Lyotropic Chromonic Liquid Crystals for Biological Sensing Applications

Shiyanovskii, Sergij V.; Lavrentovich, Oleg D.; Schneider, Tod; Ishikawa, Taro; Smalyukh, Ivan I.; Woolverton, Christopher J.; Niehaus, G. D.; Doane, Kathleen J.

doi:10.1080/15421400590957288

Cited by 100 publications

(72 citation statements)

References 15 publications

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“…There is considerable interest currently in chromonic systems as media for alignment of nanorods, 6 for thin film fabrication, 7 and for real-time microbial sensors. 8,9 Most well-studied chromonics molecules are ionic systems, composed of a large disc-shaped chromonic anion and a small cation. However, in principle it is possible to design non-ionic chromonic systems.…”

Section: Introductionmentioning

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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Section: Introductionmentioning

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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“…As a result, their mesophases differ significantly from thermotropic and amphiphilic lyotropic liquid crystals. Patterned films of LCLCs have a wide variety of emerging applications distinct from other types of liquid crystals, including inexpensive polarizing films, [12][13][14] holographic displays, 15,16 organic electronics and solar cells, 17,18 biosensors, 19,20 , aqueous colloidal, nanotube and bacterial assembly, [21][22][23][24][25] and precursors to structured graphene-based materials. 26,27 LCLCs also offer useful attributes for fundamental investigation of the effects of elasticity on self-assembly behavior, since their elastic properties can be tuned via control of mesogen concentration, 28 depletants and ions.…”

Section: Introductionmentioning

confidence: 99%

Elasticity-dependent self-assembly of micro-templated chromonic liquid crystal films

et al. 2014

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We explore micropatterned director structures of aqueous lyotropic chromonic liquid crystal (LCLC) films created on squarelattice cylindrical-micropost substrates. The structures are manipulated by modulating the LCLC mesophases and their elastic properties via concentration through drying. Nematic LCLC films exhibit preferred bistable alignment along the diagonals of the micropost lattice. Columnar LCLC films, dried from nematics, form two distinct director and defect configurations: a diagonally aligned director pattern with local squares of defects, and an off-diagonal configuration with zig-zag defects. The formation of these states appears to be tied to the relative splay and bend free energy costs of the initial nematic films. The observed nematic and columnar configurations are understood numerically using a Landau-de Gennes free energy model. Among other attributes, the work provide first examples of quasi-2D micropatterning of LC films in the columnar phase and lyotropic LC films in general, and it demonstrates alignment and configuration switching of typically difficult-to-align LCLC films via bulk elastic properties.

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“…The temperature dependence of the SDC of the surfactant distinctly shows transition from the mesophase to iso tropic state of the system in a region of 357-370 K. In the mesophase the diffusion of the surfactant mo lecules is characterized by an activation energy of 24-26 kJ mol -1 , which is quite reasonable for molecular diffusion of axially oriented surfactant molecules along the long axis of cylindrical aggregates forming the hexa Table 1. Chemical shifts of protons of different groups in С 12 EO 10 and С 12 EO 10 -La III in an aqueous solution with C Surf = 1•10 -4 mol L -1 (Me 4 Si as reference) Group δ С 12 EO 10 -Н 2 О С 12 EO 10 -La III -Н 2 О Me 0.821 0.741 (СН 2 ) 9 1.236 1.145 СН 2 1.534 1.426 СН 2 О 3.401 3.307 (СН 2 СН 2 О) 10 3.646 3.554 gonal phase. On going to the isotropic phase, the system under study can be considered as a concentrated di sordered medium in which diffusion of a molecule is more energy consuming because of steric hindrance.…”

Section: Resultsmentioning

confidence: 99%

Self-diffusion in the isotropic and mesomorphic states of the lanthanide-containing system based on nonionic surfactant according to the NMR data

et al. 2008

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Molecular self organization in a system based on lanthanum nitrate and the nonionogenic surfactant, viz., decaethylene glycol monododecyl ether, was studied in an aqueous solution and in the liquid crystalline state. Molecular motion and phase transitions in the system were characterized by the high resolution pulsed gradient spin echo 1 H NMR method.Considerable attention is presently given to studies of the structural and phase properties of lyotropic liquid crystals (LLC). 1-5 Metal containing LLC are widely used in the template synthesis of nanomaterials, as well as in biotechnology, nanocatalysis, and molecular optoelec tronics. 6-12 Lanthanides having unique physical proper ties are of special significance among the metals under study. 13 The Eu 3+ , Tr 3+ , and Tm 3+ ions manifest intense photo and electroluminescence in different spectral re gions. Inclusion of these ions in the structure of a liquid crystal (LC) allows the ions to be potentially used in LC displays as luminescent materials. 14 Some trivalent lan thanide ions are paramagnetics possessing high magnetic moments and magnetic susceptibility anisotropy, which provides their orientation in magnetic field. 15 In some systems, lanthanide ions exhibit strong catalytic ef fects. 16,17 However, despite increased interest in lyotro pic metallomesogens, the number of works devoted to the lanthanide containing lyotropic systems is rather re stricted. 18-21Considerable part of mesomorphic lyophases repre sent supramolecular associates based on spherical, cylin drical, or plate like micelles formed by surfactant (Surf) molecules. Their phase state and behavior are determined to a great extent by the structure of these structural units. Therefore, in the context of studying the properties of LLC, certain attention is given to the examination of micellar self organization of surfactant molecules. 22-24 The NMR method in different modifications is very informative for investigation of the structure and phase transformations of micellar systems and meso phases. 25-28 We have earlier 21 determined the critical micelle concentrations (CMC), identified the hexagonal type of the mesophase, and constructed the isobaric phase diagrams for binary (C 12 EO 10 -H 2 O) and ternary (C 12 EO 10 -Lа(NO 3 ) 3 •6H 2 O-H 2 O) systems containing decaethylene glycol monododecyl ether (C 12 EO 10 ). This work continues the studies of the lanthanide containing LLC and is devoted to the study of molecular motion in a micellar solution and in the LC state by high resolution pulsed gradient spin echo 1 H NMR spectroscopy. ExperimentalCommercial decaethylene glycol monododecyl ether C 12 H 25 O(CH 2 CH 2 O) 10 H (C 12 EO 10 ) and lanthanum nitrate hexa hydrate Lа(NO 3 ) 3 •6H 2 O (La III ) (Aldrich) were used. Mi cellar solutions were prepared using bidistilled water, and the C 12 EO 10 -Ln(NO 3 ) 3 •6H 2 O molar ratio was maintained constant and equal to 0.5. The micellar solutions were studied in a concen tration range of 10 -5 -10 -1 mol L -1 at the temperature 298 K. A С 12 EO ...

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Lyotropic Chromonic Liquid Crystals for Biological Sensing Applications

Cited by 100 publications

References 15 publications

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

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

Elasticity-dependent self-assembly of micro-templated chromonic liquid crystal films

Self-diffusion in the isotropic and mesomorphic states of the lanthanide-containing system based on nonionic surfactant according to the NMR data

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