Most Hydrophobic Region? Benzopurpurine Self-Assembly at the Calcite–Water Interface

et al. 2017

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“…3,4,23,39,40 In the simulations, the EO groups cause the molecules to lie at a slightly larger distance apart than would be preferred for the pure aromatic stacking. Two literature values have been reported for TP6EO2M.…”

Section: Distance Between the Molecules In The Stackmentioning

confidence: 99%

“…5,23,39 For Sunset Yellow (SSY) and disodium cromoglycate (DSCG) the stacking free energy is about -7 RT 5, 23 , for benzopurpurin 4B (Direct Red 2) it was found to be -10.2 RT 39 and -12 RT for the dye Blue 27 5 . A collection of free energy values for several chromonic dyes is given by Dickinson et al in their chromonics review.…”

Section: Free Energy Of Associationmentioning

confidence: 99%

Thermodynamics of the self-assembly of non-ionic chromonic molecules using atomistic simulations. The case of TP6EO2M in aqueous solution

et al. 2015

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(2015) 'Thermodynamics of the self-assembly of non-ionic chromonic molecules using atomistic simulations.The case of TP6EO2M in aqueous solution.', Soft matter., 11 (4). pp. 680-691. Further information on publisher's website:http://dx.doi.org/10.1039/C4SM02275KPublisher's copyright statement:Additional information: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. ABSTRACTAtomistic molecular dynamic simulations have been performed for the non-ionic chromonic liquid crystal 2,3,6,7,10,11-hexa-(1,4,7-trioxa-octyl)-triphenylene (TP6EO2M) in aqueous solution. TP6EO2M molecules consist of a central poly-aromatic core (a triphenylene ring) functionalized by six hydrophilic ethyleneoxy (EO) chains, and have a strong tendency to aggregate face-to-face into stacks even in very dilute solution. We have studied self-assembly of the molecules in the low concentration range corresponding to an isotropic solution of aggregates, using two force fields GAFF and OPLS. Our results reveal that the GAFF force field, even though it was successfully used previously for modelling of ionic chromonics, overestimates the attraction of TP6EO2M molecules in water. This results in an aggregation free energy which is too high, a reduced hydration of EO chains and, therefore, molecular self-assembly into compact disordered clusters instead of stacks. In contrast, use of the OPLS force field, leads to self-assembly into ordered stacks in agreement with earlier experimental studies of triphenylene-based chromonics. The free energy of association follows a "quasi-isodesmic" pattern, where the binding free energy of two molecules to form a dimer is of the order of 3 RT larger than the corresponding energy of addition of a molecule into a stack. The obtained value for the binding free energy, ∆ agg G 0 = -12 RT, is found to be in line with the published values for typical ionic chromonics (-7 to -12 RT), and agrees reasonably well with the experimental results for this system. The calculated interlayer distance between the molecules in a stack is 0.37 nm, which is at the top of the range found for typical chromonics (0.33-0.37 nm). We suggest that the relatively large layer spacing can be attributed to the repulsion between EO side chains.2

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“…However, at high temperaturesthe foldamerstend to form long fibrils with a diameter corresponding to their length in the extended state, which also indicates that the preferential direction of stacking is parallel to the ring planes. 3 Schematic representation of cyanine dye smecticmesophase in water with director n: rectangles represent the dye molecules [35]. Molecular structure of the studied dyes is also shown.…”

Section: Page 22 Of 31mentioning

confidence: 99%

WITHDRAWN: Hydrogen-bonding versus π–π stacking in the design of organic semiconductors: From dyes to oligomers

Gospodinova¹,

Tomšík²

2014

Progress in Polymer Science

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This review discusses some general aspects of the highly directional intermolecular interactions in organic solids, followed by an overview of π-conjugated systems exhibiting directional preference in the intermolecular connection and demonstrating enhanced energy and/or charge carrier transfer. As examples, "small" dyes and pigments, "intermediate-sized" N-heteroacenes, and "large" hydrogen-bonded oligomers are considered. In all of these systems the intermolecular interactions between polarized peripheries of the π-conjugated moieties ensure a preferential direction in the molecular packing. The most important among these interactions are hydrogen bonds (both strong and weak). As demonstrated recently, hydrogen bonding represents a dominant attractive force even for molecules with different polarization of the π-conjugated aromatic or heterocyclic moieties, considered to be the most favorable condition for "face-to-face" orientation (π−π stacking).The solid-state anisotropy, most likely, results from the nematic liquid-crystalline ordering of both thermotropic and lyotropic origin. Moreover, the unique efficiency of the exciton diffusion in the J-aggregates of dyes indicates significant potential of the nematic liquidcrystalline state itself for the design of organic semiconductors.

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Aggregation Properties of the Chromonic Liquid Crystal Benzopurpurin 4B

Cited by 35 publications

References 26 publications

Where Is the Most Hydrophobic Region? Benzopurpurine Self-Assembly at the Calcite–Water Interface

Where Is the Most Hydrophobic Region? Benzopurpurine Self-Assembly at the Calcite–Water Interface

Thermodynamics of the self-assembly of non-ionic chromonic molecules using atomistic simulations. The case of TP6EO2M in aqueous solution

WITHDRAWN: Hydrogen-bonding versus π–π stacking in the design of organic semiconductors: From dyes to oligomers

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