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Sample records for liquid crystalline block

  1. Liquid-crystalline ordering helps block copolymer self-assembly.

    PubMed

    Yu, Haifeng; Kobayashi, Takaomi; Yang, Huai

    2011-08-01

    Interaction between liquid-crystalline elastic deformation and microphase separation in liquid-crystalline block copolymers enables them to supramolecularly assemble into ordered nanostructures with high regularity. With the help of liquid-crystalline alignment, parallel and perpendicular patterning of nanostructures is fabricated with excellent reproducibility and mass production, which provides nanotemplates and nanofabrication processes for preparing varieties of nanomaterials. Furthermore, nanoscale microphase separation improves the optical performance of block-copolymer fi lms by eliminating the scattering of visible light, leading to advanced applications in optical devices and actuators. Recent progress in liquid-crystalline block copolymers, including their phase diagram, structure-property relationship, nanostructure control and nanotemplate applications, is reviewed. PMID:21910267

  2. Liquid Crystalline Block Copolymers with Brush Type Architecture: Toward Functional Membranes by Magnetic Field Alignment

    NASA Astrophysics Data System (ADS)

    Choo, Youngwoo; Gopinadhan, Manesh; Mahajan, Lalit; Kasi, Rajeswari; Osuji, Chinedum

    2015-03-01

    We introduce a novel liquid crystalline block copolymer with brush type architecture for membrane applications by magnetic field directed self-assembly. Ring-opening metathesis of n-alkyloxy cyanobiphenyl and polylactide (PLA) functionalized norbornene monomers provides efficient polymerization yielding low polydispersity block copolymers. The molecular weight of the PLA side chains, spacer length of the cyanobiphenyl mesogens are systematically varied to form well-ordered BCP morphologies at varying volume fractions. Interestingly, the system features morphology dependent anchoring condition where mesogens adopt planar anchoring on cylindrical interface while homeotropic anchoring was preferred on a planar block interface. The minority PLA domains from highly aligned materials can be readily degraded by hydrolysis to produce vertically aligned nanoporous polymer films which exhibit reversible thermal switching behavior. The polymers introduced here provide a versatile platform for scalable fabrication of aligned membranes and further functional materials based on such templates. This work was supported by NSF(CCMI-1246804).

  3. Hydrogen-bonded side chain liquid crystalline block copolymer: Molecular design, synthesis, characterization and applications

    NASA Astrophysics Data System (ADS)

    Chao, Chi-Yang

    Block copolymers can self-assemble into highly regular, microphase-separated morphologies with dimensions at nanometer length scales. Potential applications such as optical wavelength photonic crystals, templates for nanolithographic patterning, or nanochannels for biomacromolecular separation take advantage of the well-ordered, controlled size microdomains of block copolymers. Side-chain liquid crystalline block copolymers (SCLCBCPs) are drawing increasing attention since the incorporation of liquid crystallinity turns their well-organized microstructures into dynamic functional materials. As a special type of block copolymer, hydrogen-bonded SCLCBCPs are unique, compositionally tunable materials with multiple dynamic functionalities that can readily respond to thermal, electrical and mechanical fields. Hydrogen-bonded SCLCBCPs were synthesized and assembled from host poly(styrene- b-acrylic acid) diblock copolymers with narrow molecular weight distributions as proton donors and guest imidazole functionalized mesogenic moieties as proton acceptors. In these studies non-covalent hydrogen bonding is employed to connect mesogenic side groups to a block copolymer backbone, both for its dynamic character as well as for facile materials preparation. The homogeneity and configuration of the hydrogen-bonded complexes were determined by both the molecular architecture of imidazolyl side groups and the process conditions. A one-dimensional photonic crystal composed of high molecular weight hydrogen-bonded SCLCBCP, with temperature dependent optical wavelength stop bands was successfully produced. The microstructures of hydrogen-bonded complexes could be rapidly aligned in an AC electric field at temperatures below the order-disorder transition but above their glass transitions. Remarkable dipolar properties of the mesogenic groups and thermal dissociation of hydrogen bonds are key elements to fast orientation switching. Studies of a wide range of mesogen and polymer

  4. Nanorods in functionalized block-copolymer gels: Flexible ladders and liquid crystalline order in curved geometries

    NASA Astrophysics Data System (ADS)

    Knorowski, C.; Travesset, A.

    2012-12-01

    Polymer nanocomposites (PNCs) hold great promise for designing novel materials. Current challenges in PNCs are achieving nanosized dispersion of the inorganic component as well as robust control of nanoparticle orientation. We show that a gel of multi-block polymers with functionalized end groups that have specific affinity towards nanorods provides a general example of a PNC where the inorganic component is dispersed at the nanometer scale and displays long range as well as orientation order. We find a novel type of liquid crystalline (LC) order consisting of thin nanorod strips, i.e., “flexible ladders” (FL). Depending on concentration and affinity, FL display positional long-range order and patch together into 2D smectic phases. We discuss implications for designing new PNCs and address possible realizations of our systems via DNA linkers. The problem of LC order on curved geometries is also discussed.

  5. Liquid-crystalline octopus dendrimers: block molecules with unusual mesophase morphologies.

    PubMed

    Gehringer, Lionel; Bourgogne, Cyril; Guillon, Daniel; Donnio, Bertrand

    2004-03-31

    The synthesis and the mesomorphic properties of several new main-chain liquid-crystalline dendrimers, thereafter designated as octopus dendrimers in accordance with their eight sidearms, are reported. In these dendritic systems, the arborescence is ensured by anisotropic segments, acting as branching cells with a double multiplicity, which are incorporated at every node of the dendritic architecture. In such a way, these compounds radically differ from the classical end-functionalized liquid-crystalline dendrimers, the most commonly reported systems. Following our previous report on purely homolithic systems, that is, the building blocks constituting the dendritic matrix are all identical, several heterolithic systems made of different anisotropic blocks have been prepared. The dendritic branches and corresponding dendrimers were synthesized using a modular construction. Polarized optical microscopy and X-ray diffraction studies showed that all of these new octopus dendrimers exhibit either smectic-like or columnar phases with novel morphologies, the nature of the mesophases depending on the number of terminal chains attached to the peripheral groups. The mesomorphism of these heterolithic dendrimers is discussed in terms of their intrinsic architecture and compared to the analogous homolithic octopus systems. Models for the molecular organizations within both the smectic and the columnar phases are proposed on the basis of small Bragg angle X-ray diffraction studies and are supported by molecular modelizations. Moreover, this study showed that the mesophase stability is very sensitive to the nature and to the mutual arrangement (the spatial location) of the mesogenic segments within the dendritic matrix, illustrating the intimate relationships existing between the mesomorphic properties and the molecular architecture of these dendrimers. PMID:15038740

  6. Influence of Variations in Liquid-Crystalline Content upon the Self-Assembly Behavior of Siloxane-Based Block Copolymers

    SciTech Connect

    Verploegen,E.; Zhang, T.; Murlo, N.; Hammond, P.

    2008-01-01

    A series of well-defined smectic side chain liquid-crystalline (LC) block copolymers with a low glass transition (Tg) siloxane block has been synthesized via anionic polymerization; these systems consist of a glassy polystyrene block and a unique low glass transition temperature LC block based on poly(vinylmethylsiloxane) to which six different LCs have been synthesized and attached. The synthesis techniques used provide systematic control over covalent LC side chain content, allowing for a range of morphologies to be obtained from a single block copolymer backbone during a one-step LC attachment reaction. Variations in the LC structure and content significantly affect the morphology of the LC mesophase, allowing the smectic-to-isotropic transition temperature to be tuned from room temperature up to 150 C. There are two key driving forces in the self-assembly behavior of these materials that are significantly affected by the LC content. The first is the segmental interaction parameter (?) between the blocks, which is a function of the amount of LC attached to the siloxane block. The attachment percent of the LCs to the siloxane block determines the packing density, which affects the stability of the LC mesophase and its interactions with the inter-material dividing surface. The self-assembled morphologies are characterized as a function of LC content and the mechanisms for the observed behavior are detailed. Additional insights into the interactions between the LC and block copolymer mesophases are gained by investigating the morphologies in response to mechanical deformation. The elastic modulus of this system can be tailored over several orders of magnitude by controlling the LC content, and the thermo-mechanical behavior is also highly dependent. The ability to precisely control the degree of LC functionalization enables the custom design and tailoring of material properties for specific applications such as electro-mechanical, damping, and mechano

  7. Magnetic Field Alignment of PS-P4VP: a Non-Liquid Crystalline Coil-Coil Block Copolymer

    NASA Astrophysics Data System (ADS)

    Rokhlenko, Yekaterina; Zhang, Kai; Larson, Steven; Gopalan, Padma; O'Hern, Corey; Osuji, Chinedum

    2015-03-01

    Magnetic fields provide the ability to control alignment of self-assembled soft materials such as block copolymers. Most prior work in this area has relied on the presence of ordered assemblies of anisotropic liquid crystalline species to ensure sufficient magnetic anisotropy to drive alignment. Recent experiments with poly(styrene-b-4-vinylpyridine), a non-liquid crystalline BCP, however, show field-induced alignment of a lamellar microstructure during cooling across the order-disorder transition. Using in situ x-ray scattering, we examine the roles of field strength and cooling rate on the alignment response of this low MW coil-coil BCP. Alignment is first observed at field strengths as low as 1 Tesla and improves markedly with both increasing field strength and slower cooling. We present a geometric argument to illustrate the origin of a finite, non-trivial magnetic susceptibility anisotropy for highly stretched surface-tethered polymer chains and corroborate this using coarse-grained molecular dynamics simulations. We rationalize the magnetic field response of the system in terms of the mobility afforded by the absence of entanglements, the intrinsic anisotropy resulting from the stretched polymer chains and sterically constrained conjugated rings, and the large grain size in these low molecular weight materials.

  8. End Groups of Functionalized Siloxane Oligomers Direct Block-Copolymeric or Liquid-Crystalline Self-Assembly Behavior

    PubMed Central

    2016-01-01

    Monodisperse oligodimethylsiloxanes end-functionalized with the hydrogen-bonding ureidopyrimidinone (UPy) motif undergo phase separation between their aromatic end groups and dimethylsiloxane midblocks to form ordered nanostructures with domain spacings of <5 nm. The self-assembly behavior of these well-defined oligomers resembles that of high degree of polymerization (N)–high block interaction parameter (χ) linear diblock copolymers despite their small size. Specifically, the phase morphology varies from lamellar to hexagonal to body-centered cubic with increasing asymmetry in molecular volume fraction. Mixing molecules with different molecular weights to give dispersity >1.13 results in disorder, showing importance of molecular monodispersity for ultrasmall ordered phase separation. In contrast, oligodimethylsiloxanes end-functionalized with an O-benzylated UPy derivative self-assemble into lamellar nanostructures regardless of volume fraction because of the strong preference of the end groups to aggregate in a planar geometry. Thus, these molecules display more classically liquid-crystalline self-assembly behavior where the lamellar bilayer thickness is determined by the siloxane midblock. Here the lamellar nanostructure is tolerant to molecular polydispersity. We show the importance of end groups in high χ–low N block molecules, where block-copolymer-like self-assembly in our UPy-functionalized oligodimethylsiloxanes relies upon the dominance of phase separation effects over directional end group aggregation. PMID:27054381

  9. End Groups of Functionalized Siloxane Oligomers Direct Block-Copolymeric or Liquid-Crystalline Self-Assembly Behavior.

    PubMed

    Zha, R Helen; de Waal, Bas F M; Lutz, Martin; Teunissen, Abraham J P; Meijer, E W

    2016-05-01

    Monodisperse oligodimethylsiloxanes end-functionalized with the hydrogen-bonding ureidopyrimidinone (UPy) motif undergo phase separation between their aromatic end groups and dimethylsiloxane midblocks to form ordered nanostructures with domain spacings of <5 nm. The self-assembly behavior of these well-defined oligomers resembles that of high degree of polymerization (N)-high block interaction parameter (χ) linear diblock copolymers despite their small size. Specifically, the phase morphology varies from lamellar to hexagonal to body-centered cubic with increasing asymmetry in molecular volume fraction. Mixing molecules with different molecular weights to give dispersity >1.13 results in disorder, showing importance of molecular monodispersity for ultrasmall ordered phase separation. In contrast, oligodimethylsiloxanes end-functionalized with an O-benzylated UPy derivative self-assemble into lamellar nanostructures regardless of volume fraction because of the strong preference of the end groups to aggregate in a planar geometry. Thus, these molecules display more classically liquid-crystalline self-assembly behavior where the lamellar bilayer thickness is determined by the siloxane midblock. Here the lamellar nanostructure is tolerant to molecular polydispersity. We show the importance of end groups in high χ-low N block molecules, where block-copolymer-like self-assembly in our UPy-functionalized oligodimethylsiloxanes relies upon the dominance of phase separation effects over directional end group aggregation. PMID:27054381

  10. Liquid-crystalline polymer and block copolymer domain alignment controlled by free-surface segregation.

    PubMed

    Fukuhara, Kei; Fujii, Yasuyoshi; Nagashima, Yuki; Hara, Mitsuo; Nagano, Shusaku; Seki, Takahiro

    2013-06-01

    An orientational change from homeotropic to planar of liquid crystal (LC) mesogens and the microphase separation (MPS) domains is attained by the segregated skin layer at the free surface. This allows for an efficient in-plane photoalignment of the cylindrical domains. The surface segregation strategy is very simple and is therefore expected to open up new possibilities for the orientation control of various types of LC materials. PMID:23616365

  11. Liquid crystalline composites containing phyllosilicates

    DOEpatents

    Chaiko, David J.

    2004-07-13

    The present invention provides phyllosilicate-polymer compositions which are useful as liquid crystalline composites. Phyllosilicate-polymer liquid crystalline compositions of the present invention can contain a high percentage of phyllosilicate while at the same time be transparent. Because of the ordering of the particles liquid crystalline composite, liquid crystalline composites are particularly useful as barriers to gas transport.

  12. Liquid crystalline composites containing phyllosilicates

    DOEpatents

    Chaiko; David J.

    2007-05-08

    The present invention provides barrier films having reduced gas permeability for use in packaging and coating applications. The barrier films comprise an anisotropic liquid crystalline composite layer formed from phyllosilicate-polymer compositions. Phyllosilicate-polymer liquid crystalline compositions of the present invention can contain a high percentage of phyllosilicate while remaining transparent. Because of the ordering of the particles in the liquid crystalline composite, barrier films comprising liquid crystalline composites are particularly useful as barriers to gas transport.

  13. Liquid crystalline order in mucus

    NASA Technical Reports Server (NTRS)

    Viney, C.; Huber, A. E.; Verdugo, P.

    1993-01-01

    Mucus plays an exceptionally wide range of important biological roles. It operates as a protective, exchange, and transport medium in the digestive, respiratory, and reproductive systems of humans and other vertebrates. Mucus is a polymer hydrogel. It is secreted as discrete packages (secretory granules) by specialized secretory cells. Mucus hydrogel is stored in a condensed state inside the secretory granules. Depending upon the architecture of their constituent macromolecules and on the composition of the solvent, polymer gels can form liquid crystalline microstructures, with orientational order being exhibited over optically resolvable distances. Individual mucin molecules consist of alternating rigid segments (heavily glycosylated; hydrophilic) and flexible segments (nonglycosylated; hydrophobic). Polymer molecules consisting of rigid units linked by flexible spacers are frequently associated with liquid crystalline behavior, which again raises the possibility that mucus could form anisotropic fluid phases. Suggestions that mucins may be self-associating in dilute solution have previously been challenged on the basis of sedimentation-equilibrium studies performed on mucus in which potential sites of association were competitively blocked with inhibitors. However, the formation of stable liquid crystalline phases does not depend on the existence of inter- or intramolecular associations; these phases can form on the basis of steric considerations alone.

  14. Mesogen-jacketed liquid crystalline polymers.

    PubMed

    Chen, Xiao-Fang; Shen, Zhihao; Wan, Xin-Hua; Fan, Xing-He; Chen, Er-Qiang; Ma, Yuguo; Zhou, Qi-Feng

    2010-08-01

    This critical review covers the recent progress in the research of mesogen-jacketed liquid crystalline polymers (MJLCPs), special side-on side-chain liquid crystalline polymers with very short spacers or without spacers. MJLCPs can self-organize into supramolecular columnar phases with the polymer chains aligned parallel to one another or smectic phases with the backbones embedded in the smectic layers. The semi-rigid rod-like MJLCP with a tunable rod shape in both length and diameter provides an excellent building block in designing novel rod-coil liquid crystalline block copolymers which can self-assemble into hierarchical supramolecular nanostructures depending on the competition between liquid crystal formation and microphase separation (229 references). PMID:20559597

  15. Liquid crystalline polymers

    NASA Technical Reports Server (NTRS)

    1990-01-01

    The remarkable mechanical properties and thermal stability of fibers fabricated from liquid crystalline polymers (LCPs) have led to the use of these materials in structural applications where weight savings are critical. Advances in processing of LCPs could permit the incorporation of these polymers into other than uniaxial designs and extend their utility into new areas such as nonlinear optical devices. However, the unique feature of LCPs (intrinsic orientation order) is itself problematic, and current understanding of processing with control of orientation falls short of allowing manipulation of macroscopic orientation (except for the case of uniaxial fibers). The current and desirable characteristics of LCPs are reviewed and specific problems are identified along with issues that must be addressed so that advances in the use of these unique polymers can be expedited.

  16. Liquid Crystalline Microemulsions

    NASA Astrophysics Data System (ADS)

    Huang, Chien-Yueh; Petschek, Rolfe G.

    2000-03-01

    If an isotropic component of an emulsion is replaced by one having liquid crystalline (e.g. nematic) order the equilibrium behavior can change dramatically. There are long range enthalpic effects which can result in either repulsive or attractive interactions between the surfaces of an emulsion and entropic effects which generally result in an attractive interaction between these surfaces. We review briefly the possibility of stable blue-phase like microemulsions in mixtures of chiral nematics, appropriate surfactants and an incompatible isotropic solvent. We discuss the entropic effects in a lamellar phase, including the effects of changes in elastic constants and surface-nematic coupling. The effects of fluctuations on blue phases will be briefly discussed.

  17. Rotationally Molded Liquid Crystalline Polymers

    NASA Technical Reports Server (NTRS)

    Rogers, Martin; Stevenson, Paige; Scribben, Eric; Baird, Donald; Hulcher, Bruce

    2002-01-01

    Rotational molding is a unique process for producing hollow plastic parts. Rotational molding offers advantages of low cost tooling and can produce very large parts with complicated shapes. Products made by rotational molding include water tanks with capacities up to 20,000 gallons, truck bed liners, playground equipment, air ducts, Nylon fuel tanks, pipes, toys, stretchers, kayaks, pallets, and many others. Thermotropic liquid crystalline polymers are an important class of engineering resins employed in a wide variety of applications. Thermotropic liquid crystalline polymers resins are composed of semi-rigid, nearly linear polymeric chains resulting in an ordered mesomorphic phase between the crystalline solid and the isotropic liquid. Ordering of the rigid rod-like polymers in the melt phase yields microfibrous, self-reinforcing polymer structures with outstanding mechanical and thermal properties. Rotational molding of liquid crystalline polymer resins results in high strength and high temperature hollow structures useful in a variety of applications. Various fillers and reinforcements can potentially be added to improve properties of the hollow structures. This paper focuses on the process and properties of rotationally molded liquid crystalline polymers.

  18. Rotationally Molded Liquid Crystalline Polymers

    NASA Technical Reports Server (NTRS)

    Rogers, Martin; Scribben, Eric; Baird, Donald; Hulcher, Bruce

    2002-01-01

    Rotational molding is a unique process for producing hollow plastic parts. Rotational molding offers low cost tooling and can produce very large parts with complicated shapes. Products made by rotational molding include water tanks with capacities up to 20,000 gallons, truck bed liners, playground equipment, air ducts, Nylon fuel tanks, pipes, toys, stretchers, kayaks, pallets, and many others. Thermotropic liquid crystalline polymers are an important class of engineering resins employed in a wide variety of applications. Thermotropic liquid crystalline polymers resins are composed of semirigid, nearly linear polymeric chains resulting in an ordered mesomorphic phase between the crystalline solid and the isotropic liquid. Ordering of the rigid rod-like polymers in the melt phase yields microfibrous, self-reinforcing polymer structures with outstanding mechanical and thermal properties. Rotational molding of liquid crystalline polymer resins results in high strength and high temperature hollow structures useful in a variety of applications. Various fillers and reinforcements can potentially be added to improve properties of the hollow structures. This paper focuses on the process and properties of rotationally molded liquid crystalline polymers. This paper will also highlight the interactions between academia and small businesses in developing new products and processes.

  19. Freely Suspended Liquid Crystalline Films

    NASA Astrophysics Data System (ADS)

    Sonin, A. A.

    2003-05-01

    Freely Suspended Liquid Crystalline Films Andrei A. Sonin Centre d'Etudes Atomiques de Saclay, France and Institute of Crystallography, Russian Academy of Sciences with a Foreword by Professor Noel Clark University of Colorado, USA This book provides a brief introduction to the physics of liquid crystals and to macroscopic physical parameters characterising freely suspended liquid crystalline (FSLC) films, and then reviews the experimental techniques for preparing these films, measuring their thicknesses, and investigating their physical properties and structural aspects. Molecular structures and defects of FSLC films and the problems of film stability, thinning and rupture are discussed in later chapters. Physical phenomena, such as orientational and phase transitions, Frederick's and flexoelectric effects, hydroelectrodynamics, etc., are also analysed. Finally, some applications of FSLC films in industry and in various branches of science are discussed. Specialists working in the physics of liquid crystals and in surface physics will find this book of interest. Industrial firms and their research centres investigating liquid crystals, biological membranes, detergent/surfactant/biomedical areas; and graduates and postgraduates in solid state physics and crystallography will also benefit from this book. The book has an easy-to-read style with just the minimum amount of mathematics necessary to explain important concepts. This is the first book dedicated exclusively to the physics of FSLC in almost a century since their discovery and last twenty years of their active studies. Andrei Sonin, a scientist in the area of FSLC and author of many articles on surface phenomena in liquid crystals, the properties and behaviour of thin liquid crystalline and surfactant films, has a long standing reputation in liquid crystals and surfactant systems and has been particularly active in issues involving surface interactions.

  20. Nanosecond liquid crystalline optical modulator

    DOEpatents

    Borshch, Volodymyr; Shiyanovskii, Sergij V.; Lavrentovich, Oleg D.

    2016-07-26

    An optical modulator includes a liquid crystal cell containing liquid crystal material having liquid crystal molecules oriented along a quiescent director direction in the unbiased state, and a voltage source configured to apply an electric field to the liquid crystal material wherein the direction of the applied electric field does not cause the quiescent director direction to change. An optical source is arranged to transmit light through or reflect light off the liquid crystal cell with the light passing through the liquid crystal material at an angle effective to undergo phase retardation in response to the voltage source applying the electric field. The liquid crystal material may have negative dielectric anisotropy, and the voltage source configured to apply an electric field to the liquid crystal material whose electric field vector is transverse to the quiescent director direction. Alternatively, the liquid crystal material may have positive dielectric anisotropy and the voltage source configured to apply an electric field to the liquid crystal material whose electric field vector is parallel with the quiescent director direction.

  1. Liquid Crystalline Materials for Biological Applications

    PubMed Central

    Lowe, Aaron M.; Abbott, Nicholas L.

    2012-01-01

    Liquid crystals have a long history of use as materials that respond to external stimuli (e.g., electrical and optical fields). More recently, a series of investigations have reported the design of liquid crystalline materials that undergo ordering transitions in response to a range of biological interactions, including interactions involving proteins, nucleic acids, viruses, bacteria and mammalian cells. A central challenge underlying the design of liquid crystalline materials for such applications is the tailoring of the interface of the materials so as to couple targeted biological interactions to ordering transitions. This review describes recent progress toward design of interfaces of liquid crystalline materials that are suitable for biological applications. Approaches addressed in this review include the use of lipid assemblies, polymeric membranes containing oligopeptides, cationic surfactant-DNA complexes, peptide-amphiphiles, interfacial protein assemblies and multi-layer polymeric films. PMID:22563142

  2. Stability of liquid crystalline bridges

    NASA Astrophysics Data System (ADS)

    Mahajan, Milind P.; Tsige, Mesfin; Taylor, P. L.; Rosenblatt, Charles

    1999-02-01

    The stability of cylindrical bridges of the liquid crystal octylcyanobiphenyl in an immiscible liquid bath was investigated in the nematic and smectic A phases. In the nematic phase the bridge was found to destabilize at a length-to-diameter (slenderness) ratio R similar to that of ordinary Newtonian fluids. On the other hand, the Bingham behavior of the smectic A phase, i.e., an apparent yield stress, enabled the formation of stable columns with R well in excess of π.

  3. Light-induced liquid crystallinity.

    PubMed

    Kosa, Tamas; Sukhomlinova, Ludmila; Su, Linli; Taheri, Bahman; White, Timothy J; Bunning, Timothy J

    2012-05-17

    Liquid crystals are traditionally classified as thermotropic, lyotropic or polymeric, based on the stimulus that governs the organization and order of the molecular system. The most widely known and applied class of liquid crystals are a subset of thermotropic liquid crystals known as calamitic, in which adding heat can result in phase transitions from or into the nematic, cholesteric and smectic mesophases. Photoresponsive liquid-crystal materials and mixtures can undergo isothermal phase transitions if light affects the order parameter of the system within a mesophase sufficiently. In nearly all previous examinations, light exposure of photoresponsive liquid-crystal materials and mixtures resulted in order-decreasing photo-induced isothermal phase transitions. Under specialized conditions, an increase in order with light exposure has been reported, despite the tendency of the photoresponsive liquid-crystal system to reduce order in the exposed state. A direct, photo-induced transition from the isotropic to the nematic phase has been observed in a mixture of spiropyran molecules and a nematic liquid crystal. Here we report a class of naphthopyran-based materials that exhibit photo-induced conformational changes in molecular structure capable of yielding order-increasing phase transitions. Appropriate functionalization of the naphthopyran molecules leads to an exceedingly large order parameter in the open form, which results in a clear to strongly absorbing dichroic state. The increase in order with light exposure has profound implications in optics, photonics, lasing and displays and will merit further consideration for applications in solar energy harvesting. The large, photo-induced dichroism exhibited by the material system has been long sought in ophthalmic applications such as photochromic and polarized variable transmission sunglasses. PMID:22596158

  4. Liquid crystalline thermosetting polyimides. Final report

    SciTech Connect

    Hoyt, A.E.; Huang, S.J.

    1993-07-01

    Phase separation of rodlike reinforcing polymers and flexible coil matrix polymers is a common problem in formulating molecular composites. One way to reduce phase separation might be to employ liquid crystalline thermosets as the matrix material. In this work, functionally terminated polyimide oligomers which exhibit lyotropic liquid crystalline behavior were successfully prepared. Materials based on 2,2{prime}-bis(trifluoromethyl)-4,4{prime}-diaminobiphenyl and 3,3{prime},4,4{prime}-biphenylenetetra-carboxylic dianhydride have been synthesized and characterized.

  5. Multiscale Control of Hierarchical Structure in Crystalline Block Copolymer Nanoparticles Using Microfluidics.

    PubMed

    Bains, Aman; Cao, Yimeng; Moffitt, Matthew G

    2015-11-01

    Hierarchical semicrystalline block copolymer nanoparticles are produced in a segmented gas-liquid microfluidic reactor with top-down control of multiscale structural features, including nanoparticle morphologies, sizes, and internal crystallinities. Control of multiscale structure on disparate length scales by a single control variable (flow rate) enables tailoring of drug delivery nanoparticle function including release rates. PMID:26305569

  6. Liquid Crystalline Compositions as Gas Sensors

    NASA Astrophysics Data System (ADS)

    Shibaev, Petr; Murray, John; Tantillo, Anthony; Wenzlick, Madison; Howard-Jennings, Jordan

    2015-03-01

    Droplets and films of nematic and cholesteric liquid crystalline mixtures were studied as promising detectors of volatile organic compounds (VOCs) in the air. Under increasing concentration of VOC in the air the detection may rely on each of the following effects sequentially observed one after the other due to the diffusion of VOC inside liquid crystalline matrix: i. slight changes in orientation and order parameter of liquid crystal, ii. formation of bubbles on the top of the liquid crystalline droplet due to the mass transfer between the areas with different order parameter, iii. complete isotropisation of the liquid crystal. All three stages can be easily monitored by optical microscopy and photo camera. Detection limits corresponding to the first stage are typically lower by a factor of 3-6 than detection limits corresponding to the beginning of mass transfer and isotropisation. The prototype of a compact sensor sensitive to the presence of organic solvents in the air is described in detail. The detection limits of the sensor is significantly lower than VOC exposure standards. The qualitative model is presented to account for the observed changes related to the diffusion, changes of order parameter and isotropisation.

  7. Stable liquid crystalline phases of colloidally dispersed exfoliated layered niobates.

    PubMed

    Nakato, Teruyuki; Miyamoto, Nobuyoshi; Harada, Akiko

    2004-01-01

    Colloidally dispersed niobium oxide nanosheets obtained by exfoliation of layered niobates HNb(3)O(8) and HTiNbO(5) formed stable liquid crystalline phases; their liquid crystallinity was dependent on the niobate species exfoliated. PMID:14737341

  8. Mirrorless lasing in liquid crystalline materials

    NASA Astrophysics Data System (ADS)

    Cao, Wenyi; Finkelmann, Heino; Kim, Seok-Tae; Munoz, Antonio; Palffy-Muhoray, Peter; Taheri, Bahman; Twieg, Robert J.

    2002-06-01

    Cholesteric liquid crystals, because of their birefringence and periodic structure, and 1-d photonic band-gap materials. In the reflection band, classical light propagation is forbidden for one of the two eigenmodes; for this mode, the material acts as a distributed cavity host. This inherent distributed cavity effect modifies the fluorescence spectrum, and, if the material is optically pumped, allows population inversion and mirrorless lasing. We have studied emission from thin samples of liquid crystalline materials optically pumped by pico- and nanosecond laser pulses. We have observed laser emission, without an external cavity, from dye-doped liquid crystals, from pure cholesteric liquid crystals without dyes, and from cholesteric liquid crystal elastomers. We present the results of these experiments, discuss the relation between material properties and the lasing process, and consider promising materials and applications.

  9. Nanoparticle Solubility in Liquid Crystalline Defects

    NASA Astrophysics Data System (ADS)

    Whitmer, Jonathan K.; Armas-Perez, Julio C.; Joshi, Abhijeet A.; Roberts, Tyler F.; de Pablo, Juan J.

    2013-03-01

    Liquid crystalline materials often incorporate regions (defects) where the orientational ordering present in the bulk phase is disrupted. These include point hedgehogs, line disclinations, and domain boundaries. Recently, it has been shown that defects will accumulate impurities such as small molecules, monomer subunits or nanoparticles. Such an effect is thought to be due to the alleviation of elastic stresses within the bulk phase, or to a solubility gap between a nematic phase and the isotropic defect core. This presents opportunities for encapsulation and sequestration of molecular species, in addition to the formation of novel structures within a nematic phase through polymerization and nanoparticle self-assembly. Here, we examine the solubility of nanoparticles within a coarse-grained liquid crystalline phase and demonstrate the effects of nanoparticle size and surface interactions in determining sequestration into defect regions.

  10. Photorefractivity in liquid crystalline composite materials

    SciTech Connect

    Wiederrecht, G.P.; Wasielewski, M.R.

    1997-09-01

    We report recent improvements in the photorefractive of liquid crystalline thin film composites containing electron donor and acceptor molecules. The improvements primarily result from optimization of the exothermicity of the intermolecular charge transfer reaction and improvement of the diffusion characteristics of the photogenerated ions. Intramolecular charge transfer dopants produce greater photorefractivity and a 10-fold decrease in the concentration of absorbing chromophores. The mechanism for the generation of mobile ions is discussed.

  11. Production of crystalline polymers via liquid crystal monomers

    NASA Technical Reports Server (NTRS)

    Labes, M.; Palos, C.

    1969-01-01

    Method produces crystalline polymers through a liquid crystalline phase of monomers. The monomer is polymerized while held in the liquid crystalline phase either thermally, photolytically, catalytically, or by X-ray or gamma ray irradiation, and can be performed in an electric or magnetic field that influences the molecular orientation.

  12. Highly crystalline covalent organic frameworks from flexible building blocks.

    PubMed

    Xu, Liqian; Ding, San-Yuan; Liu, Junmin; Sun, Junliang; Wang, Wei; Zheng, Qi-Yu

    2016-03-28

    Two novel 2D covalent organic frameworks (TPT-COF-1 and TPT-COF-2) were synthesized from the flexible 2,4,6-triaryloxy-1,3,5-triazine building blocks on a gram scale, which show high crystallinity and large surface area. The controllable formation of highly ordered frameworks is mainly attributed to the self-assembly Piedfort unit of 2,4,6-triaryloxy-1,3,5-triazine. PMID:26954751

  13. Columnar Liquid-Crystalline Dibenzopentacenodithiophenes by Photocyclization.

    PubMed

    Cabral, Marilia G Belarmino; Pereira de Oliveira Santos, Deise M; Bentaleb, Ahmed; Hillard, Elizabeth A; Cristiano, Rodrigo; Gallardo, Hugo; Durola, Fabien; Bock, Harald

    2016-06-01

    The twofold glyoxylic Perkin reaction of perylene-3,9-diglyoxylic acid with thiophene-diacetic acid followed by oxidative photocylization and reaction with α-branched primary alkylamines yields columnar liquid-crystalline diimides with two sulfur atoms in the condensed arene system. A broad temperature range of the hexagonal columnar mesophase is induced by racemic doubly branched alkyl chains. The HOMO and LUMO energy levels of these thiophene-derived diimides qualify them as electron donors with respect to perylene diimides. PMID:27141916

  14. Synthesis of new liquid crystalline diglycidyl ethers.

    PubMed

    Mohammed, Issam Ahmed; Hamidi, Rashidah Mohamed

    2012-01-01

    The phenolic Schiff bases I-VI were synthesized by condensation reactions between various diamines, namely o-dianisidine, o-tolidine and ethylenediamine with vanillin or p-hydroxybenzaldehyde and subsequent reactions between these phenolic Schiff bases and epichlorohydrin to produce new diglycidyl ethers Ia-VIa. The structures of these compounds were confirmed by CHN, FT-IR, (1)H-NMR, and (13)C-NMR spectroscopy. Their thermotropic liquid crystalline behavior was studied using differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). All the diglycidyl ethers prepared exhibit nematic mesophases, except for Va and VIa, which did not show any transition mesophases, but simply flow to liquids. PMID:22233565

  15. Strong liquid-crystalline polymeric compositions

    DOEpatents

    Dowell, F.

    1993-12-07

    Strong liquid-crystalline polymeric (LCP) compositions of matter are described. LCP backbones are combined with liquid crystalline (LC) side chains in a manner which maximizes molecular ordering through interdigitation of the side chains, thereby yielding materials which are predicted to have superior mechanical properties over existing LCPs. The theoretical design of LCPs having such characteristics includes consideration of the spacing distance between side chains along the backbone, the need for rigid sections in the backbone and in the side chains, the degree of polymerization, the length of the side chains, the regularity of the spacing of the side chains along the backbone, the interdigitation of side chains in sub-molecular strips, the packing of the side chains on one or two sides of the backbone to which they are attached, the symmetry of the side chains, the points of attachment of the side chains to the backbone, the flexibility and size of the chemical group connecting each side chain to the backbone, the effect of semiflexible sections in the backbone and the side chains, and the choice of types of dipolar and/or hydrogen bonding forces in the backbones and the side chains for easy alignment. 27 figures.

  16. Strong liquid-crystalline polymeric compositions

    DOEpatents

    Dowell, Flonnie

    1993-01-01

    Strong liquid-crystalline polymeric (LCP) compositions of matter. LCP backbones are combined with liquid crystalline (LC) side chains in a manner which maximizes molecular ordering through interdigitation of the side chains, thereby yielding materials which are predicted to have superior mechanical properties over existing LCPs. The theoretical design of LCPs having such characteristics includes consideration of the spacing distance between side chains along the backbone, the need for rigid sections in the backbone and in the side chains, the degree of polymerization, the length of the side chains, the regularity of the spacing of the side chains along the backbone, the interdigitation of side chains in sub-molecular strips, the packing of the side chains on one or two sides of the backbone to which they are attached, the symmetry of the side chains, the points of attachment of the side chains to the backbone, the flexibility and size of the chemical group connecting each side chain to the backbone, the effect of semiflexible sections in the backbone and the side chains, and the choice of types of dipolar and/or hydrogen bonding forces in the backbones and the side chains for easy alignment.

  17. Templating gold nanorods with liquid crystalline DNA

    NASA Astrophysics Data System (ADS)

    De Sio, Luciano; Annesi, Ferdinanda; Placido, Tiziana; Comparelli, Roberto; Bruno, Vincenzo; Pane, Alfredo; Palermo, Giovanna; Curri, Maria Lucia; Umeton, Cesare; Bartolino, Roberto

    2015-02-01

    A liquid crystalline, negatively charged, whole-genome DNA is exploited to organize positively charged gold nanorods (GNRs) by means of electrostatic interaction. A mesoscopic alignment of the composite system along a preferred direction is obtained by casting a droplet of the DNA-nanorods solution onto an untreated glass substrate. Gel electrophoresis analysis enables evaluating the effective electric charge of the system, thus minimizing the DNA fragmentation. Polarized optical microscopy, combined with transmission and scanning electron microscopy, shows that, up to 20% in weight of GNR solution, the system exhibits both a long range order, induced by the liquid crystalline phase of the DNA, and a nanoscale organization, due to the DNA self-assembly. These evidences are confirmed by a polarized spectral analysis, which also points out that the optical properties of GNRs strongly depend on the polarization of the impinging probe light. The capability to organize plasmonic nanoparticles by means of DNA material represents a significant advance towards the realization of life science inspired optical materials.

  18. Liquid crystalline spinning of spider silk.

    PubMed

    Vollrath, F; Knight, D P

    2001-03-29

    Spider silk has outstanding mechanical properties despite being spun at close to ambient temperatures and pressures using water as the solvent. The spider achieves this feat of benign fibre processing by judiciously controlling the folding and crystallization of the main protein constituents, and by adding auxiliary compounds, to create a composite material of defined hierarchical structure. Because the 'spinning dope' (the material from which silk is spun) is liquid crystalline, spiders can draw it during extrusion into a hardened fibre using minimal forces. This process involves an unusual internal drawdown within the spider's spinneret that is not seen in industrial fibre processing, followed by a conventional external drawdown after the dope has left the spinneret. Successful copying of the spider's internal processing and precise control over protein folding, combined with knowledge of the gene sequences of its spinning dopes, could permit industrial production of silk-based fibres with unique properties under benign conditions. PMID:11279484

  19. Actuators Based on Liquid Crystalline Elastomer Materials

    PubMed Central

    Jiang, Hongrui; Li, Chensha; Huang, Xuezhen

    2013-01-01

    Liquid crystalline elastomers (LCEs) exhibit a number of remarkable physical effects, including the unique, high-stroke reversible mechanical actuation when triggered by external stimuli. This article reviews some recent exciting developments in the field of LCEs materials with an emphasis on their utilization in actuator applications. Such applications include artificial muscles, industrial manufacturing, health and microelectromechanical systems (MEMS). With suitable synthetic and preparation pathways and well-controlled actuation stimuli, such as heat, light, electric and magnetic field, excellent physical properties of LCE materials can be realized. By comparing the actuating properties of different systems, general relationships between the structure and the property of LCEs are discussed. How these materials can be turned into usable devices using interdisciplinary techniques is also described. PMID:23648966

  20. Synthesis of liquid crystalline epoxy monomers

    NASA Astrophysics Data System (ADS)

    Fabia, J.; Galina, H.; Mossety-Leszczak, B.; Ulanski, J.; Wojciechowski, Piotr; Wlochowicz, Andrzej

    2002-06-01

    A two-stage method of synthesis of liquid-crystalline diepoxy monomers has been developed. In the first stage, esterification of 4-hydroxyphenyl-4-hydroxybenzoate or 4,4'- biphenol or 4,4'-dihydroxyazobenzene was carried out using 4-penetenoic acid. The resulting olefinic precursors were oxidized with m-chloroperoxybenzoic acid to introduce the epoxy groups. The structure of products was confirmed by FT- IR and 1H NMR. Examinations on a polarization microscope with a hot plate confirmed the presence of mesomorphic phases in both the precursors and monomers. The phase transition temperatures were in the range of 73.5 (at cooling) to 128.0 degree(s)C for olefinic precursors and in the range 57.1 (at cooling) to 143 degree(s)C for epoxy compounds, as determined by DSC and thermo-optical analysis (TOA).

  1. Switchable tackiness and wettability of a liquid crystalline polymer

    PubMed

    de Crevoisier G; Fabre; Corpart; Leibler

    1999-08-20

    The spreading velocity of liquids on the surface of a liquid crystalline polymer can be tremendously affected by a slight temperature change. Indeed, a bulk transition between a highly ordered smectic and an isotropic phase induces a sharp change from a rigid to a soft behavior, with consequent effects on the tack properties of the liquid crystalline polymer and on the dewetting dynamics of a liquid on its surface. PMID:10455047

  2. Highly viscous liquid crystalline mixtures: the alternative to liquid crystalline elastomers

    NASA Astrophysics Data System (ADS)

    Shibaev, Petr; Schlesier, Cristina; Newman, Leah; McDonald, Scott

    2012-02-01

    Novel highly viscous liquid crystalline materials based on mixtures of glass forming oligomers and low molar mass liquid crystals were recently designed [1, 2] and studied. In this communication the novel data are presented, the analysis and discussion are extended. It is shown that viscoelastic properties of the materials are due to the physical entanglements between cyclic oligomers and low molar mass mesogens, not due to the chemical crosslinks between molecular moities. However, the mechanical properties of these viscoelastic materials resemble those of chemically crosslinked elastomers (elasticity and reversibility of deformations). The properties of chiral and non-chiral materials loaded with ferromagnetic nanoparticles are discussed in detail. Cholesteric materials undergo gigantic color changes in the wide spectral range under the deformation that allows distant detection of deformation and determination the anisotropy of deformation and its type. The materials doped with laser dyes become mechanically tunable lasers themselves and emit coherent light while pumped by external laser. A simple model is suggested to account for the observed effects; physical properties of the novel materials and liquid crystalline elastomers are compared and discussed. [4pt] [1] P.V. Shibaev, C. Schlesier, R. Uhrlass, S. Woodward, E. Hanelt, Liquid Crystals, 37:12, 1601-1604 [0pt] [2] P.V. Shibaev, P. Riverra, D. Teter, S. Marsico, M. Sanzari, V. Ramakrishnan, E. Hanelt, Optics Express, 16, 2965 (2008)

  3. Free-surface molecular command systems for photoalignment of liquid crystalline materials.

    PubMed

    Fukuhara, Kei; Nagano, Shusaku; Hara, Mitsuo; Seki, Takahiro

    2014-01-01

    The orientation of liquid crystal molecules is very sensitive towards contacting surfaces, and this phenomenon is critical during the fabrication of liquid crystal display panels, as well as optical and memory devices. To date, research has focused on designing and modifying solid surfaces. Here we report an approach to control the orientation of liquid crystals from the free (air) surface side: a skin layer at the free surface was prepared using a non-photoresponsive liquid crystalline polymer film by surface segregation or inkjet printing an azobenzene-containing liquid crystalline block copolymer. Both planar-planar and homoeotropic-planar mode patterns were readily generated. This strategy is applicable to various substrate systems, including inorganic substrates and flexible polymer films. These versatile processes require no modification of the substrate surface and are therefore expected to provide new opportunities for the fabrication of optical and mechanical devices based on liquid crystal alignment. PMID:24534881

  4. Free-surface molecular command systems for photoalignment of liquid crystalline materials

    PubMed Central

    Fukuhara, Kei; Nagano, Shusaku; Hara, Mitsuo; Seki, Takahiro

    2014-01-01

    The orientation of liquid crystal molecules is very sensitive towards contacting surfaces, and this phenomenon is critical during the fabrication of liquid crystal display panels, as well as optical and memory devices. To date, research has focused on designing and modifying solid surfaces. Here we report an approach to control the orientation of liquid crystals from the free (air) surface side: a skin layer at the free surface was prepared using a non-photoresponsive liquid crystalline polymer film by surface segregation or inkjet printing an azobenzene-containing liquid crystalline block copolymer. Both planar-planar and homoeotropic-planar mode patterns were readily generated. This strategy is applicable to various substrate systems, including inorganic substrates and flexible polymer films. These versatile processes require no modification of the substrate surface and are therefore expected to provide new opportunities for the fabrication of optical and mechanical devices based on liquid crystal alignment. PMID:24534881

  5. Wholly aromatic liquid crystalline polyetherimide (LC-PEI) resins

    NASA Technical Reports Server (NTRS)

    Weiser, Erik S. (Inventor); Dingemans, Theodorus J. (Inventor); St. Clair, Terry L. (Inventor); Hinkley, Jeffrey A. (Inventor)

    2011-01-01

    The benefits of liquid crystal polymers and polyetherimides are combined in an all-aromatic thermoplastic liquid crystalline polyetherimide. Because of the unique molecular structure, all-aromatic thermotropic liquid crystal polymers exhibit outstanding processing properties, excellent barrier properties, low solubilities and low coefficients of thermal expansion in the processing direction. These characteristics are combined with the strength, thermal, and radiation stability of polyetherimides.

  6. Metal nanoparticles with liquid-crystalline ligands: controlling nanoparticle superlattice structure and properties.

    PubMed

    Lewandowski, Wiktor; Wójcik, Michał; Górecka, Ewa

    2014-05-19

    Nanoparticle ordered aggregates are promising candidates for future application in a variety of sensing, optical and electronic technologies, mainly based on collective interactions between individual nano-building blocks. Physicochemical properties of such assemblies depend on nanoparticle spacing, therefore a lot of effort throughout the last years was put on development of assembly methods allowing control over aggregates structure. In this minireview we describe efficient self-assembly process based on the utilization of liquid-crystalline ligands grafted onto nanoparticle surface. We show strategies used to synthesize liquid-crystalline nanoparticles as well as discuss parameters influencing structural and thermal characteristic of aggregates. It is also demonstrated that the liquid-crystalline approach offers access to dynamic self-assembly and metamaterials with anisotropic plasmonic properties, which makes this strategy unique among others. PMID:24789440

  7. Silylene-diethynyl-arylene polymers having liquid crystalline properties

    DOEpatents

    Barton, T.J.; Yiwei Ding.

    1993-09-07

    The present invention provides linear organosilicon polymers including diethynyl-(substituted)arylene units, and a process for their preparation. These novel polymers possess useful properties including electrical conductivity, liquid crystallinity, and/or photoluminescence. These polymers possess good solubility in organic solvents. A preferred example is produced according to the following reaction scheme. ##STR1## These polymers can be solvent-cast to yield excellent films and can also be pulled into fibers from concentrated solutions. All possess substantial crystallinity as revealed by DSC analysis and observation through a polarizing microscope, and possess liquid crystalline properties.

  8. Development and evaluation of liquid embolic agents based on liquid crystalline material of glyceryl monooleate.

    PubMed

    Du, Ling-Ran; Lu, Xiao-Jing; Guan, Hai-Tao; Yang, Yong-Jie; Gu, Meng-Jie; Zheng, Zhuo-Zhao; Lv, Tian-Shi; Yan, Zi-Guang; Song, Li; Zou, Ying-Hua; Fu, Nai-Qi; Qi, Xian-Rong; Fan, Tian-Yuan

    2014-08-25

    New type of liquid embolic agents based on a liquid crystalline material of glyceryl monooleate (GMO) was developed and evaluated in this study. Ternary phase diagram of GMO, water and ethanol was constructed and three isotropic liquids (ILs, GMO:ethanol:water=49:21:30, 60:20:20 and 72:18:10 (w/w/w)) were selected as potential liquid embolic agents, which could spontaneously form viscous gel cast when contacting with water or physiological fluid. The ILs exhibited excellent microcatheter deliverability due to low viscosity, and were proved to successfully block the saline flow when performed in a device to simulate embolization in vitro. The ILs also showed good cytocompatibility on L929 mouse fibroblast cell line. The embolization of ILs to rabbit kidneys was performed successfully under monitoring of digital subtraction angiography (DSA), and embolic degree was affected by the initial formulation composition and used volume. At 5th week after embolization, DSA and computed tomography (CT) confirmed the renal arteries embolized with IL did not recanalize in follow-up period, and an obvious atrophy of the embolized kidney was observed. Therefore, the GMO-based liquid embolic agents showed feasible and effective to embolize, and potential use in clinical interventional embolization therapy. PMID:24858389

  9. Sulfonated Polymerized Ionic Liquid Block Copolymers.

    PubMed

    Meek, Kelly M; Elabd, Yossef A

    2016-07-01

    The successful synthesis of a new diblock copolymer, referred to as sulfonated polymerized ionic liquid (PIL) block copolymer, poly(SS-Li-b-AEBIm-TFSI), is reported, which contains both sulfonated blocks (sulfonated styrene: SS) and PIL blocks (1-[(2-acryloyloxy)ethyl]-3-butylimidazolium: AEBIm) with both mobile cations (lithium: Li(+) ) and mobile anions (bis(trifluoromethylsulfonyl)imide: TFSI(-) ). Synthesis consists of polymerization via reversible addition-fragmentation chain transfer, followed by post-functionalization reactions to covalently attach the imidazolium cations and sulfonic acid anions to their respective blocks, followed by ion exchange metathesis resulting in mobile Li(+) cations and mobile TFSI(-) anions. Solid-state films containing 1 m Li-TFSI salt dissolved in ionic liquid result in an ion conductivity of >1.5 mS cm(-1) at 70 °C, where small-angle X-ray scattering data indicate a weakly ordered microphase-separated morphology. These results demonstrate a new ion-conducting block copolymer containing both mobile cations and mobile anions. PMID:27125600

  10. Liquid crystallinity driven highly aligned large graphene oxide composites

    SciTech Connect

    Lee, Kyung Eun; Oh, Jung Jae; Yun, Taeyeong; Kim, Sang Ouk

    2015-04-15

    Graphene is an emerging graphitic carbon materials, consisting of sp{sup 2} hybridized two dimensinal honeycomb structure. It has been widely studied to incorporate graphene with polymer to utilize unique property of graphene and reinforce electrical, mechanical and thermal property of polymer. In composite materials, orientation control of graphene significantly influences the property of composite. Until now, a few method has been developed for orientation control of graphene within polymer matrix. Here, we demonstrate facile fabrication of high aligned large graphene oxide (LGO) composites in polydimethylsiloxane (PDMS) matrix exploiting liquid crystallinity. Liquid crystalline aqueous dispersion of LGO is parallel oriented within flat confinement geometry. Freeze-drying of the aligned LGO dispersion and subsequent infiltration with PDMS produce highly aligned LGO/PDMS composites. Owing to the large shape anisotropy of LGO, liquid crystalline alignment occurred at low concentration of 2 mg/ml in aqueous dispersion, which leads to the 0.2 wt% LGO loaded composites. - Graphical abstract: Liquid crystalline LGO aqueous dispersions are spontaneous parallel aligned between geometric confinement for highly aligned LGO/polymer composite fabrication. - Highlights: • A simple fabrication method for highly aligned LGO/PDMS composites is proposed. • LGO aqueous dispersion shows nematic liquid crystalline phase at 0.8 mg/ml. • In nematic phase, LGO flakes are highly aligned by geometric confinement. • Infiltration of PDMS into freeze-dried LGO allows highly aligned LGO/PDMS composites.

  11. Photoresponsive Liquid Crystalline Epoxy Networks with Shape Memory Behavior and Dynamic Ester Bonds.

    PubMed

    Li, Yuzhan; Rios, Orlando; Keum, Jong K; Chen, Jihua; Kessler, Michael R

    2016-06-22

    Functional polymers are intelligent materials that can respond to a variety of external stimuli. However, these materials have not yet found widespread real world applications because of the difficulties in fabrication and the limited number of functional building blocks that can be incorporated into a material. Here, we demonstrate a simple route to incorporate three functional building blocks (azobenzene chromophores, liquid crystals, and dynamic covalent bonds) into an epoxy-based liquid crystalline network (LCN), in which an azobenzene-based epoxy monomer is polymerized with an aliphatic dicarboxylic acid to create exchangeable ester bonds that can be thermally activated. All three functional building blocks exhibited good compatibility, and the resulting materials exhibits various photomechanical, shape memory, and self-healing properties because of the azobenzene molecules, liquid crystals, and dynamic ester bonds, respectively. PMID:27245744

  12. Liquid crystallinity driven highly aligned large graphene oxide composites

    NASA Astrophysics Data System (ADS)

    Lee, Kyung Eun; Oh, Jung Jae; Yun, Taeyeong; Kim, Sang Ouk

    2015-04-01

    Graphene is an emerging graphitic carbon materials, consisting of sp2 hybridized two dimensinal honeycomb structure. It has been widely studied to incorporate graphene with polymer to utilize unique property of graphene and reinforce electrical, mechanical and thermal property of polymer. In composite materials, orientation control of graphene significantly influences the property of composite. Until now, a few method has been developed for orientation control of graphene within polymer matrix. Here, we demonstrate facile fabrication of high aligned large graphene oxide (LGO) composites in polydimethylsiloxane (PDMS) matrix exploiting liquid crystallinity. Liquid crystalline aqueous dispersion of LGO is parallel oriented within flat confinement geometry. Freeze-drying of the aligned LGO dispersion and subsequent infiltration with PDMS produce highly aligned LGO/PDMS composites. Owing to the large shape anisotropy of LGO, liquid crystalline alignment occurred at low concentration of 2 mg/ml in aqueous dispersion, which leads to the 0.2 wt% LGO loaded composites.

  13. [Structural nucleic acid nanotechnology: liquid-crystalline approach].

    PubMed

    2013-01-01

    The properties of the particles of cholesteric liquid-crystalline dispersions formed by double-stranded DNA molecules obtained as a result of phase exclusion of these molecules from water-salt polymer-containing solutions are briefly described. Physicochemical properties of quasinematic layers of dispersion particles and double-stranded DNA molecules in their content are taken into account in the course of developing fundamental background of the liquid-crystalline approach to the DNA structural nanotechnology. According to different versions of this approach, which is based on intraparticle gelation of cholesteric liquid-crystalline dispersions, spatial structures (DNA nanoconstructions, "rigid" DNA particles) with unique properties, are created. By means of atomic force microscopy images of "rigid" DNA particles of different type are registered. Specific properties of metallic nanoparticles (in particular, gold nanoparticles) are considered while developing the other approach to DNA structural nanotechnology, which provides the basis for "metallized" DNA nanoconstructions. PMID:25508888

  14. [Structural nucleic acid nanotechnology: liquid-crystalline approach].

    PubMed

    Evdokimov, Iu M; Salianov, V I; Kats, E I; Skuridin, S G

    2013-01-01

    The properties of the particles of cholesteric liquid-crystalline dispersions formed by double-stranded DNA molecules obtained as a result of phase exclusion of these molecules from water-salt polymer-containing solutions are briefly described. Physicochemical properties of quasinematic layers of dispersion particles and double-stranded DNA molecules in their content are taken into account in the course of developing fundamental background of the liquid-crystalline approach to the DNA structural nanotechnology. According to different versions of this approach, which is based on intraparticle gelation of cholesteric liquid-crystalline dispersions, spatial structures (DNA nanoconstructions, "rigid" DNA particles) with unique properties, are created. By means of atomic force microscopy images of "rigid" DNA particles of different type are registered. Specific properties of metallic nanoparticles (in particular, gold nanoparticles) are considered while developing the other approach to DNA structural nanotechnology, which provides the basis for "metallized" DNA nanoconstructions. PMID:25486757

  15. High magnetic field processing of liquid crystalline polymers

    DOEpatents

    Smith, Mark E.; Benicewicz, Brian C.; Douglas, Elliot P.

    1998-01-01

    A process of forming bulk articles of oriented liquid crystalline thermoset material, the material characterized as having an enhanced tensile modulus parallel to orientation of an applied magnetic field of at least 25 percent greater than said material processed in the absence of a magnetic field, by curing a liquid crystalline thermoset precursor within a high strength magnetic field of greater than about 2 Tesla, is provided, together with a resultant bulk article of a liquid crystalline thermoset material, said material processed in a high strength magnetic field whereby said material is characterized as having a tensile modulus parallel to orientation of said field of at least 25 percent greater than said material processed in the absence of a magnetic field.

  16. High magnetic field processing of liquid crystalline polymers

    DOEpatents

    Smith, M.E.; Benicewicz, B.C.; Douglas, E.P.

    1998-11-24

    A process of forming bulk articles of oriented liquid crystalline thermoset material, the material characterized as having an enhanced tensile modulus parallel to orientation of an applied magnetic field of at least 25 percent greater than said material processed in the absence of a magnetic field, by curing a liquid crystalline thermoset precursor within a high strength magnetic field of greater than about 2 Tesla, is provided, together with a resultant bulk article of a liquid crystalline thermoset material, said material processed in a high strength magnetic field whereby said material is characterized as having a tensile modulus parallel to orientation of said field of at least 25 percent greater than said material processed in the absence of a magnetic field.

  17. Liquid crystalline thermotropic and lyotropic nanohybrids

    NASA Astrophysics Data System (ADS)

    Saliba, Sarmenio; Mingotaud, Christophe; Kahn, Myrtil L.; Marty, Jean-Daniel

    2013-07-01

    This review is meant to give the reader an insight into hybrids incorporating different types of nanoparticles, e.g. metallic or metal oxides, within different types of lyotropic and thermotropic liquid crystals, from relatively small calamitic molecules to the larger discotics and polymers. In particular, this review highlights the importance of nanoparticle-liquid crystal interactions in accessing hybrid materials that exhibit synergetic properties.

  18. Liquid Crystalline Networks Composed of Pentagonal, Square, and Triangular Cylinders

    NASA Astrophysics Data System (ADS)

    Chen, Bin; Zeng, Xiangbing; Baumeister, Ute; Ungar, Goran; Tschierske, Carsten

    2005-01-01

    T-shaped molecules are designed in such a way that they self-organize into nanoscale liquid crystalline honeycombs based on polygons with any chosen number of sides. One of the phases reported here is a periodic organization of identical pentagonal cylinders; the other one is a structure composed of square-shaped and triangular cylinders in the ratio 2:1. These two different packing motifs represent duals of the same topological class. The generalization of the concept applied here allows the prediction of a whole range of unusual complex liquid crystalline phases.

  19. A liquid crystalline chirality balance for vapours

    NASA Astrophysics Data System (ADS)

    Ohzono, Takuya; Yamamoto, Takahiro; Fukuda, Jun-Ichi

    2014-04-01

    Chiral discrimination of vapours plays an important role in olfactory perception of biological systems and its realization by artificial sensors has been an intriguing challenge. Here, we report a simple method that tangibly visualizes the chirality of a diverse variety of molecules dissolved from vapours with high sensitivity, by making use of a structural change in a periodic microstructure of a nematic liquid crystal confined in open microchannels. This microstructure is accompanied by a topological line defect of a zigzag form with equal lengths of ‘zig’ and ‘zag.’ We find that a tiny amount of vapour of chiral molecules injected onto the liquid crystal induces the imbalance of ‘zig’ and ‘zag’ depending on its enantiomeric excess within a few seconds. Our liquid-crystal-based ‘chirality balance’ offers a simple, quick and versatile chirality-sensing/-screening method for gas-phase analysis (for example, for odours, environmental chemicals or drugs).

  20. Plateau borders of smectic liquid crystalline films

    NASA Astrophysics Data System (ADS)

    Trittel, Torsten; Aldred, Ruth; Stannarius, Ralf

    2011-06-01

    We investigate the geometrical properties of Plateau borders in an arrangement of connected smectic A free standing films. The geometry is chosen such that a circular Plateau border surrounds a planar smectic film and connects it with two smectic catenoids. It is demonstrated that, similar to soap films, the smectic film geometry can be described by a negative line tension of the circular contact region. Thus, the equilibrium angle between the films depends upon the liquid content in this region, and with increasing liquid content, deviations from Plateau's rule are observed. The experimental results are qualitatively comparable to soap films. A possible origin of slight quantitative differences is discussed.

  1. Crystalline, liquid crystalline, and isotropic phases of sodium deoxycholate in water

    SciTech Connect

    Su, Ziyang; Luthra, Suman; Krzyzaniak, Joseph F.; Agra-Kooijman, Dena M.; Kumar, Satyendra; Byrn, Stephen R.; Shalaev, Evgenyi Y.

    2012-09-06

    Sodium deoxycholate (NaDC) is an important example of bile salts, representing systems with complex phase behavior involving both crystalline and mesophase structures. In this study, properties of NaDC-water mixtures were evaluated as a function of composition and temperature via X-ray diffraction with synchrotron (sXRD) and laboratory radiation sources, water sorption, polarized light, hot-stage microscopy, and freezing-point osmometry. Several phases were detected depending on the composition and temperature, including isotropic solution phase, liquid crystalline (LC) phase, crystalline hydrate, and ice. The LC phase was identified as hexagonal structure by sXRD, with up to 14 high-order reflections detected. The crystalline phase was found to be nonstoichiometric hydrate, based on XRD and water sorption data. The phase diagram of NaDC-water system has been refined based on both results of this study and other reports in literature.

  2. [Circular dichroism of DNA liquid-crystalline dispersion particles].

    PubMed

    Semenov, S V; Yevdokimov, Yu M

    2015-01-01

    The optical activity of DNA liquid-crystalline dispersions is being investigated based on a theory for absorption of electromagnetic waves by large molecular aggregates. The impact on the dispersions-optical properties, exerted by the interaction between the complexes of nucleic acid molecules and nanoparticles, is being considered. PMID:26016021

  3. Entropy Calculations for a Supercooled Liquid Crystalline Blue Phase

    ERIC Educational Resources Information Center

    Singh, U.

    2007-01-01

    We observed, using polarized light microscopy, the supercooling of the blue phase (BPI) of cholesteryl proprionate and measured the corresponding liquid crystalline phase transition temperatures. From these temperatures and additional published data we have provided, for the benefit of undergraduate physics students, a nontraditional example…

  4. 21 CFR 524.2620 - Liquid crystalline trypsin, Peru balsam, castor oil.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 6 2014-04-01 2014-04-01 false Liquid crystalline trypsin, Peru balsam, castor... NEW ANIMAL DRUGS § 524.2620 Liquid crystalline trypsin, Peru balsam, castor oil. (a) Specifications—(1) Each gram of liquid or aerosol contains 0.12 milligram of crystalline trypsin, 87.0 milligrams of...

  5. Tribological properties of paraffin oil doped with liquid crystalline mezogenes

    NASA Astrophysics Data System (ADS)

    Ważyńska, B.; Okowiak, J.; Kołacz, S.; Małysa, A.

    2008-09-01

    The paper presents description and analysis of the results obtained in the investigation performed on a disc-ball tribotester T-11. Samples of 100Cr6 steel were tested, while as lubricant the mixtures of paraffin oil, with addition of 0.5%, 1%, and 2% of liquid crystalline compounds, from two homologous series defined with nOBCAB and nCBB symbols, were used. The friction force and wear of a sample and a counter-sample were measured. The improvement in tribological and anti-wear properties was found for all mixtures in relation to paraffin oil. The best tribological properties and the best wearability were obtained for mixtures with a compound 8CBB. This compound differs from the others in formation of different liquid crystalline phases.

  6. Birefringence and DNA Condensation of Liquid Crystalline Chromosomes ▿

    PubMed Central

    Chow, Man H.; Yan, Kosmo T. H.; Bennett, Michael J.; Wong, Joseph T. Y.

    2010-01-01

    DNA can self-assemble in vitro into several liquid crystalline phases at high concentrations. The largest known genomes are encoded by the cholesteric liquid crystalline chromosomes (LCCs) of the dinoflagellates, a diverse group of protists related to the malarial parasites. Very little is known about how the liquid crystalline packaging strategy is employed to organize these genomes, the largest among living eukaryotes—up to 80 times the size of the human genome. Comparative measurements using a semiautomatic polarizing microscope demonstrated that there is a large variation in the birefringence, an optical property of anisotropic materials, of the chromosomes from different dinoflagellate species, despite their apparently similar ultrastructural patterns of bands and arches. There is a large variation in the chromosomal arrangements in the nuclei and individual karyotypes. Our data suggest that both macroscopic and ultrastructural arrangements affect the apparent birefringence of the liquid crystalline chromosomes. Positive correlations are demonstrated for the first time between the level of absolute retardance and both the DNA content and the observed helical pitch measured from transmission electron microscopy (TEM) photomicrographs. Experiments that induced disassembly of the chromosomes revealed multiple orders of organization in the dinoflagellate chromosomes. With the low protein-to-DNA ratio, we propose that a highly regulated use of entropy-driven force must be involved in the assembly of these LCCs. Knowledge of the mechanism of packaging and arranging these largest known DNAs into different shapes and different formats in the nuclei would be of great value in the use of DNA as nanostructural material. PMID:20400466

  7. Originating super-strong liquid crystalline polymers (SSLCPs). Final report

    SciTech Connect

    1994-12-31

    The work at the University of North Carolina at Chapel Hill focused on the experimental characterization of ring mobility in labeled polyaramides with deuterium Nuclear Magnetic Resonance (NMR). Los Alamos National Laboratory prepared the deuterium-labeled analogs of Super-Strong (SS), Liquid Crystalline Polymers (LCPs) and oligomers. These materials were studied to ascertain the influence of substituent size (at the diacid moiety) on the mobility of the labeled diamine. The results are currently being finalized for publication.

  8. The effect of graphene on liquid-crystalline blue phases

    NASA Astrophysics Data System (ADS)

    Lavrič, M.; Tzitzios, V.; Kralj, S.; Cordoyiannis, G.; Lelidis, I.; Nounesis, G.; Georgakilas, V.; Amenitsch, H.; Zidanšek, A.; Kutnjak, Z.

    2013-09-01

    The stabilization of liquid-crystalline blue phases is recently attracting considerable interest because of the envisioned applications in fast optical displays and tunable photonic crystals. We report on the effect of surface-functionalized graphene nanosheets on the blue phase range of a chiral liquid crystal. Calorimetric and optical measurements, reproducible on heating and cooling, demonstrate that the resulting soft nanocomposite exhibits an increased blue phase temperature stability range for a minute concentration of dispersed graphene. The impact is stronger on the ordered, cubic structured blue phase I. These findings suggest that anisotropic nanoparticles may be of great usefulness for stabilizing blue phases.

  9. Effects of molecular architecture on liquid crystalline thermosets

    NASA Astrophysics Data System (ADS)

    Gavrin, Arthur John

    This work incorporates three studies on the influence of molecular architecture on liquid crystalline phase transitions, physical transformations, and thermal stability for acetylene functionalized liquid crystalline thermosets (LCTs). The first study focuses on synthesis and liquid crystalline phase characterization of acetylene functionalized LCTs. The second examines architecture's influence on liquid crystalline phase transitions and physical transformations that occur during isothermal curing of LCTs. The third deals with architecture and the thermal stability of the uncured and fully cured thermosets. Two homologous series of LCT monomers, differing in mesogen length, were synthesized: with monomers composed of an aromatic mesogen based on either hydroquinone (nHQ) or biphenol (nBP), end-capped with acetylene functional groups, and terminated with flexible alkyl chains of 3 to 8 carbons in length. The nHQ monomers melt and clear at lower temperatures than the nBP series. The monomers were characterized with differential scanning calorimetry (DSC), dynamic thermogravimetric analysis (TGA), and cross-polarized optical microscopy (POM). The monomers displayed liquid crystalline behavior similar to that of a related small molecule liquid crystal series. A related fully aromatic monomer was also synthesized (PEBP). It possesses higher melting and clearing temperatures, displays only a nematic phase, and has higher thermal stability. The monomers of the two series were isothermally cured in a rheometer. Gelation times were determined from the shear moduli crossover point. Both series display an odd-even effect for gel times, even though the entire nHQ series is isotropic during the isothermal cure. This is the first time such behavior has been seen for an unordered system. From POM, the monomers lose their molecular ordering during initial chain extension, but may regain some order at later extents of curing if at low enough temperatures. TGA and isothermal

  10. Self-assembly Morphology and Crystallinity Control of Di-block Copolymer Inspired by Spider Silk

    NASA Astrophysics Data System (ADS)

    Huang, Wenwen; Krishnaji, Sreevidhya; Kaplan, David; Cebe, Peggy

    2012-02-01

    To obtain a fuller understanding of the origin of self-assembly behavior, and thus be able to control the morphology of biomaterials with well defined amino acid sequences for tissue regeneration and drug delivery, we created a family of synthetic silk-based block copolymers inspired by the genetic sequences found in spider dragline, HABn and HBAn (n=1,2,3,6), where B = hydrophilic block, A = hydrophobic block, and H is a histidine tag. We assessed the secondary structure of water cast films by Fourier transform infrared spectroscopy (FTIR). The crystallinity was determined by Fourier self-deconvolution of amide I spectra and confirmed by wide angle X-ray diffraction (WAXD). Results indicate that we can control the self-assembled morphology and the crystallinity by varying the block length, and a minimum of 3 A-blocks are required to form beta sheet crystalline regions in water-cast spider silk block copolymers. The morphology and crystallinity can also be tuned by annealing. Thermal properties of water cast films and films annealed at 120 C were determined by differential scanning calorimetry and thermogravimetry. The sample films were also treated with 1,1,1,3,3,3-Hexafluoro-2-propanol (HFIP) to obtain wholly amorphous samples, and crystallized by exposure to methanol. Using scanning and transmission electron microscopies, we observe that fibrillar networks and hollow micelles are formed in water cast and methanol cast samples, but not in samples cast from HFIP.

  11. Experimental Results on Electrorheology of Liquid Crystalline Polymer Solutions

    NASA Astrophysics Data System (ADS)

    Neves, S.; Leal, C. R.; Cidade, M. T.

    2008-07-01

    The electrorheological (ER) effect is known as the enhancement of the apparent viscosity upon application of an external electric field. Suspensions of polarizable particles in non-conducting solvents are the most studied electrorheological fluids, however, liquid crystalline materials may also present ER effect as long as their dielectric anisotropy is positive. In the liquid crystalline state of a positive dielectric anisotropy, the application of the electric field makes the director align perpendicular to the flow direction, thus increasing the apparent viscosity. In this work results of two liquid crystalline polymer solutions, acetoxypropylcellulose (APC) in dimethylacetamide (DMAc) and poly-γ-benzyl-L-glutamate (PBLG) in 1,4-dioxane, presenting opposite behavior upon application of the electric field, will be presented. APC/DMAc (negative dielectric anisotropy) presents a decrease of the apparent viscosity upon application of the electric field, as expected, while PBLG/1,4-dioxane (positive dielectric anisotropy) presents the opposite behavior. For this last solution we will present the shear flow curves for different electric fields in function of polymer molecular weight and solution concentration.

  12. Structural Formation Process of Microphase Separated Films with Liquid Crystalline Phase Transition

    NASA Astrophysics Data System (ADS)

    Komura, Motonori; Iyoda, Tomokazu

    2008-03-01

    Ordered nanostructures arising from the microphase separation of block copolymers have driven one to fabricate nanofunctional materials as fundamental technology of the coming electronic and photonic materials. Thin films of a series of newly designed amphiphilic block copolymer consisting of hydrophilic polyethylene oxide (PEO) and hydrophobic polymethacrylate with azobenzene-mesogen in side-chain (PMA(Az)) show highly ordered microphase separation with PEO cylinders perpendicularly oriented to the film surface. In the present report, we investigated a structural formation process of the microphase separated films by temperature controlled atomic force microscopy (AFM) and grazing incidence small angle X-ray scattering (GISAXS). These measurements revealed that homeotropic alignments of Az liquid crystalline layers predominated the cylinder orientation, which corresponded to a <110> direction of body centered cubic structure under annealing condition, in disagreement with cylinder orientation of order-order transition of traditional block copolymers.

  13. Computational analysis of ordering in non-liquid crystalline versus liquid crystalline materials with special reference to nBAC

    SciTech Connect

    Lakshmi Praveen, P.; Veera Bhadra Reddy, K.; Ajeetha, N.; Ojha, D. P.

    2009-12-15

    A computational analysis of ordering in non-liquid crystalline p-n-alkyl benzoic acid, having 1 (1BAC), 2 (2BAC) and 3(3BAC) carbon atoms in the alkyl chain has been carried out with respect to translatory and orientational motions, but detailed results are reported only for 3BAC. The evaluation of net atomic charges and dipole moments at each atomic center has been carried out using complete neglect differential overlap (CNDO/2) method. The modified Rayleigh-Schrodinger perturbation theory along with the multicentered-multipole expansion method has been employed to evaluate long-range interactions, while a '6-exp' potential function has been assumed for short-range interactions. On the basis of stacking, in-plane and terminal interaction energy calculations, all possible arrangements of a molecular pair have been considered. A comparative picture of molecular parameters, such as total energy, binding energy, and total dipole moment of 3BAC with higher homologous series liquid crystalline compounds having 4(4BAC), 5(5BAC), and 6(6BAC) alkyl chain carbon atoms, has been given. It is found that, if a suitable functional group is attached to 3BAC, so that the length to breadth ratio is increased, the molecule will show a change in the long-range order, the phase transition temperature and other liquid crystalline properties.

  14. Non-lamellar lipid liquid crystalline structures at interfaces.

    PubMed

    Chang, Debby P; Barauskas, Justas; Dabkowska, Aleksandra P; Wadsäter, Maria; Tiberg, Fredrik; Nylander, Tommy

    2015-08-01

    The self-assembly of lipids leads to the formation of a rich variety of nano-structures, not only restricted to lipid bilayers, but also encompassing non-lamellar liquid crystalline structures, such as cubic, hexagonal, and sponge phases. These non-lamellar phases have been increasingly recognized as important for living systems, both in terms of providing compartmentalization and as regulators of biological activity. Consequently, they are of great interest for their potential as delivery systems in pharmaceutical, food and cosmetic applications. The compartmentalizing nature of these phases features mono- or bicontinuous networks of both hydrophilic and hydrophobic domains. To utilize these non-lamellar liquid crystalline structures in biomedical devices for analyses and drug delivery, it is crucial to understand how they interact with and respond to different types of interfaces. Such non-lamellar interfacial layers can be used to entrap functional biomolecules that respond to lipid curvature as well as the confinement. It is also important to understand the structural changes of deposited lipid in relation to the corresponding bulk dispersions. They can be controlled by changing the lipid composition or by introducing components that can alter the curvature or by deposition on nano-structured surface, e.g. vertical nano-wire arrays. Progress in the area of liquid crystalline lipid based nanoparticles opens up new possibilities for the preparation of well-defined surface films with well-defined nano-structures. This review will focus on recent progress in the formation of non-lamellar dispersions and their interfacial properties at the solid/liquid and biologically relevant interfaces. PMID:25435157

  15. Properties of ER Fluids Comprised of Liquid Crystalline Polymers

    NASA Astrophysics Data System (ADS)

    Inoue, Akio; Ide, Yoichiroh; Maniwa, Shyunji; Yamada, Hiroyuki; Oda, Hiroji

    Side-chain liquid crystalline polysiloxanes (LCS) diluted with solvents show a large increase in viscosity and a newtonian flow under an electric field. Two types of solvent-diluted LCSs, A and B, are presented and their properties are described in this paper. Type A shows a large temperature-dependent ER effect a quick response of msec. order to an electric field and a dynamic behavior similar to that of a low molecular weight liquid crystal. Type B shows a stable ER effect throughout a wide range of temperatures up to 150°C, a two-step response of shear stress curve upon application of DC electric field and a micron-sized droplets structure which deforms with the electric field. The generation mechanisms of ER effect on the two types were discussed with the data of dynamic and morphological changes, referring those on a low molecular liquid crystal and a particle dispersion type ER fluid.

  16. Electrorheology of miscible blended liquid crystalline polymer: A dielectric property approach

    NASA Astrophysics Data System (ADS)

    Kawai, A.; Ide, Y.; Inoue, A.; Ikazaki, F.

    1998-09-01

    A miscible blended liquid crystalline polymer prepared by Asahi Chemical Industry Co. Ltd. was used to study the effect of temperature on electrorheology. The electrorheological (ER) effect was measured using a rotational viscometer at temperatures between 20 and 60 °C. The polymer showed no yield shear stress under an external electric field, and its ER effect increased with decreasing temperature. We explain the electrorheology of the miscible blended liquid crystalline polymer using our ER mechanism, based on Block's model. In our mechanism, for an ER fluid to have an appreciable ER effect, its relaxation frequency must be between 100 and 105 Hz and the difference in the dielectric constant must be large below and above the relaxation frequency. The relaxation frequency of the miscible blended liquid crystalline polymer increased with increasing temperature, and the difference in its dielectric constant below and above the relaxation frequency increased with decreasing temperature. These dielectric properties are explained by the Debye theory and account for the electrorheology of the polymer.

  17. Structure of nematic liquid crystalline elastomers under uniaxial deformation

    SciTech Connect

    Zhang Fan; Heiney, Paul A.; Srinivasan, Amritha; Naciri, Jawad; Ratna, Banahalli

    2006-02-15

    We have used in situ x-ray diffraction and calorimetry to study liquid crystalline elastomers prepared using a one-step photopolymerization method. We used suspended weights to stretch free-standing crystalline elastomer films. With the mechanical stress parallel to the initial director, we observed a gradual nematic to isotropic transition with increasing temperature. The thermal evolution of the nematic order parameter on cooling, together with the observation of isotropic-nematic coexistence over a broad temperature range, suggests that the heterogeneity in the samples introduces a distribution of transition temperatures. With the mechanical stress perpendicular to the initial director, we observed both uniform director rotation and stripe formation, depending on the details of sample preparation.

  18. A Molecular View of Liquid Crystalline Elastomers and Gels

    NASA Astrophysics Data System (ADS)

    de Pablo, Juan

    2011-03-01

    A combination of Monte Carlo and molecular dynamics simulations is used to examine the order-disorder transitions that arise in model liquid crystalline elastomers and colloidal gels as a function of concentration and strain, respectively. Two models are considered. In the first, a lattice model is used to represent a colloidal gel of nematogens and nanoparticles. In the second, a cross-linked elastomer of Gay-Berne mesogens is adopted to examine the order-disroder transition that arises as a function of strain. The results of simulations are compared to those of recent experiments for these two classes of systems.

  19. Polymerization in the liquid crystalline state of vinyl ether monomers

    SciTech Connect

    Andersson, H.; Jonsson, H.; Gedde, U.W.; Hult, A.

    1993-12-31

    Liquid crystalline phenylbenzoate vinyl ether was polymerized cationically in both anisotropic and isotropic monomeric melts, using photochemical initiation by onium salts. High molecular mass polymers with a narrow molecular mass distribution (around 2) were produced by cationic polymerization at high temperatures ({<=}{degrees}C). The initial state of the monomer, nematic or isotropic, did not affect neither molecular mass, molecular mass distribution, nor polymerization rate. {sup 13}C-NMR studies show that the polymer formed is atactic. Ordered 30-50 {mu}m films were produced by polymerization of mesogenic vinyl ether monomers oriented in the nematic and smectic phase.

  20. Blends of thermoplastic and elastomeric matrices with liquid crystalline polymers

    SciTech Connect

    Roggero, A.; Pedretti, U.; La Mantia, F.P.

    1995-12-01

    Liquid crystalline polymers (LCPs) present a unique balance of properties and, when added to thermoplastic (TP) or elastomeric (EL) matrices, can impart to the relevant blends specific properties that can be utilized for specific applications. As regards TP/LCP blends, the proclivity of LCPs to form fibrous structures and their low melt viscositiy allowed to obtain blends reinforced and easier to process than the pure TPs: particularly, depending on the LCP-TP structures and on the processing parameters, materials with improved processability, high modulus, enhanced impact strength and creeping resistance were obtained. As regards EL/LCP blends, that based on fluoroelastomers were in depth investigated and offered outstanding properties.

  1. Optical pendulum generator based on photomechanical liquid-crystalline actuators.

    PubMed

    Tang, Rong; Liu, Ziyi; Xu, Dandan; Liu, Jian; Yu, Li; Yu, Haifeng

    2015-04-29

    For converting light energy into electricity, an optical pendulum generator was designed by combining photomechanical movement of liquid-crystalline actuator (LCA) with Faraday's law of electromagnetic induction. Bilayer cantilever actuators were first fabricated with LDPE and LCA. Their photomechanical movement drove the attached copper coils to cut magnetic line of force generating electricity. The output electricity was proportional to the changing rate of the magnetic flux, which was greatly influenced by light intensity, film thickness, and sample size. Continuous electrical output was also achieved. This simple strategy may expand applications of photoactive materials in the capture and storage of light energy. PMID:25875214

  2. Phase behavior and local structure of liquid crystalline polymers

    NASA Astrophysics Data System (ADS)

    Fynewever, Herb

    In this work we use a combination of theory and computer simulation to study the phase behavior of liquid crystalline polymers and the local structure of polymer melts. We review experimental and simulation evidence which shows that long and stiff molecules form orientationally ordered phases at packing fractions intermediate between the liquid and the solid. With the aid of a two-molecule simulation, we are able to apply Onsager's theory [Ann. N. Y. Acad. Sci. 51, 627 (1949)] for liquid crystal formation to flexible molecules without any additional approximations. Our results have a quantitative advantage over other theories in comparison with computer simulation data such as for the liquid-liquid crystal phase diagram. We also study the local structure of polymer melts using a two-molecule simulation to apply the density functional theories of Donley, Curro, and McCoy [J. Chem. Phys. 101 , 3205 (1994)1; and Yethiraj and Woodward [J. Chem. Phys 102 , 5499 (1995)]. The accuracy of these methods rivals that of integral equation theories in their predictions of local order. Further, the two-molecule simulation facilitates a more direct calculation of the equation of state via the monitoring of orientational correlations.

  3. Liquid water in the domain of cubic crystalline ice Ic

    NASA Technical Reports Server (NTRS)

    Jenniskens, P.; Banham, S. F.; Blake, D. F.; McCoustra, M. R.

    1997-01-01

    Vapor-deposited amorphous water ice when warmed above the glass transition temperature (120-140 K), is a viscous liquid which exhibits a viscosity vs temperature relationship different from that of liquid water at room temperature. New studies of thin water ice films now demonstrate that viscous liquid water persists in the temperature range 140-210 K. where it coexists with cubic crystalline ice. The liquid character of amorphous water above the glass transition is demonstrated by (1) changes in the morphology of water ice films on a nonwetting surface observed in transmission electron microscopy (TEM) at around 175 K during slow warming, (2) changes in the binding energy of water molecules measured in temperature programmed desorption (TPD) studies, and (3) changes in the shape of the 3.07 micrometers absorption band observed in grazing angle reflection-absorption infrared spectroscopy (RAIRS) during annealing at high temperature. whereby the decreased roughness of the water surface is thought to cause changes in the selection rules for the excitation of O-H stretch vibrations. Because it is present over such a wide range of temperatures, we propose that this form of liquid water is a common material in nature. where it is expected to exist in the subsurface layers of comets and on the surfaces of some planets and satellites.

  4. Structure analysis methods for crystalline solids and supercooled liquids

    NASA Astrophysics Data System (ADS)

    Yu, Da-Qi; Chen, Min; Han, Xiu-Jun

    2005-11-01

    The three most widely used methods for analyzing atomic structures are evaluated by simulating crystalline solids and supercooled liquids. The local order parameter approach due to Volkov [Phys. Rev. E 66, 061401 (2002)] fails in randomly perturbed body-centered-cubic environments, while the pair analysis method behaves as an approximate approach depending on how the neighborhood is defined. As to the Voronoi analysis method, we improve the procedure of Brostow [Phys. Rev. B 57, 13448 (1998)] to eliminate distorted Voronoi faces and edges which originate from thermal vibrations and computational rounding errors. The improved procedure works robustly in face-centered-cubic, body-centered-cubic, and hexagonal close-packed environments. When the pair analysis technique and the Voronoi analysis method are applied to detect the microstructure and its evolution in supercooled liquids, qualitatively consistent results are attained.

  5. Liquid crystalline human recombinant collagen: the challenge and the opportunity.

    PubMed

    Yaari, Amit; Posen, Yehudit; Shoseyov, Oded

    2013-07-01

    Collagen is a key component of the extracellular matrix, and by far the most prominent constituent of all load-bearing tissues. Its abundance and self-assembly capacities render it a practical scaffold material for tissue repair and regeneration applications. However, some difficulties exist in artificially regenerating functional collagen structures to match native tissues and their respective performances. There are two major limitations of existing collagen-based scaffolds: The first one is poor mechanical performance, and the second one is the failure to closely mimic natural tissues as to provide the necessary topographic and mechanical cues required for cell propagation and differentiation. The complexity of inducing sufficient order and alignment stands at the base of the impediments to successful formation of artificial collagen scaffolds, which closely match native tissue strength and morphology. Recombinant human collagen produced in transgenic tobacco plants has the capacity of forming highly concentrated liquid crystalline dope that can be aligned by application of shear force. Leveraging shear alignment of liquid crystalline recombinant human collagen opens new possibilities toward obtaining scaffolds that may be able to provide the necessary mechanical support, while closely mimicking the molecular signals and mechanical cues displayed to natural cell milieu. Such scaffolds may prove advantageous in the development of improved medical devices in fields, such as ophthalmology, neurology, and orthopedics. PMID:23368756

  6. Textures in multiphase polymer-liquid crystalline materials

    NASA Astrophysics Data System (ADS)

    Das, Susanta Kumar; Rey, Alejandro D.

    2004-03-01

    Textures in multiphase polymer-liquid crystalline materials Susanta K. Das, Alejandro D. Rey Department of Chemical Engineering, McGill University, 3610 University Street, Montreal, Quebec, H3A 2B2 Canada. Email: alejandro.rey@mcgill.ca Abstract: A nonlocal kinetic model for phase separation in the presence of liquid crystalline order has been formulated, and solved using high performance numerical methods. The model takes into account couplings between phase separation, phase ordering, and texture formation. The phase separation-phase ordering coupling leads to orientation normal concentration gradients, and curvature in the isotropic phase leads to defect nucleation in the nematic phase. The phase separation and phase ordering process is characterized by simulating quenches into unstable and metastable regions of the phase diagram. Emerging two-dimensional morphologies include nematic emulsions and filled nematics. Droplets in nematic emulsions display the classical bipolar director field. The director field in filled nematics display a stable defect polygonal network. The local density of defects is proportional to the ambient curvature of the isotropic droplet phase, such that defects accumulate near smaller groups of droplets. Morphological pinning by texture elasticity is discussed.

  7. 21 CFR 524.2620 - Liquid crystalline trypsin, Peru balsam, castor oil.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 false Liquid crystalline trypsin, Peru balsam, castor... NEW ANIMAL DRUGS § 524.2620 Liquid crystalline trypsin, Peru balsam, castor oil. (a)(1) Specifications. The drug is a liquid for direct application or an aerosol preparation formulated so that each...

  8. 21 CFR 524.2620 - Liquid crystalline trypsin, Peru balsam, castor oil.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 false Liquid crystalline trypsin, Peru balsam, castor... NEW ANIMAL DRUGS § 524.2620 Liquid crystalline trypsin, Peru balsam, castor oil. (a)(1) Specifications. The drug is a liquid for direct application or an aerosol preparation formulated so that each...

  9. 21 CFR 524.2620 - Liquid crystalline trypsin, Peru balsam, castor oil.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 false Liquid crystalline trypsin, Peru balsam, castor... NEW ANIMAL DRUGS § 524.2620 Liquid crystalline trypsin, Peru balsam, castor oil. (a)(1) Specifications. The drug is a liquid for direct application or an aerosol preparation formulated so that each...

  10. Synthesis and characterization of liquid-crystalline supramolecular architecture by a combination of molecular recognition and polymerization reaction

    NASA Astrophysics Data System (ADS)

    Ahn, Cheol-Hee

    In nature, self-assembly with well defined shapes obtained from combinations of polymeric building blocks with complex architecture are abundant since they are responsible for the production of structural materials and for the generation of some of the most efficient mechanisms. One of the many roles liquid crystallinity plays in natural systems is in their self-assembly and organization. The assembly of these complex natural systems is largely under thermodynamic control which is manipulated by their liquid crystallinity. The goal of this thesis is to use Nature as a model for the development of new synthetic concepts and strategies in the field of polymer science. The two models selected are rod-like and icosahedral viruses. The strategy involved in this thesis requires the design of libraries of monodendritic building blocks with well defined flat tapered and conical shapes which self-assemble into cylindrical and respectively spherical shapes. By analogy with viruses these supermolecules will generated hexagonal columnar and spherical cubic thermotropic phases. These liquid crystalline phases allow the determination of their shape by X-ray diffraction and Scanning Force Microscopy. Libraries of flat tapered and conical monodendritic building blocks will be functionalized with polymerizable groups and polymerized to generate the first examples of polymers of cylindrical and spherical shapes with diameter and length, and diameter controlled at the nanoscale level. The organization of these dendritic monomers in a liquid crystalline assembly is also used to aggregate their polymerizable groups in a reactor of artificially enhanced concentration and restricted geometry during the polymerization process and therefore, generate a new approach to the control of polymerization. The resulting liquid crystallinity provides access to the thermodynamically controlled assembly and characterization of these newly developed polymers. With few exceptions, there is no precedent

  11. Synthesis, structure and phase behavior of liquid crystalline polyurethanes

    SciTech Connect

    Papadimitrakopoulos, F.

    1993-01-01

    This dissertation describes the synthesis, structure and phase behavior of polyurethanes based on the mesogenic biphenol 4,4'-bis (6-hydroxyhexoxy)biphenyl (BHHBP) and meta substituted tolylene/phenylene diisocynates. The structure-property relationships were determined as a function of hydrogen-bonding, the position of the methyl group in the tolylene diisocyanate moiety (TDI) and the biphenol moiety. The liquid crystalline phase (mesophase) and crystalline phase were investigated primarily with differential scanning calorimetry (DSC), wide angle X-ray scattering (WAXS) and infrared spectroscopy. The influence of H-bonding on the structure and phase behavior of 1,4-LCPU-6 was determined by the synthesis of high molecular weight N-Methyl2,4-LCPU-65, using a novel high temperature polymerization of a biscarbamoyl chloride with the BHHBP mesogenic diol. In contrast to the regular ([alpha], [omega]-hexane diol) based polyurethanes (PUs), BHHBP derived polyurethanes (LCPUs) crystallize rapidly from their melts. Hexafluoroisopropanol fast solvent-evaporation casting or rapid cooling from the melt resulted in thin films or bulk samples with a glassy mesophase morphology. During the subsequent heating scan, the mesophase to crystal transition occurs. Highly oriented fibers were obtained for the mesogenic polyurethanes. Atomistic molecular simulations coupled with X-ray intensity refinement allowed determination of the crystalline chain conformation and packing characteristics for the 2,6-LCPU-6 and 1,3-LCPU-6 (2,6-TDI and 1,3-Phenylene Diisocynate (1,3-PDI) derived LCPUs). On the basis of structural similarity and well resolved WAXS powder patterns similar analysis was extended to the regular polyurethanes as well (2,6-PU-6 and 1,3-PU-6). The good correlation polymers suggest that melting is primarily controlled by the dissociation of H-bonds in the ordered domains.

  12. Volume phase transitions of cholesteric liquid crystalline gels.

    PubMed

    Matsuyama, Akihiko

    2015-05-01

    We present a mean field theory to describe anisotropic deformations of a cholesteric elastomer without solvent molecules and a cholesteric liquid crystalline gel immersed in isotropic solvents at a thermal equilibrium state. Based on the neoclassical rubber theory of nematic elastomers, we derive an elastic energy and a twist distortion energy, which are important to determine the shape of a cholesteric elastomer (or gel). We demonstrate that when the elastic energy dominates in the free energy, the cholesteric elastomer causes a spontaneous compression in the pitch axis and elongates along the director on the plane perpendicular to the pitch axis. Our theory can qualitatively describe the experimental results of a cholesteric elastomer. We also predict the first-order volume phase transitions and anisotropic deformations of a gel at the cholesteric-isotropic phase transition temperature. Depending on a chirality of a gel, we find a prolate or oblate shape of cholesteric gels. PMID:25956120

  13. Volume phase transitions of cholesteric liquid crystalline gels

    SciTech Connect

    Matsuyama, Akihiko

    2015-05-07

    We present a mean field theory to describe anisotropic deformations of a cholesteric elastomer without solvent molecules and a cholesteric liquid crystalline gel immersed in isotropic solvents at a thermal equilibrium state. Based on the neoclassical rubber theory of nematic elastomers, we derive an elastic energy and a twist distortion energy, which are important to determine the shape of a cholesteric elastomer (or gel). We demonstrate that when the elastic energy dominates in the free energy, the cholesteric elastomer causes a spontaneous compression in the pitch axis and elongates along the director on the plane perpendicular to the pitch axis. Our theory can qualitatively describe the experimental results of a cholesteric elastomer. We also predict the first-order volume phase transitions and anisotropic deformations of a gel at the cholesteric-isotropic phase transition temperature. Depending on a chirality of a gel, we find a prolate or oblate shape of cholesteric gels.

  14. Orientational Phase Ordering in Disordered Liquid Crystalline Heteropolymers

    NASA Astrophysics Data System (ADS)

    Gutman, Lorin; Shakhnovich, Eugene I.

    2000-03-01

    Liquid-crystalline disordered heteropolymers (DLCPs) are studied by a novel creation-annihilation method and replica field theory. The 0 disorder limit of theory is the non-perturbative (A. M. Gupta and S. F. Edwards J. Chem. Phys., 98, 1588, (1993)) result for long homopolymer chains. Sequence disorder, alignment propensity, stiffness and lyotropic effects on orientational phase ordering and coexistence width are studied numerically by unconstrained iteration of principal axis of segment orientational tensors; It is shown that sequence heterogeneity impacts strongly the density order/disorder threshold and the Maxwell construction shows a three fold increase in coexistence width compared with the homopolymer analogue. The non-equilibrium meta-stable domain scale, obtained by calculation of Doring free energy from field theory and nucleation theory is of the order of μ m, in agreement with recent experiments on DLCPs.

  15. Orientational and Domain Ordering in Disordered Liquid Crystalline Heteropolymers

    NASA Astrophysics Data System (ADS)

    Gutman, Lorin; Shakhnovich, Eugene

    2001-03-01

    Liquid-crystalline disordered heteropolymers (DLCPs) are studied by a novel creation-annihilation method and replica field theory. The 0 disorder limit of theory is the non-perturbative (A. M. Gupta and S. F. Edwards J. Chem. Phys., 98, 1588, (1993)) result for long homopolymer chains. Sequence disorder, alignment propensity, stiffness and lyotropic effects on orientational phase ordering and coexistence width are studied numerically by unconstrained iteration of principal axis of segment orientational tensors; It is shown that sequence heterogeneity impacts strongly the density order/disorder threshold and the Maxwell construction shows a three fold increase in coexistence width compared with the homopolymer analogue. The non-equilibrium meta-stable domain scale, obtained by calculation of Doring free energy from field theory and nucleation theory is of the order of μ m, in agreement with recent experiments on DLCPs.

  16. Volume phase transitions of cholesteric liquid crystalline gels

    NASA Astrophysics Data System (ADS)

    Matsuyama, Akihiko

    2015-05-01

    We present a mean field theory to describe anisotropic deformations of a cholesteric elastomer without solvent molecules and a cholesteric liquid crystalline gel immersed in isotropic solvents at a thermal equilibrium state. Based on the neoclassical rubber theory of nematic elastomers, we derive an elastic energy and a twist distortion energy, which are important to determine the shape of a cholesteric elastomer (or gel). We demonstrate that when the elastic energy dominates in the free energy, the cholesteric elastomer causes a spontaneous compression in the pitch axis and elongates along the director on the plane perpendicular to the pitch axis. Our theory can qualitatively describe the experimental results of a cholesteric elastomer. We also predict the first-order volume phase transitions and anisotropic deformations of a gel at the cholesteric-isotropic phase transition temperature. Depending on a chirality of a gel, we find a prolate or oblate shape of cholesteric gels.

  17. Isotropic and nematic liquid crystalline phases of adaptive rotaxanes

    NASA Astrophysics Data System (ADS)

    He, Hao; Sevick, Edith M.; Williams, David R. M.

    2016-03-01

    We describe the thermodynamics of a solution of rotaxanes which can change their length from a short state of length L to a long state of length qL in response to their surrounding environment. We call these rotaxanes "adaptive." We show that such a system can exhibit both isotropic and nematic liquid crystalline phases. The system shows several interesting kinds of behaviour. First we predict that the fraction of short-length rotaxanes increases linearly with concentration and is a maximum at the critical concentration that marks the isotropic to nematic transition. Second, the critical concentration shows a minimum at a certain value of q. Our model suggests that the effect of adaptive length changes is most dramatic at small q and where the long state is slightly favoured.

  18. Liquid crystalline state of some fatty acids and mixtures

    NASA Astrophysics Data System (ADS)

    Ghelmez, Mihaela A.; Honciuc, Maria; Piscureanu, Mihai C.

    1998-09-01

    The role of the fatty acids in the biological membrane structure and properties is partially known. They can exhibit a mesogenic feature and behavior in terms of the temperature, the presence of many acids of cholesterol, or other important substances for the metabolism, of external stimuli etc. We studied the arachidic, lauric, elaidic, arachidonic and butiric acids. The most important seems to be the arachidonic acid, a forerunner of phospholipids. This is an unsaturated fatty acid,with four double bounds. We found that it displayed liquid crystalline properties between 4-20 grades centrigrades; in mixture with other fatty acids or cholesterol, these properties change. The paper present considerations on the biological role of the fatty acids and mixtures, in interactions with some physical fields experimental results and some theoretical considerations.

  19. Dynamic-Mechanical Analysis of Monodomain Nematic Liquid Crystalline Elastomers

    NASA Astrophysics Data System (ADS)

    Hotta, Atsushi; Terentjev, Eugene

    2003-03-01

    Dynamic-mechanical analysis was performed in the glassy, nematic and isotropic states of several monodomain nematic liquid crystalline elastomers (LCE) which differ in their degrees of anisotropy and internal microstructure. It was found that the type of network crosslinker makes a significant difference in the equilibrium properties of these elastomers, in particular, in their effective anisotropy. In spite of these differences, the observed dynamic-mechanical behaviour was very similar. The fact that there is a consistently high and wide loss over the whole nematic region, where storage modulus G' behaves non-monotonically, is most likely an indicator of the fact that the dynamic-mechanical response is not linear. Master curves have been built between the glassy state and the nematic-isotropic phase transition, where the modulus reaches a low-level soft plateau. Above the nematic-isotropic transition temperature Tni, the modulus rises substantially, since internal relaxation is no longer able to reduce the elastic response - and further time-temperature superposition fails. The dynamics of these elastomers are dominated by power laws, which was confirmed by the successful procedure of the master curve inversion (time-frequency inversion) to describe the static stress relaxation. Interestingly, it was found that mechanical properties characterized by power laws (in time) of stress relaxation match very well with the dynamic properties, where power laws (in frequency) were also observed in the dynamic modulus in the appropriate range of temperatures. The work demonstrates the potential for the use of nematic liquid crystalline elastomers in many acoustic and vibration damping applications.

  20. 31 CFR 537.209 - Expenses of maintaining blocked property; liquidation of blocked account.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 31 Money and Finance:Treasury 3 2011-07-01 2011-07-01 false Expenses of maintaining blocked property; liquidation of blocked account. 537.209 Section 537.209 Money and Finance: Treasury Regulations Relating to Money and Finance (Continued) OFFICE OF FOREIGN ASSETS CONTROL, DEPARTMENT OF THE...

  1. 31 CFR 537.209 - Expenses of maintaining blocked property; liquidation of blocked account.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 31 Money and Finance: Treasury 3 2010-07-01 2010-07-01 false Expenses of maintaining blocked property; liquidation of blocked account. 537.209 Section 537.209 Money and Finance: Treasury Regulations Relating to Money and Finance (Continued) OFFICE OF FOREIGN ASSETS CONTROL, DEPARTMENT OF THE...

  2. Thermal Characterization of Thermotropic Nematic Liquid-Crystalline Elastomers

    NASA Astrophysics Data System (ADS)

    Thomas, David; Cardarelli, Matt; Sanchez-Ferrer, Antoni; Mbanga, Badel L.; Atherton, Timothy J.; Cebe, Peggy

    Nematic Liquid-Crystallline Elastomers (LCEs) are weakly crosslinked polymeric networks that exhibit rubber elasticity and liquid-crystalline orientational order due to the presence of mesogenic groups. Three end-on side-chain nematic LCEs were investigated using real-time synchrotron wide-angle X-ray scattering (WAXS), differential scanning calorimetry (DSC), and thermogravimetry (TG) to correlate thermal behavior with structural and chemical differences among them. The elastomers differed in crosslinking density and mesogen composition. Thermally reversible glass transition temperature, Tg, and nematic-to-isotropic transition temperature, Tni, were observed upon heating and cooling for all samples. By varying the heating rate, Tg0 and Tni0 were determined at zero heating rate. The temperature dependence of the orientational order parameter was determined from the anisotropic azimuthal angular distribution of the equatorial reflection seen during real-time WAXS experiments. Our results show that the choice of crosslinking unit, its shape, density, as well as the structure of co-monomers, all influence the temperature range over which the thermal transitions take place.

  3. Giant lateral electrostriction in ferroelectric liquid-crystalline elastomers

    NASA Astrophysics Data System (ADS)

    Lehmann, W.; Skupin, H.; Tolksdorf, C.; Gebhard, E.; Zentel, R.; Krüger, P.; Lösche, M.; Kremer, F.

    2001-03-01

    Mechanisms for converting electrical energy into mechanical energy are essential for the design of nanoscale transducers, sensors, actuators, motors, pumps, artificial muscles, and medical microrobots. Nanometre-scale actuation has to date been mainly achieved by using the (linear) piezoelectric effect in certain classes of crystals (for example, quartz), and `smart' ceramics such as lead zirconate titanate. But the strains achievable in these materials are small-less than 0.1 per cent-so several alternative materials and approaches have been considered. These include grafted polyglutamates (which have a performance comparable to quartz), silicone elastomers (passive material-the constriction results from the Coulomb attraction of the capacitor electrodes between which the material is sandwiched) and carbon nanotubes (which are slow). High and fast strains of up to 4 per cent within an electric field of 150MVm-1 have been achieved by electrostriction (this means that the strain is proportional to the square of the applied electric field) in an electron-irradiated poly(vinylidene fluoride-trifluoroethylene) copolymer. Here we report a material that shows a further increase in electrostriction by two orders of magnitude: ultrathin (less than 100nanometres) ferroelectric liquid-crystalline elastomer films that exhibit 4 per cent strain at only 1.5 MVm-1. This giant electrostriction was obtained by combining the properties of ferroelectric liquid crystals with those of a polymer network. We expect that these results, which can be completely understood on a molecular level, will open new perspectives for applications.

  4. "Liquid Knife" to Fabricate Patterning Single-Crystalline Perovskite Microplates toward High-Performance Laser Arrays.

    PubMed

    Feng, Jiangang; Yan, Xiaoxu; Zhang, Yifan; Wang, Xuedong; Wu, Yuchen; Su, Bin; Fu, Hongbin; Jiang, Lei

    2016-05-01

    A facile and effective "liquid knife" is created by controlling the dewetting process of the liquid precursor, yielding patterning single-crystalline perovskite microplates with uniform size, precise positioning, high quality, and low lasing thresholds. The sizes and location of single-crystalline perovskite are controllable, leading to mode-tunable lasing emission and patterned lasers. PMID:27000628

  5. Theory of microphase separation on side-chain liquid-crystalline polymers with flexible spacers.

    PubMed

    Hernández-Jiménez, M; Westfahl, H

    2007-05-01

    We model a melt of monodisperse side-chain liquid-crystalline polymers as a melt of comb copolymers in which the side groups are rod-coil diblock copolymers. We consider both excluded-volume and Maier-Saupe interactions. The first acts among any pair of segments while the latter acts only between rods. Using a free-energy functional calculated from this microscopic model, we study the spinodal stability of the isotropic phase against density and orientational fluctuations. The phase diagram obtained in this way predicts nematic and smectic instabilities as well as the existence of microphases or phases with modulated wave vector but without nematic ordering. Such microphases are the result of the competition between the incompatibility among the blocks and the connectivity constraints imposed by the spacer and the backbone. Also the effects of the polymerization degree and structural conformation of the monomeric units on the phase behavior of the side-chain liquid-crystalline polymers are studied. PMID:17541501

  6. Ion Transport in Nanostructured Block Copolymer/Ionic Liquid Membranes

    NASA Astrophysics Data System (ADS)

    Hoarfrost, Megan Lane

    Incorporating an ionic liquid into one block copolymer microphase provides a platform for combining the outstanding electrochemical properties of ionic liquids with a number of favorable attributes provided by block copolymers. In particular, block copolymers thermodynamically self-assemble into well-ordered nanostructures, which can be engineered to provide a durable mechanical scaffold and template the ionic liquid into continuous ion-conducting nanochannels. Understanding how the addition of an ionic liquid affects the thermodynamic self-assembly of block copolymers, and how the confinement of ionic liquids to block copolymer nanodomains affects their ion-conducting properties is essential for predictable structure-property control. The lyotropic phase behavior of block copolymer/ionic liquid mixtures is shown to be reminiscent of mixtures of block copolymers with selective molecular solvents. A variety of ordered microstructures corresponding to lamellae, hexagonally close-packed cylinders, body-centered cubic, and face-centered cubic oriented micelles are observed in a model system composed of mixtures of imidazolium bis(trifluoromethylsulfonyl)imide ([Im][TFSI]) and poly(styrene- b-2-vinyl pyridine) (PS-b-P2VP). In contrast to block copolymer/molecular solvent mixtures, the interfacial area occupied by each PS-b-P2VP chain decreases upon the addition of [Im][TFSI], indicating a considerable increase in the effective segregation strength of the PS-b-P2VP copolymer with ionic liquid addition. The relationship between membrane structure and ionic conductivity is illuminated through the development of scaling relationships that describe the ionic conductivity of block copolymer/ionic liquid mixtures as a function of membrane composition and temperature. It is shown that the dominant variable influencing conductivity is the overall volume fraction of ionic liquid in the mixture, which means there

  7. Observations on the development of the crystalline bacterial biofilms that encrust and block Foley catheters.

    PubMed

    Stickler, D J; Morgan, S D

    2008-08-01

    The care of many patients undergoing long-term bladder catheterisation is complicated when the flow of urine through the catheter is blocked by encrustation. The problem results from infection by urease-producing bacteria, especially Proteus mirabilis, and the subsequent formation of crystalline biofilms on the catheter. The aim of this study was to discover how P. mirabilis initiates the development of these crystalline biofilms. The early stages in the formation of the biofilms were observed on a range of Foley catheters in a laboratory model of the catheterised bladder. Scanning electron micrographs revealed that when all-silicone, silicone-coated latex, hydrogel-coated latex, hydrogel/silver-coated latex and nitrofurazone silicone catheters were inserted into bladder models containing P. mirabilis and alkaline urine, their surfaces were rapidly coated with a microcrystalline foundation layer. X-ray microanalysis showed that this material was composed of calcium phosphate. Bacterial colonisation of the foundation layer followed and by 18h the catheters were encrusted by densely populated crystalline P. mirabilis biofilms. These observations have important implications for the development of encrustation-resistant catheters. In the case of silver catheters for example, bacterial cells can attach to the crystalline foundation layer and continue to grow, protected from contact with the underlying silver. If antimicrobials are to be incorporated into catheters to prevent encrustation, it is important that they diffuse into the urine and prevent the rise in pH that triggers crystal formation. PMID:18550219

  8. Liquid-Nitrogen Test for Blocked Tubes

    NASA Technical Reports Server (NTRS)

    Wagner, W. R.

    1984-01-01

    Nondestructive test identifies obstructed tube in array of parallel tubes. Trickle of liquid nitrogen allowed to flow through tube array until array accumulates substantial formation of frost from moisture in air. Flow stopped and warm air introduced into inlet manifold to heat tubes in array. Tubes still frosted after others defrosted identified as obstructed tubes. Applications include inspection of flow systems having parallel legs.

  9. Molecular dynamics simulation studies of liquid crystalline materials

    NASA Astrophysics Data System (ADS)

    Tian, Pu

    Molecular dynamics (MD) simulation studies of the phase behavior, the response to an applied field of nematic liquid crystalline (LC) materials and interactions of nanoparticles in isotropic mesogenic materials are presented in this work. Molecular models used include the rigid bead-necklace model and soft spherocylinders. Free energy calculations applying thermodynamic integration and the Gibbs-Duhem integration method were used to establish the (T, P) phase diagram of the repulsive bead-necklace model, subsequently the Gibbs-Duhem integration method was further utilized to investigate the influence of attractive interactions on the phase behavior of the bead-necklace model. Analysis of order and thermodynamics of LC phase transitions (Isotropic-Nematic transition and Nematic-Smectic A transition) demonstrate that this simple model can capture the basic physics of liquid crystalline phases, and good agreement with experimental results is obtained. Further addition of chemical details to this multiple interaction sites model is much easier than to the idealized models (Gay-Berne, Spherocylinders) while the computation cost increase with respect to these idealized models is minimal. With a mean field representation of field-molecules interaction, MD simulation studies of the switching behavior of nematic LC, which is the basis of many LC devices, were performed. The switching mechanisms were explained in terms of the compromise between the elastic energy and field-molecules interactions. Qualitative agreement with experiments confirmed the validity of the mean field approximation. Finally, using the standard umbrella sampling technique and MD simulations, the potential of mean force between two nanoparticles in solvent of spherocylinders is calculated. It is found that while dispersed nanoparticles will delay the Isotropic-Nematics transition to higher density (lower temperature), they can induce local ordering fluctuations (within a few molecular lengths of the

  10. Identification of crystalline elastic anisotropy in PZT ceramics from in-situ blocking stress measurements

    SciTech Connect

    Daniel, L.; Hall, D. A.; Withers, P. J.; Webber, K. G.; King, A.

    2014-05-07

    High energy x-ray diffraction measurements of lattice strains were performed on a rhombohedral Lead Zirconate Titanate ceramic (PZT 55-45) under combinations of applied electric field and compressive stress. These measurements allow the construction of blocking stress curves for different sets of crystallographic orientations which reflect the single crystal elastic anisotropy. A micro-mechanical interpretation of the results is then proposed. Assuming cubic symmetry for the crystalline elastic stiffness tensor and isotropy for the macroscopic elastic properties, the elastic properties of the single crystal are extracted from the measured data. An anisotropy ratio close to 0.3 is found (compared to 1 for isotropic materials). The high level of anisotropy found in this work suggests that crystalline elastic anisotropy should not be neglected in the modelling of ferroelectric materials.

  11. [Examination of liquid crystalline gel systems containing chlorhexidine on the structure and the drug release].

    PubMed

    Farkas, E

    2001-10-01

    The aim of the thesis was to examine liquid crystalline gel systems as novel, locally applied drug delivery systems. For developing liquid crystalline vehicle, different ratio of Synperonic A7--water mixtures was prepared. Chlorhexidine, chlorhexidine acetate and chlorhexidine gluconate were used as model drugs. Liquid crystalline structure, drug release and drug release kinetic of the samples were studied at increasing surfactant concentration and the effect of the different drugs on the physicochemical properties of the samples and on the membrane transport was examined. For the analysis of the prepared liquid crystalline systems polarising microscopy, rheology test, differential scanning calorimetry, small-angle neutron scattering and transmission electron microscopy were carried out. The drug release and membrane transport experiments were performed by Franz type vertical diffusion cell and Sartorius Resorptionsmodell apparatus. According to our results liquid crystalline vehicles of lamellar and hexagonal structure formed by increasing the surfactant concentration. The drug release studies indicated, that the kinetic of the release strongly depend on the liquid crystalline structure, zero order release occurs from hexagonal structures and anomalous transport occurs from lamellar structures. The addition of chlorhexidine species to the systems modified the structure of the liquid crystalline system. As a results of liquid crystal-drug interaction the solubility of chlorhexidine base and its diffusion through lipophilic membranes increased in comparison with those of the chlorhexidine salts. PMID:11961906

  12. Giant lateral electrostriction in ferroelectric liquid-crystalline elastomers.

    PubMed

    Lehmann, W; Skupin, H; Tolksdorf, C; Gebhard, E; Zentel, R; Krüger, P; Lösche, M; Kremer, F

    2001-03-22

    Mechanisms for converting electrical energy into mechanical energy are essential for the design of nanoscale transducers, sensors, actuators, motors, pumps, artificial muscles, and medical microrobots. Nanometre-scale actuation has to date been mainly achieved by using the (linear) piezoelectric effect in certain classes of crystals (for example, quartz), and 'smart' ceramics such as lead zirconate titanate. But the strains achievable in these materials are small--less than 0.1 per cent--so several alternative materials and approaches have been considered. These include grafted polyglutamates (which have a performance comparable to quartz), silicone elastomers (passive material--the constriction results from the Coulomb attraction of the capacitor electrodes between which the material is sandwiched) and carbon nanotubes (which are slow). High and fast strains of up to 4 per cent within an electric field of 150 MV x m(-1) have been achieved by electrostriction (this means that the strain is proportional to the square of the applied electric field) in an electron-irradiated poly(vinylidene fluoride-trifluoroethylene) copolymer. Here we report a material that shows a further increase in electrostriction by two orders of magnitude: ultrathin (less than 100 nanometres) ferroelectric liquid-crystalline elastomer films that exhibit 4 per cent strain at only 1.5 MV x m(-1). This giant electrostriction was obtained by combining the properties of ferroelectric liquid crystals with those of a polymer network. We expect that these results, which can be completely understood on a molecular level, will open new perspectives for applications. PMID:11260707

  13. Liquid Crystalline Properties of Amyloid Protein Fibers in Water

    NASA Astrophysics Data System (ADS)

    Mezzenga, Raffaele; Jung, Jin-Mi

    2010-03-01

    We have studied the liquid crystalline features of two colloidal systems consisting of food protein amyloid fibrils in water, obtained by heat-denaturation and aggregation of β-lactoglobulin, a globular dairy protein. The resulting fibrils, have a monodisperse cross section of about 4 nm and two groups of polydisperse contour lengths: (i) fibrils 1-10 μm long, showing semiflexible polyeletrolyte-like behaviour and (ii) rigid rods 100-200 nm long. In both systems, the fibers are highly charged (+5 e/nm) and stable in water at low ionic strength (0.01 M) and low pH (pH 2). The physical properties of these systems are studied using a polymer physics approach and phase diagrams of these two systems are obtained by changing concentration and pH. Both systems exhibit rich phase behaviours. Interestingly, the experimentally measured isotropic-nematic phase transition was found to occur at concentrations more than one order of magnitude lower than what expected based on Onsager theory. Experimental results are revisited in terms of the Flory theory developed for rigid polymers in solvent of varying conditions.

  14. A least squares closure approximation for liquid crystalline polymers

    NASA Astrophysics Data System (ADS)

    Sievenpiper, Traci Ann

    2011-12-01

    An introduction to existing closure schemes for the Doi-Hess kinetic theory of liquid crystalline polymers is provided. A new closure scheme is devised based on a least squares fit of a linear combination of the Doi, Tsuji-Rey, Hinch-Leal I, and Hinch-Leal II closure schemes. The orientation tensor and rate-of-strain tensor are fit separately using data generated from the kinetic solution of the Smoluchowski equation. The known behavior of the kinetic solution and existing closure schemes at equilibrium is compared with that of the new closure scheme. The performance of the proposed closure scheme in simple shear flow for a variety of shear rates and nematic polymer concentrations is examined, along with that of the four selected existing closure schemes. The flow phase diagram for the proposed closure scheme under the conditions of shear flow is constructed and compared with that of the kinetic solution. The study of the closure scheme is extended to the simulation of nematic polymers in plane Couette cells. The results are compared with existing kinetic simulations for a Landau-deGennes mesoscopic model with the application of a parameterized closure approximation. The proposed closure scheme is shown to produce a reasonable approximation to the kinetic results in the case of simple shear flow and plane Couette flow.

  15. In situ deuteron NMR investigations of sheared liquid crystalline polymers.

    PubMed

    Siebert, Hartmut; Becker, Patrick; Quijada-Garrido, Isabel; Grabowski, David A; Schmidt, Claudia

    2002-01-01

    The flow behavior of nematic liquid crystalline polysiloxanes of the side-chain type is studied by in situ 2H NMR spectroscopy on samples under shear in a cone-and-plate cell. The director orientation as a function of applied shear rate is determined from the quadrupole splitting of the spectra. The data analysis yields the two Leslie viscosity coefficients alpha2 and alpha3 and the flow-alignment parameter lambda = -(alpha3 + alpha2)/(alpha3 - alpha2). The values of lambda were determined for several homopolymers with only one type of side chain and random copolymers containing two different side chains. The results show that the flow behavior is related to the phase structure of the polymers, which varies with their composition. Only polymers with large amounts of smectic clusters in the nematic state show the tumbling instability (absolute value(lambda) < 1); other polymers are flow aligning (absolute value(lambda) > or = 1). For some polymers, a transition from tumbling at low temperature to flow aligning at high temperatures was observed. PMID:12469817

  16. Oriented Liquid Crystalline Polymer Semiconductor Films with Large Ordered Domains.

    PubMed

    Xue, Xiao; Chandler, George; Zhang, Xinran; Kline, R Joseph; Fei, Zhuping; Heeney, Martin; Diemer, Peter J; Jurchescu, Oana D; O'Connor, Brendan T

    2015-12-01

    Large strains are applied to liquid crystalline poly(2,5-bis(3-tetradecylthiophen-2yl)thieno(3,2-b)thiophene) (pBTTT) films when held at elevated temperatures resulting in in-plane polymer alignment. We find that the polymer backbone aligns significantly in the direction of strain, and that the films maintain large quasi-domains similar to that found in spun-cast films on hydrophobic surfaces, highlighted by dark-field transmission electron microscopy imaging. The highly strained films also have nanoscale holes consistent with dewetting. Charge transport in the films is then characterized in a transistor configuration, where the field effect mobility is shown to increase in the direction of polymer backbone alignment, and decrease in the transverse direction. The highest saturated field-effect mobility was found to be 1.67 cm(2) V(-1) s(-1), representing one of the highest reported mobilities for this material system. The morphology of the oriented films demonstrated here contrast significantly with previous demonstrations of oriented pBTTT films that form a ribbon-like morphology, opening up opportunities to explore how differences in molecular packing features of oriented films impact charge transport. Results highlight the role of grain boundaries, differences in charge transport along the polymer backbone and π-stacking direction, and structural features that impact the field dependence of charge transport. PMID:26552721

  17. Proton Transport in Nanostructured Block Copolymer/Ionic Liquid Membranes

    NASA Astrophysics Data System (ADS)

    Hoarfrost, Megan; Tyagi, Madhu; Reimer, Jeffrey; Segalman, Rachel

    2011-03-01

    Nanostructured block copolymer/ionic liquid mixtures are of interest for creating membranes having high proton conductivity coupled with high thermal stability. In these mixtures, it is anticipated that nanoconfinement to block copolymer domains will affect ionic liquid proton transport properties. Using pulsed-field gradient NMR and quasi-elastic neutron scattering, this relationship has been investigated for mixtures of poly(styrene-b- 2-vinylpyridine) (S2VP) with ionic liquids composed of imidazole and bis(trifluoromethane)sulfonimide (HTFSI), where the ionic liquids selectively reside in the P2VP domains of the block copolymer. Proton mobility is highest in the neat ionic liquids when there is an excess of imidazole compared to HTFSI due to proton hopping between hydrogen-bonded imidazoles. As predicted, the amount of proton hopping can be tuned by nanoconfinement, as evidenced by the finding that a lamellar mixture of an imidazole- excess ionic liquid with S2VP has greater proton mobility than a corresponding disordered mixture of the ionic liquid with P2VP homopolymer.

  18. Azobenzene-based organic salts with ionic liquid and liquid crystalline properties

    DOE PAGESBeta

    Stappert, Kathrin; Muthmann, Johanna; Spielberg, Eike T.; Mudring, Anja -Verena

    2015-07-23

    Two sets of new azobenzene-based bromide salts are synthesized, and their thermal photochromic properties are studied. Both sets are based on the imidazolium cation. The first set (1) features a symmetric biscation where two imidazolium head groups (Im) with different alkyl chains (Cn) are connected to a central azobenzene unit (Azo): [Azo(C1-Im-Cn)2]; n = 6, 8, 10, 12, 14. The other one contains an n-alkyl-imidazolium cation (Cn-Im) bearing a terminal azobenzene unit (C1-Azo) substituted with an alkoxy chain (O-Cm) of either two (2) or six (3) carbon atoms: [C1-Azo-O-Cm-Im-Cn]; m = 2, n = 8, 10, 12 and m =more » 6, n = 8, 10, 12, 14, 16. For both cation classes, the influence of alkyl chains of varying length on the thermal phase behavior was investigated by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). For five compounds (Azo(-C1-Im-C12)2 (1d), Azo(-C1-Im-C12)2 (1e), C1-Azo-O-C2-Im-C10 (2b), C1-Azo-O-C2-Im-C12 (2c), and C1-Azo-O-C6-Im-C16 (3e)), the formation of a liquid crystalline phase was observed. The biscationic salts (1) are all comparatively high melting organic salts (180–240 °C), and only the two representatives with long alkylchains (C12 and C14) exhibit liquid crystallinity. The monocationic salts with an O–C2 bridge (2) melt between 140 and 170 °C depending on the alkyl chain length, but from an alkyl chain of 10 and more carbon atoms on they form a smectic A liquid crystalline phase. The representatives of the third set with a O–C6 bridge qualify as ionic liquids with melting points less than 100 °C. However, only the representative with a hexadecyl chain forms a liquid crystalline phase. Representative single crystals for all sets of cations could be grown that allowed for single crystal structure analysis. Together with small-angle X-ray scattering experiments they allow for a more detailed understanding of the thermal properties. As a result, through irradiation with UV-light (320–366 nm) all

  19. Azobenzene-based organic salts with ionic liquid and liquid crystalline properties

    SciTech Connect

    Stappert, Kathrin; Muthmann, Johanna; Spielberg, Eike T.; Mudring, Anja -Verena

    2015-07-23

    Two sets of new azobenzene-based bromide salts are synthesized, and their thermal photochromic properties are studied. Both sets are based on the imidazolium cation. The first set (1) features a symmetric biscation where two imidazolium head groups (Im) with different alkyl chains (Cn) are connected to a central azobenzene unit (Azo): [Azo(C1-Im-Cn)2]; n = 6, 8, 10, 12, 14. The other one contains an n-alkyl-imidazolium cation (Cn-Im) bearing a terminal azobenzene unit (C1-Azo) substituted with an alkoxy chain (O-Cm) of either two (2) or six (3) carbon atoms: [C1-Azo-O-Cm-Im-Cn]; m = 2, n = 8, 10, 12 and m = 6, n = 8, 10, 12, 14, 16. For both cation classes, the influence of alkyl chains of varying length on the thermal phase behavior was investigated by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). For five compounds (Azo(-C1-Im-C12)2 (1d), Azo(-C1-Im-C12)2 (1e), C1-Azo-O-C2-Im-C10 (2b), C1-Azo-O-C2-Im-C12 (2c), and C1-Azo-O-C6-Im-C16 (3e)), the formation of a liquid crystalline phase was observed. The biscationic salts (1) are all comparatively high melting organic salts (180–240 °C), and only the two representatives with long alkylchains (C12 and C14) exhibit liquid crystallinity. The monocationic salts with an O–C2 bridge (2) melt between 140 and 170 °C depending on the alkyl chain length, but from an alkyl chain of 10 and more carbon atoms on they form a smectic A liquid crystalline phase. The representatives of the third set with a O–C6 bridge qualify as ionic liquids with melting points less than 100 °C. However, only the representative with a hexadecyl chain forms a liquid crystalline phase. Representative single crystals for all sets of cations could be grown that allowed for single crystal structure analysis. Together with small-angle X-ray scattering experiments they allow for a more detailed understanding of the thermal properties. As a result, through irradiation with UV

  20. Effects of alkaline or liquid-ammonia treatment on crystalline cellulose: changes in crystalline structure and effects on enzymatic digestibility

    PubMed Central

    2011-01-01

    Background In converting biomass to bioethanol, pretreatment is a key step intended to render cellulose more amenable and accessible to cellulase enzymes and thus increase glucose yields. In this study, four cellulose samples with different degrees of polymerization and crystallinity indexes were subjected to aqueous sodium hydroxide and anhydrous liquid ammonia treatments. The effects of the treatments on cellulose crystalline structure were studied, in addition to the effects on the digestibility of the celluloses by a cellulase complex. Results From X-ray diffractograms and nuclear magnetic resonance spectra, it was revealed that treatment with liquid ammonia produced the cellulose IIII allomorph; however, crystallinity depended on treatment conditions. Treatment at a low temperature (25°C) resulted in a less crystalline product, whereas treatment at elevated temperatures (130°C or 140°C) gave a more crystalline product. Treatment of cellulose I with aqueous sodium hydroxide (16.5 percent by weight) resulted in formation of cellulose II, but also produced a much less crystalline cellulose. The relative digestibilities of the different cellulose allomorphs were tested by exposing the treated and untreated cellulose samples to a commercial enzyme mixture (Genencor-Danisco; GC 220). The digestibility results showed that the starting cellulose I samples were the least digestible (except for corn stover cellulose, which had a high amorphous content). Treatment with sodium hydroxide produced the most digestible cellulose, followed by treatment with liquid ammonia at a low temperature. Factor analysis indicated that initial rates of digestion (up to 24 hours) were most strongly correlated with amorphous content. Correlation of allomorph type with digestibility was weak, but was strongest with cellulose conversion at later times. The cellulose IIII samples produced at higher temperatures had comparable crystallinities to the initial cellulose I samples, but achieved

  1. Review of Crystalline Structures of Some Selected Homologous Series of Rod-Like Molecules Capable of Forming Liquid Crystalline Phases

    PubMed Central

    Zugenmaier, Peter

    2011-01-01

    The crystal structures of four homologous series of rod-like molecules are reviewed, two of which form hydrogen bonds and two with a symmetric chemical constitution. Many of the compounds investigated turn into liquid crystalline phases upon temperature increase. It is of valuable interest to know possible conformations and possible packing arrangements as prerequisites to model liquid crystalline structures. The hydrogen bonds of homologous series of pure 4-(ω-hydroxyalkyloxy)-4′-hydroxybiphenyl (HnHBP, n the alkyloxy tail length) are realized through head to tail arrangements of the hydroxyl groups and crystallize except one compound in chiral space groups without the molecules containing any asymmetric carbon. The hydrogen bonds of the homologous series of 4-substituted benzoic acids with various lengths of the tail provide dimers through strong polar bonding of adjacent carboxyl groups and thus provide the stiff part of a mesogenic unit prerequisite for liquid crystalline phases. The homologous series of dialkanoyloxybiphenyls (BP-n, n = 1, 19), of which nine compounds could be crystallized, show liquid crystalline behavior for longer alkane chain lengths, despite the high mobility of the alkane chain ends already detectable in the crystal phase. A single molecule, half a molecule or two half molecules form the asymmetric unit in a centrosymmetric space group. The homologous series of 1,4-terephthalidene-bis-N-(4′-n-alkylaniline) (TBAA-n) exhibit a large variety of packing arrangements in the crystalline state, with or without relying on the symmetry center within the molecules. PMID:22174604

  2. Physics of liquid and crystalline plasmas: Future perspectives

    NASA Astrophysics Data System (ADS)

    Morfill, G. E.

    It has been shown that under certain conditions "complex plasmas" (plasma containing ions, electrons and charged microspheres) may undergo spontaneous phase changes to become liquid and crystalline, without recombination of the charge components. Hence these systems may be regarded as new plasma states "condensed plasmas". The ordering forces are mainly electrostatic, but dipolar effects, anisotropic pressure due shielding, ion flow focussing etc. may all play a role, too. Complex plasmas are of great interest from a fundamental research point of view because the individual particles of one plasma component (the charged microspheres) can be visualised and hence the plasma can be studied at the kinetic level. Also, the relevant time scales (e.g. 1/plasma frequency) are of order 0.1 sec, the plasma processes occur practically in "slow motion". We will discuss some physical processes (e.g. wave propagation, shocks, phase transitions) of these systems and outline the potential of the research for the understanding of strongly coupled systems. Technologically, it is expected that colloidal plasmas will also become very important, because both plasma technology and colloid technology are widely developed already. In this overview first the basic forces between the particles are discussed, then the phase transitions, the lattice structures and results from active experiments will be presented. Finally the future perspectives will be discussed, from the scientific potential point of view and the experimental approaches in the laboratory and in space. Experiments under microgravity conditions are of great importance, because the microspheres are 10's of billions times heavier than the ions.

  3. Multiscale modeling of liquid crystalline/nanotube composites

    NASA Astrophysics Data System (ADS)

    Patrale, Sharil

    The objective of this research is to synthesize structural composites designed with particular areas defined with custom modulus, strength and toughness values in order to improve the overall mechanical behavior of the composite. Such composites are defined and referred to as 3D-designer composites. These composites will be formed from liquid crystalline polymers and carbon nanotubes. The fabrication process is a variation of rapid prototyping process, which is a layered, additive-manufacturing approach. Composites formed using this process can be custom designed by apt modeling methods for superior performance in advanced applications. The focus of this research is on enhancement of Young's modulus in order to make the final composite stiffer. Strength and toughness of the final composite with respect to various applications is also discussed. We have taken into consideration the mechanical properties of final composite at different fiber volume content as well as at different orientations and lengths of the fibers. The orientation of the LC monomers is supposed to be carried out using electric or magnetic fields. A computer program is modeled incorporating the Mori-Tanaka modeling scheme to generate the stiffness matrix of the final composite. The final properties are then deduced from the stiffness matrix using composite micromechanics. Eshelby's tensor, required to calculate the stiffness tensor using Mori-Tanaka method, is calculated using a numerical scheme that determines the components of the Eshelby's tensor (Gavazzi and Lagoudas 1990). The numerical integration is solved using Gaussian Quadrature scheme and is worked out using MATLAB as well. MATLAB provides a good deal of commands and algorithms that can be used efficiently to elaborate the continuum of the formula to its extents. Graphs are plotted using different combinations of results and parameters involved in finding these results.

  4. Optical and topographic changes in water-responsive patterned cholesteric liquid crystalline polymer coatings

    NASA Astrophysics Data System (ADS)

    Stumpel, Jelle E.; Broer, Dirk J.; Bastiaansen, Cees W. M.; Schenning, Albert P. H. J.

    2014-05-01

    In this work, we present patterned water-responsive coatings, which alter both their topological and optical properties. The polymer coatings are based on a hydrogen-bonded cholesteric liquid crystalline polymer network. A two-step photopolymerization procedure leads to a patterned coating with repeating liquid crystalline and isotropic areas. The cholesteric liquid crystalline areas reflect green light, whilst the isotropic areas are transparent for visible light. Treatment with alkaline solution results in a hygroscopic polymer salt coating. When placed in demineralized water, the polymer films swells, leading to an enhancement of the surface topography structure in which the liquid crystalline areas swell more. Moreover, the pitch of the helical organization in the cholesteric areas increases due to this swelling leading to a color change from green to red.

  5. Liquid film flow in a fracture between two porous blocks

    SciTech Connect

    Dindoruk, B.; Firoozabadi, A. )

    1994-12-01

    Liquid film flow in a fracture between two porous bodies is mainly driven by pressure. The pressure drop across such a small distance could be significant. The flow of a liquid film is governed by the pressure drop across the fracture space, and therefore, understanding of liquid film flow in a single liquid bridge along a solid wall between two porous bodies is needed. The shape of the liquid bridge between the porous blocks is an unknown. The first step is to determine the shape of the free surface. Due to the nature of the problem, a boundary integral technique is found to provide the solution to the whole problem. Solutions are reported for a range of capillary numbers observed in cracked porous media. Pressure drop is correlated using a dimensionless capillary number group. Using analogy from the Darcy flow in porous media, a correlation for the equivalent Darcy permeability is developed.

  6. Selection of thermotropic liquid crystalline polymers for rotational molding

    NASA Astrophysics Data System (ADS)

    Scribben, Eric

    Thermotropic liquid crystalline polymers (TLCPs) possess a number of physical and mechanical properties such as: excellent chemical resistance, low permeability, low coefficient of thermal expansion, high tensile strength and modulus, and good impact resistance, which make them desirable for use in the storage of cryogenic fluids. Rotational molding was selected as the processing method for these containers because it is convenient for manufacturing large storage vessels from thermoplastics. Unfortunately, there are no reports of successful TLCP rotational molding in the technical literature. The only related work reported involved the static coalescence of two TLCP powders, where three key results were reported that were expected to present problems that preclude the rotational molding process. The first result was that conventional grinding methods produced powders that were composed of high aspect ratio particles. Secondly, coalescence was observed to be either slow or incomplete and speculated that the observed difficulties with coalescence may be due to large values of the shear viscosity at low deformation rates. Finally, complete densification was not observed for the high aspect ratio particles. However, the nature of these problems were not evaluated to determine if they did, in fact, create processing difficulties for rotational molding or if it was possible to develop solutions to the problems to achieve successful rotational molding. This work is concerned with developing a resin selection method to identify viable TLCP candidates and establish processing conditions for successful rotational molding. This was accomplished by individually investigating each of the phenomenological steps of rotational molding to determine the requirements for acceptable performance in, or successful completion of, each step. The fundamental steps were: the characteristics and behavior of the powder in solids flow, the coalescence behavior of isolated particles, and the

  7. Shape-Selectivity with Liquid Crystal and Side-Chain Liquid Crystalline Polymer SAW Sensor Interfaces

    SciTech Connect

    FRYE-MASON,GREGORY CHARLES; OBORNY,MICHAEL C.; PUGH,COLEEN; RICCO,ANTONIO; THOMAS,ROSS C.; ZELLERS,EDWARD T.; ZHANG,GUO-ZHENG

    1999-09-23

    A liquid crystal (LC) and a side-chain liquid crystalline polymer (SCLCP) were tested as surface acoustic wave (SAW) vapor sensor coatings for discriminating between pairs of isomeric organic vapors. Both exhibit room temperature smectic mesophases. Temperature, electric-field, and pretreatment with self-assembled monolayers comprising either a methyl-terminated or carboxylic acid-terminated alkane thiol anchored to a gold layer in the delay path of the sensor were explored as means of affecting the alignment and selectivity of the LC and SCLCP films. Results for the LC were mixed, while those for the SCLCP showed a consistent preference for the more rod-like isomer of each isomer pair examined.

  8. Formation of a liquid-crystalline interpenetrating poly-(ionic liquid) network hydrogel.

    SciTech Connect

    Becht, G. A.; Sofos, M.; Seifert, S.; Firestone, M. A.

    2011-02-21

    Preparation of a liquid-crystalline ionic-liquid (IL)-based interpenetrating polymer network (IPN) is described. The IPN is prepared sequentially by first photopolymerizing a self-assembled aqueous mixture of an IL monomer (1-(10-(acryloyloxy)decyl)-3-methylimidazolium chloride) that possesses an acryloyl moiety at the terminus of a C{sub 10} alkyl chain of the IL cation. In the second step, an acrylate counteranion is introduced and then photopolymerized to yield a durable self-supporting network polymer. Thermal analysis indicates the formation of a homogeneous (well-blended constituent polymers) IPN. The IPN adopts a lamellar structure possessing some residual in-plane tetragonal perforations, as evidenced by small-angle X-ray scattering (SAXS). The IPN can absorb large quantities of water, swelling to nearly 60 times its original volume, but retains mechanical integrity making it a durable hydrogel.

  9. Liquid-crystalline elastomer-nanoparticle hybrids with reversible switch of magnetic memory.

    PubMed

    Haberl, Johannes M; Sánchez-Ferrer, Antoni; Mihut, Adriana M; Dietsch, Hervé; Hirt, Ann M; Mezzenga, Raffaele

    2013-03-25

    A stimuli-responsive material is synthesized that combines the actuation potential of liquid-crystalline elastomers with the anisotropic magnetic properties of ellipsoidal iron oxide nanoparticles. The resulting nanocomposite exhibits unique shape-memory features with magnetic information, which can be reversibly stored and erased via parameters typical of soft materials, such as high deformations, low stresses, and liquid-crystalline smectic-isotropic transition temperatures. PMID:23359417

  10. Chain exchange kinetics of block copolymer micelles in ionic liquids

    NASA Astrophysics Data System (ADS)

    Ma, Yuanchi; Lodge, Timothy

    The chain exchange kinetics of block copolymer micelles has been studied using time-resolved small-angle neutron scattering (TR-SANS), a key tool in determining the average micelle composition in contrast-matched solvents. In this work, PMMA-block-PnBMA was selected as the model block copolymer, which has a LCST behavior in the common ionic liquids, [EMIM][TFSI] and [BMIM][TFSI]. We examined the chain exchange kinetics of three PMMA-block-PnBMA copolymers, with identical PMMA block length (MPMMA = 25000) and different PnBMA block lengths (MPnBMA = 24000, 35000 and 53000); the Flory-Huggins interaction parameter (χ) between the core (PnBMA) and the solvent were varied by mixing [EMIM][TFSI] and [BMIM][TFSI] in different ratios. We found that the relaxation of the initial segregation of h- and d- micelles followed the same form with the time as previously developed by our group. Assuming that single chain expulsion is the rate limiting step, the thermal barrier was found to depend linearly on the core block length (Ncore) . Furthermore, the effect of χ on the chain exchange kinetics will also be discussed.

  11. Gel formation in a mixture of a block copolymer and a nematic liquid crystal.

    PubMed

    Khazimullin, Maxim; Müller, Thomas; Messlinger, Stephan; Rehberg, Ingo; Schöpf, Wolfgang; Krekhov, Alexei; Pettau, Robin; Kreger, Klaus; Schmidt, Hans-Werner

    2011-08-01

    The viscoelastic properties of a binary mixture of a mesogenic side-chain block copolymer in a low molecular weight nematic liquid crystal are studied for mass concentrations ranging from the diluted regime up to a liquid crystalline gel state at about 3%. In the gel state, the system does not flow, exhibits a polydomain structure on a microscopic level, and strongly scatters light. Below the gelation point, the system is homogeneous and behaves like a usual nematic, so the continuum theory of liquid crystals can be applied for interpreting the experimental data. Using the dynamic Fréedericksz transition technique, the dependence of the splay elastic constant and the rotational viscosity on the polymer concentration have been obtained. Comparing the dynamic behavior of block copolymer solutions with the respective homopolymer solutions reveals that, above a mass concentration of 1%, self-assembling of the block copolymer chain segments in clusters occurred, resulting in a gel state at higher concentrations. The effective cluster size is estimated as a function of the concentration, and a scaling-law behavior near the sol-gel transition is confirmed. This technique may serve as an alternative method for determining the gelation point. PMID:21929007

  12. Gel formation in a mixture of a block copolymer and a nematic liquid crystal

    NASA Astrophysics Data System (ADS)

    Khazimullin, Maxim; Müller, Thomas; Messlinger, Stephan; Rehberg, Ingo; Schöpf, Wolfgang; Krekhov, Alexei; Pettau, Robin; Kreger, Klaus; Schmidt, Hans-Werner

    2011-08-01

    The viscoelastic properties of a binary mixture of a mesogenic side-chain block copolymer in a low molecular weight nematic liquid crystal are studied for mass concentrations ranging from the diluted regime up to a liquid crystalline gel state at about 3%. In the gel state, the system does not flow, exhibits a polydomain structure on a microscopic level, and strongly scatters light. Below the gelation point, the system is homogeneous and behaves like a usual nematic, so the continuum theory of liquid crystals can be applied for interpreting the experimental data. Using the dynamic Fréedericksz transition technique, the dependence of the splay elastic constant and the rotational viscosity on the polymer concentration have been obtained. Comparing the dynamic behavior of block copolymer solutions with the respective homopolymer solutions reveals that, above a mass concentration of 1%, self-assembling of the block copolymer chain segments in clusters occurred, resulting in a gel state at higher concentrations. The effective cluster size is estimated as a function of the concentration, and a scaling-law behavior near the sol-gel transition is confirmed. This technique may serve as an alternative method for determining the gelation point.

  13. Structure and interactions in isotropic and liquid crystalline neurofilament networks

    NASA Astrophysics Data System (ADS)

    Jones, Jayna Bea

    2007-12-01

    Neurofilaments (NFs) are cytoskeletal proteins that are localized within nerve cells, which form long oriented bundles running the length of axons. While abnormal aggregations of these proteins have been implicated in several neurological disorders including Parkinson's disease and ALS, interfilament interactions in both the normal and diseased states are not well understood. In vivo, NFs are supramolecular structures composed of three subunit proteins of low (NF-L), medium (NF-M), and high molecular (NF-H) weight that assemble into a 10 nm diameter rod with radiating sidearms, forming a bottle-brush conformation. In this study we alter the subunit composition and probe the resulting networks with polarized microscopy and synchrotron small angle x-ray scattering (SAXS), in order to isolate the role of each subunit in interfilament interactions. By reassembling NFs in vitro from varying ratios of the subunit proteins, purified from bovine spinal cord, we form filaments with controlled subunit compositions. The resulting filaments, at a high volume fraction, are nematic liquid crystalline gels with a well defined spacing, determined with SAXS. Upon dilution the difference between the subunits is realized with NF-M grafted filaments being dominated by attractive interactions and remaining aligned, while those flanked with NF-H sidearms repel and become isotropic gels. Interplay between these forces is seen in the ternary system composed of all three subunit proteins (NF-LMH). The polyampholytic subunits have a charge distribution that varies along the length of the sidearm, which forms the brush layer, and the distribution is different for each subunit. The interfilament interactions are highly dependent on environmental conditions including salt concentration, pH, and osmotic pressure. Increasing ionic strength induces attractive interactions and a stabilization of the nematic phase in filaments that were repulsive at lower monovalent salt concentration. The

  14. Liquid Crystalline Thermosets from Ester, Ester-imide, and Ester-amide Oligomers

    NASA Technical Reports Server (NTRS)

    Dingemans, Theodorus J. (Inventor); Weiser, Erik S. (Inventor); St. Clair, Terry L. (Inventor)

    2009-01-01

    Main chain thermotropic liquid crystal esters, ester-imides, and ester-amides were prepared from AA, BB, and AB type monomeric materials and end-capped with phenylacetylene, phenylmaleimide, or nadimide reactive end-groups. The end-capped liquid crystal oligomers are thermotropic and have, preferably, molecular weights in the range of approximately 1000-15,000 grams per mole. The end-capped liquid crystaloligomers have broad liquid crystalline melting ranges and exhibit high melt stability and very low melt viscosities at accessible temperatures. The end-capped liquid crystal oli-gomers are stable forup to an hour in the melt phase. They are highly processable by a variety of melt process shape forming and blending techniques. Once processed and shaped, the end-capped liquid crystal oigomers were heated to further polymerize and form liquid crystalline thermosets (LCT). The fully cured products are rubbers above their glass transition temperatures.

  15. An azobenzene-based photochromic liquid crystalline amphiphile for a remote-controllable light shutter.

    PubMed

    Kim, Dae-Yoon; Lee, Sang-A; Kim, Huisu; Min Kim, Soo; Kim, Namil; Jeong, Kwang-Un

    2015-07-14

    By considering intramolecular conformations and intermolecular interactions, an azobenzene-based photochromic liquid crystalline amphiphile is synthesized for demonstrating a remote-controllable light shutter by the photo-induced isothermal phase transition between the highly ordered crystal phase and the isotropic liquid phase. PMID:26067781

  16. One-piece micropumps from liquid crystalline core-shell particles

    NASA Astrophysics Data System (ADS)

    Fleischmann, Eva-Kristina; Liang, Hsin-Ling; Kapernaum, Nadia; Giesselmann, Frank; Lagerwall, Jan; Zentel, Rudolf

    2012-11-01

    Responsive polymers are low-cost, light weight and flexible, and thus an attractive class of materials for the integration into micromechanical and lab-on-chip systems. Triggered by external stimuli, liquid crystalline elastomers are able to perform mechanical motion and can be utilized as microactuators. Here we present the fabrication of one-piece micropumps from liquid crystalline core-shell elastomer particles via a microfluidic double-emulsion process, the continuous nature of which enables a low-cost and rapid production. The liquid crystalline elastomer shell contains a liquid core, which is reversibly pumped into and out of the particle by actuation of the liquid crystalline shell in a jellyfish-like motion. The liquid crystalline elastomer shells have the potential to be integrated into a microfluidic system as micropumps that do not require additional components, except passive channel connectors and a trigger for actuation. This renders elaborate and high-cost micromachining techniques, which are otherwise required for obtaining microstructures with pump function, unnecessary.

  17. Clustomesogens: Liquid Crystalline Hybrid Nanomaterials Containing Functional Metal Nanoclusters.

    PubMed

    Molard, Yann

    2016-08-16

    Inorganic phosphorescent octahedral metal nanoclusters fill the gap between metal complexes and nanoparticles. They are finite groups of metal atoms linked by metal-metal bonds, with an exact composition and structure at the nanometer scale. As their phosphorescence internal quantum efficiency can approach 100%, they represent a very attractive class of molecular building blocks to design hybrid nanomaterials dedicated to light energy conversion, optoelectronic, display, lighting, or theragnostic applications. They are obtained as AnM6X(i)8X(a)6 ternary salt powders (A = alkali cation, M = Mo, Re, W, X(i): halogen inner ligand, X(a) = halogen apical ligand) by high temperature solid state synthesis (750-1200 °C). However, their ceramic-like behavior has largely restricted their use as functional components in the past. Since these last two decades, several groups, including ours, started to tackle the challenge of integrating them in easy-to-process materials. Within this context, we have extensively explored the nanocluster ternary salt specificities to develop a new class of self-organized hybrid organic-inorganic nanomaterials known as clustomesogens. These materials, combine the specific properties of nanoclusters (magnetic, electronic, luminescence) with the anisotropy-related properties of liquid crystals (LCs). This Account covers the research and development of clustomesogens starting from the design concepts and synthesis to their introduction in functional devices. We developed three strategies to build such hybrid super- or supramolecules. In the covalent approach, we capitalized on the apical ligand-metal bond iono-covalent character to graft tailor-made organic LC promoters on the {M6X(i)8}(n+) nanocluster cores. The supramolecular approach relies on the host-guest complexation of the ternary cluster salt alkali cations with functional crown ether macrocycles. We showed that the hybrid LC behavior depends on the macrocycles structural features

  18. Self-assembled monolayers of alkanethiols on gold prepared in a hexagonal lyotropic liquid crystalline phase of Triton X-100/water system.

    PubMed

    Ganesh, V; Lakshminarayanan, V

    2006-02-14

    In this paper, we have reported a new method of preparing self-assembled monolayers (SAMs) of decanethiol and hexadecanethiol on gold surface by using a lyotropic liquid crystalline phase as an adsorbing medium. The stability and blocking ability of these SAMs were characterized using grazing angle Fourier transform infrared (FTIR) spectroscopy and electrochemical techniques such as cyclic voltammetry and electrochemical impedance spectroscopy. The lyotropic liquid crystalline medium possesses a hexagonal structure consisting of a nonionic surfactant Triton X-100, water, and the corresponding thiol, which provides a highly hydrophobic environment to solubilize the alkanethiols and later to facilitate their delivery to the gold surface. We find that the SAMs formed from the hexagonal liquid crystalline phase are highly compact and have excellent electrochemical blocking ability towards the redox probes compared to conventional SAMs prepared from commonly used organic solvents such as ethanol. From the impedance studies, we have determined the capacitance of the monolayer-coated electrodes and the surface coverage of the SAM, which has been found to be >99.98% on gold surface. We have also estimated the extent of ionic permeability through the film and measured the rate constants for the redox reactions on the SAM-modified electrodes. Our results show that the rate constants of [Fe(CN)6](3-/4-) and [Ru(NH3)6](2+/3+) redox couples are very much lower in the case of monolayers prepared in liquid crystalline phase compared to the SAM formed in 1 mM thiol in ethanol solution, suggesting a better blocking ability of the SAMs in the former case. From the grazing angle FTIR spectroscopic studies and capacitance measurements, we have ruled out any coadsorption of surfactant molecules on the Au surface. These results suggest that SAMs of very low defect density and extremely low ionic permeability can be obtained when a hexagonal lyotropic liquid crystalline phase is used as

  19. Optical Behaviors of Cholesteric Liquid-Crystalline Polyester Composites with Various Chiral Photochromic Dopants.

    PubMed

    Chien, Chih-Chieh; Liu, Jui-Hsiang

    2015-12-15

    New developments in the field of chiral nematic liquid crystals, such as color displays, are now being widely proposed. This article describes the tunable incident reflection band based on composite materials of low-molecular-weight chiroptical dopants and polymeric networks. These materials have advantages including easily manageable color according to a change in the helical pitch of the cholesteric liquid crystal upon exposure to light. A series of novel chiral dopants of isosorbide derivatives containing photochromic groups and three new main-chain liquid crystalline polyesters were synthesized and identified using nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR), and elemental analyses. The phase-transition temperatures and the liquid-crystal phase determination of the synthesized polymers were estimated using DSC, WAXD, and POM analyses. The influence of the dopant concentrations and the solubility in a liquid crystalline polymer blend were also studied. The reflection band of the cholesteric liquid crystalline composites could be adjusted and tuned with a wide range of color variation across the entire visible region. A real image recording of the chiral photochromic liquid crystalline polymer blend was achieved by exposing it to UV light through a mask. PMID:26636344

  20. Mouldable liquid-crystalline elastomer actuators with exchangeable covalent bonds.

    PubMed

    Pei, Zhiqiang; Yang, Yang; Chen, Qiaomei; Terentjev, Eugene M; Wei, Yen; Ji, Yan

    2014-01-01

    Liquid-crystal elastomers (LCEs) are a class of actively moving polymers with remarkable practical potential for converting external stimuli into mechanical actuation. However, real-world applications of LCEs are lacking because macroscopic orientation of liquid-crystal order, which is required for reversible actuations, is hard to achieve in practice. Here we show that the processing bottleneck of LCEs can be overcome by introducing exchangeable links in place of permanent network crosslinks, a concept previously demonstrated for vitrimers. Liquid-crystal elastomers with exchangeable links (xLCEs) are mouldable, allow for easy processing and alignment, and can be subsequently altered through remoulding with different stress patterns, thus opening the way to practical xLCE actuators and artificial muscles. Surprisingly, instead of external-stress relaxation through the creep of non-liquid-crystal transient networks with exchangeable links, xLCEs develop strong liquid-crystal alignment as an alternative mechanism of mechanical relaxation. PMID:24292422

  1. A study of the structure of the crystalline bacterial biofilms that can encrust and block silver Foley catheters.

    PubMed

    Morgan, Sheridan D; Rigby, Deborah; Stickler, David J

    2009-04-01

    The aim of this study was to examine the structure of the crystalline bacterial biofilms that encrust and block silver/hydrogel-coated latex catheters. Scanning electron microscopy was used to examine the crystalline deposits that were found encrusting catheters obtained from six patients undergoing long-term catheterization in a community setting. Large populations of bacilli and cocci were seen on all catheters developing on a basal foundation layer of crystalline material. These observations show that in patients prone to catheter encrustation, crystalline material formed in the urine can cover the surfaces of silver catheters. Extensive bacterial biofilms then develop on the crystals, shielded from the underlying silver. It is suggested that if antimicrobials are to be incorporated into catheters to prevent encrustation, they must diffuse out from the catheter surface and reduce the viable cell populations of the urease producing bacteria that elevate the urinary pH and trigger crystal formation. PMID:19189089

  2. The effect of side-chain liquid crystalline concentration in liquid crystal on dielectric properties

    NASA Astrophysics Data System (ADS)

    Gökçen, M.; Köysal, O.; Yıldırım, M.; Altındal, Ş.

    2012-08-01

    As liquid crystal (LC), E63 and as doping material, side-chain liquid crystalline polymer (SLCP) were used in this study. In order to observe the effect of SLCP concentration in LC on the dielectric properties in a wide range of frequency and bias voltage, SLCP was doped into E63 with 0 (pure E63), 1 and 10 wt%. The bias voltage and frequency dependence of the dielectric properties of pure E63 and doped mixtures (E63/SCLP) have been investigated using the admittance spectroscopy method (C-V and G/ω-V) in the frequency range of 10 kHz-10 MHz at room temperature. The values of dielectric constant (ɛ‧) and real (M‧) and imaginary (M″) parts of electric modulus of the pure E63 and E63/SLCP (1 and 10%) were calculated using the measured admittance values. Moreover, dielectric anisotropy (Δɛ) was also obtained for each sample as a function of frequency. Results show that the values of dielectric parameters are strong functions of frequency and applied bias voltage depending on the concentration amount. Furthermore, dielectric anisotropy has negative values according to p/n type changing for each sample after a critical frequency value.

  3. Dynamic focusing microlens array using liquid crystalline polymer and a liquid crystal

    NASA Astrophysics Data System (ADS)

    Choi, Yoonseuk; Lee, Kwang-Ho; Kim, Hak-Rin; Kim, Jae-Hoon

    2006-09-01

    An active microlens device is demonstrated by using a stacked layer structure of UV curable polymer, liquid crystalline polymer (LCP) and a liquid crystal (LC). The incident linearly polarized light is focused after passing through the combined refractive type microlens array system of UV curable polymer and LCP. Because used LCP shows highly birefringent macroscopic property from the well-ordered molecular structure, the additional polarization state control layer was inserted to modulate the dynamic focusing characteristics of the device. From the additional twisted LC layer's electro-optic response, we obtained good focal switching characteristics of microlens array with a small operation voltage application. This enhanced dynamic focusing characteristic of device was originated from the separate operation of polymer lens structure's beam focusing and twisted LC layer's polarization control ability. The measured focal length was well matched to the calculated one. This proposed LC microlens array is expected to play a critical role in the various real photonic components such as highly reliable optical switch, beam modulator and key device for 3-D imaging system.

  4. Enhanced light absorption in graphene via a liquid-crystalline optical diode

    NASA Astrophysics Data System (ADS)

    Pantazi, Aikaterini Iria; Yannopapas, Vassilios

    2016-09-01

    We demonstrate theoretically that light absorption in graphene can be boosted via a light-trapping mechanism based on a liquid-crystalline optical diode. The optical diode consists of twisted-nematic and nematic liquid-crystalline slabs. In particular, we show that, using a proper optical-diode setup, the absorption in a single graphene layer can be enhanced by a factor of four. By varying the pitch of the twisted-nematic liquid-crystalline slabs comprising the diode, one can tune the operating spectral region of the diode and thus enhance the absorption of graphene within a desired spectral window. Our calculations are based on Berreman's 4×4 method which treats anisotropic, isotropic and/ or inhomogeneous layered systems on equal footing.

  5. Topological Control of Columnar Stacking Made of Liquid-Crystalline Thiophene-Fused Metallonaphthalocyanines.

    PubMed

    Suzuki, Hiroyuki; Kawano, Koki; Ohta, Kazuchika; Shimizu, Yo; Kobayashi, Nagao; Kimura, Mutsumi

    2016-04-01

    The spontaneous organization of two-dimensional polyaromatic molecules into well-defined nanostructures through noncovalent interactions is important in the development of organic-based electronic and optoelectronic devices. Two regioisomers of thiophene-fused zinc naphthalocyanines ZnTNcendo and ZnTNcexo have been designed and synthesized to obtain photo- and electroactive liquid crystalline materials. Both compounds exhibited liquid crystalline behavior over a wide temperature range through intermolecular π-π interactions and local phase segregation between the aromatic cores and peripheral side chains. The structural differences between ZnTNcendo and ZnTNcexo affected the stacking mode in self-assembled columns, as well as symmetry of the two-dimensional rectangular columnar lattice. The columnar structure in liquid crystalline phase exhibited an ambipolar charge-transport behavior. PMID:27308226

  6. Viewing angle compensation of various LCD modes by using a liquid crystalline polymer film

    NASA Astrophysics Data System (ADS)

    Matsumoto, Takuya; Nishimura, Suzushi

    2013-09-01

    The authors have developed liquid crystalline retardation films to improve certain aspects of LCD image quality such as viewing angle performance and coloration. We have successfully created several types of optical retardation films using a rod-like liquid crystalline polymer. The resulting liquid crystalline polymer films have several advantages over conventional uni- or biaxially stretched retardation films. Precisely controlled structures such as twisted nematic, homogeneous nematic, hybrid nematic and homeotropic structures can provide ideal compensation of various LCD types, such as STN, TN, ECB, VA and IPS-LCDs. Twisted nematic film effectively prevents coloration of STN-LCDs, which is a critical flaw affecting color representation. Short pitch cholesteric film, which utilizes said rod-like liquid crystalline polymer and is the optical equivalent of a negative C-plate, can expand the viewing angle of VA-LCDs. Hybrid nematic film is quite unique in that the film functions not only as a wave plate but also as a viewing angle compensator for TN and ECB-LCDs. Homeotropic film, which acts as a positive-C plate, greatly improves the viewing angle performance of IPS and CPVA-LCDs. Our homeotropically aligned liquid crystalline film, called "NV film", is the world's thinnest retardation film. The thickness of the liquid crystalline layer is a mere 1 micrometer. Homeotropic film can be used to expand the viewing angle not only of LCDs but also OLED displays. And NV film, when used in in combination with a quarter wavelength plate, can expand the viewing angles of the circular polarizers used to prevent reflection in OLED displays.

  7. Supramolecular Liquid Crystallinity: Spherical Coils of Levan Surrounding Cylindrical Rods of DNA

    NASA Astrophysics Data System (ADS)

    Huber, Anne E.; Viney, Christopher

    1998-01-01

    Levan, which adopts a compact spherical conformation in aqueous solution, can form a liquid crystalline phase if DNA is also present. We propose that supramolecular rodlike structures, assembled by the noncovalent aggregation of levan around DNA, stabilize the lyotropic phase. We describe a geometric model for the aggregates. The model is quantitatively consistent with the relative amounts of DNA and levan needed for liquid crystallinity, and it agrees qualitatively with the shape of the boundary between the isotropic and heterogeneous fields on an experimentally determined phase diagram.

  8. Mechanisms of dielectric polarization in thermotropic liquid-crystalline complexes based on lanthanides

    NASA Astrophysics Data System (ADS)

    Dobrun, L. A.; Kovshik, A. P.; Ryumtsev, E. I.; Knyazev, A. A.; Galyametdinov, Yu. G.

    2016-06-01

    The components of the dielectric constant of a terbium-based liquid-crystalline complex have been measured in the frequency range of 350-5 × 106 Hz. The magnitude and sign of the dielectric anisotropy of the complex have been determined. Dispersion of the dielectric constants in the liquid-crystalline and isotropic phases has been found. The mechanisms responsible for the relaxation phenomena that appear in the studied sample have been determined. The time of dielectric relaxation, the activation energy, and the dipole moment of the complex have been obtained.

  9. Organic solar cells based on liquid crystalline and polycrystalline thin films

    NASA Astrophysics Data System (ADS)

    Yoo, Seunghyup

    This dissertation describes the study of organic thin-film solar cells in pursuit of affordable, renewable, and environmentally-friendly energy sources. Particular emphasis is given to the molecular ordering found in liquid crystalline or polycrystalline films as a way to leverage the efficiencies of these types of cells. Maximum efficiencies estimated based on excitonic character of organic solar cells show power conversion efficiencies larger than 10% are possible in principle. However, their performance is often limited due to small exciton diffusion lengths and poor transport properties which may be attributed to the amorphous nature of most organic semiconductors. Discotic liquid crystal (DLC) copper phthalocyanine was investigated as an easily processible building block for solar cells in which ordered molecular arrangements are enabled by a self-organization in its mesophases. An increase in photocurrent and a reduction in series resistance have been observed in a cell which underwent an annealing process. X-ray diffraction (XRD) and atomic force microscopy (AFM) measurements suggest that structural and morphological changes induced after the annealing process are related to these improvements. In an alternative approach, p-type pentacene thin films prepared by physical vapor deposition were incorporated into heterojunction solar cells with C60 as n-type layers. Power conversion efficiencies of 2.7% under broadband illumination (350--900 nm) with a peak external quantum efficiency of 58% have been achieved with the broad spectral coverage across the visible spectrum. Analysis using an exciton diffusion model shows this efficient carrier generation is mainly due to the large exciton diffusion length of pentacene films. Joint XRD and AFM studies reveal that the highly crystalline nature of pentacene films can account for the observed large exciton diffusion length. In addition, the electrical characteristics are studied as a function of light intensity using

  10. Structure and mechanical properties of liquid crystalline filaments

    SciTech Connect

    Eremin, Alexey; Nemes, Alexandru; Stannarius, Ralf; Schulz, Mario; Nadasi, Hajnalka; Weissflog, Wolfgang

    2005-03-01

    The formation of stable freely suspended filaments is an interesting peculiarity of some liquid crystal phases. So far, little is known about their structure and stability. Similarly to free-standing smectic films, an internal molecular structure of the mesophase stabilizes these macroscopically well-ordered objects with length to diameter ratios of 10{sup 3} and above. In this paper, we report observations of smectic liquid crystal fibers formed by bent-shaped molecules in different mesophases. Our study, employing several experimental techniques, focuses on mechanical and structural aspects of fiber formation such as internal structure, stability, and mechanical and optical properties.

  11. Orientational energy of anisometric particles in liquid-crystalline suspensions

    NASA Astrophysics Data System (ADS)

    Burylov, S. V.; Zakhlevnykh, A. N.

    2013-07-01

    We obtain a general expression for the orientational energy of an individual anisometric particle suspended in uniform nematic liquid crystals when the main axis of the particle rotates with respect to the nematic director. We show that there is a qualitative and quantitative analogy between the internal and external problems for cylindrical volumes of nematic liquid crystals, and on this basis we obtain an estimate of the orientational energy of a particle of cylindrical (rodlike, needlelike, or ellipsoidal) shape. For an ensemble of such particles we propose a modified form of their orientational energy in the nematic matrix. This orientational energy has the usual second-order term, and additional fourth-order term in the scalar product of the nematic director and the vector which characterizes an average direction of the main axes of the particles. As an example we obtain the expression for the free energy density of ferronematics, i.e., colloidal suspensions of needlelike magnetic particles in nematic liquid crystals. Unlike previous models, the free energy density includes the proposed modified form of the particle orientational energy, and also a contribution describing the surface saddle-splay deformations of the liquid crystal matrix.

  12. Double-twist cylinders in liquid crystalline cholesteric blue phases observed by transmission electron microscopy.

    PubMed

    Tanaka, Shu; Yoshida, Hiroyuki; Kawata, Yuto; Kuwahara, Ryusuke; Nishi, Ryuji; Ozaki, Masanori

    2015-01-01

    Cholesteric blue phases are liquid crystalline phases in which the constituent rod-like molecules spontaneously form three-dimensional, helical structures. Despite theoretical predictions that they are composed of cylindrical substructures within which the liquid crystal molecules are doubly twisted, real space observation of the arrangement of such structures had not been performed. Through transmission electron microscopy of photopolymerized blue phases with controlled lattice plane orientations, we report real space observation and comparison of the lattice structures of blue phases I and II. The two systems show distinctly different contrasts, reflecting the theoretically predicted, body centred and simple cubic arrangement of the double-twist cylinders. Transmission electron microscopy also reveals different tendencies of the two blue phases to align on unidirectionally rubbed surfaces. We thus show that TEM observation of alignment-controlled, photopolymerized liquid crystals can be a powerful tool to investigate complex liquid crystalline order. PMID:26530779

  13. Double-twist cylinders in liquid crystalline cholesteric blue phases observed by transmission electron microscopy

    PubMed Central

    Tanaka, Shu; Yoshida, Hiroyuki; Kawata, Yuto; Kuwahara, Ryusuke; Nishi, Ryuji; Ozaki, Masanori

    2015-01-01

    Cholesteric blue phases are liquid crystalline phases in which the constituent rod-like molecules spontaneously form three-dimensional, helical structures. Despite theoretical predictions that they are composed of cylindrical substructures within which the liquid crystal molecules are doubly twisted, real space observation of the arrangement of such structures had not been performed. Through transmission electron microscopy of photopolymerized blue phases with controlled lattice plane orientations, we report real space observation and comparison of the lattice structures of blue phases I and II. The two systems show distinctly different contrasts, reflecting the theoretically predicted, body centred and simple cubic arrangement of the double-twist cylinders. Transmission electron microscopy also reveals different tendencies of the two blue phases to align on unidirectionally rubbed surfaces. We thus show that TEM observation of alignment-controlled, photopolymerized liquid crystals can be a powerful tool to investigate complex liquid crystalline order. PMID:26530779

  14. Double-twist cylinders in liquid crystalline cholesteric blue phases observed by transmission electron microscopy

    NASA Astrophysics Data System (ADS)

    Tanaka, Shu; Yoshida, Hiroyuki; Kawata, Yuto; Kuwahara, Ryusuke; Nishi, Ryuji; Ozaki, Masanori

    2015-11-01

    Cholesteric blue phases are liquid crystalline phases in which the constituent rod-like molecules spontaneously form three-dimensional, helical structures. Despite theoretical predictions that they are composed of cylindrical substructures within which the liquid crystal molecules are doubly twisted, real space observation of the arrangement of such structures had not been performed. Through transmission electron microscopy of photopolymerized blue phases with controlled lattice plane orientations, we report real space observation and comparison of the lattice structures of blue phases I and II. The two systems show distinctly different contrasts, reflecting the theoretically predicted, body centred and simple cubic arrangement of the double-twist cylinders. Transmission electron microscopy also reveals different tendencies of the two blue phases to align on unidirectionally rubbed surfaces. We thus show that TEM observation of alignment-controlled, photopolymerized liquid crystals can be a powerful tool to investigate complex liquid crystalline order.

  15. Liquid crystalline thermosets from ester, ester-imide, and ester-amide oligomers

    NASA Technical Reports Server (NTRS)

    Dingemans, Theodorous J. (Inventor); Weiser, Erik S. (Inventor); St. Clair, Terry L. (Inventor)

    2005-01-01

    Main chain thermotropic liquid crystal esters, ester-imides, and ester-amides were prepared from AA, BB, and AB type monomeric materials and were end-capped with phenylacetylene, phenylmaleimide, or nadimide reactive end-groups. The resulting reactive end-capped liquid crystal oligomers exhibit a variety of improved and preferred physical properties. The end-capped liquid crystal oligomers are thermotropic and have, preferably, molecular weights in the range of approximately 1000-15,000 grams per mole. The end-capped liquid crystal oligomers have broad liquid crystalline melting ranges and exhibit high melt stability and very low melt viscosities at accessible temperatures. The end-capped liquid crystal oligomers are stable for up to an hour in the melt phase. These properties make the end-capped liquid crystal oligomers highly processable by a variety of melt process shape forming and blending techniques including film extrusion, fiber spinning, reactive injection molding (RIM), resin transfer molding (RTM), resin film injection (RFI), powder molding, pultrusion, injection molding, blow molding, plasma spraying and thermo-forming. Once processed and shaped, the end-capped liquid crystal oligomers were heated to further polymerize and form liquid crystalline thermosets (LCT). The fully cured products are rubbers above their glass transition temperatures. The resulting thermosets display many properties that are superior to their non-end-capped high molecular weight analogs.

  16. Liquid Crystalline Thermosets from Ester, Ester-Imide, and Ester-Amide Oligomers

    NASA Technical Reports Server (NTRS)

    Dingemans, Theodornus J. (Inventor); Weiser, Erik S. (Inventor); SaintClair, Terry L. (Inventor)

    2005-01-01

    Main chain thermotropic liquid crystal esters, ester-imides, and ester-amides were prepared from AA, BB, and AB type monomeric materials and were end-capped with phenylacetylene, phenylmaleimide, or nadimide reactive end-groups. The resulting reactive end-capped liquid crystal oligomers exhibit a variety of improved and preferred physical properties. The end-capped liquid crystal oligomers are thermotropic and have, preferably, molecular weights in the range of approximately 1000-15,OOO grams per mole. The end-capped liquid crystal oligomers have broad liquid crystalline melting ranges and exhibit high melt stability and very low melt viscosities at accessible temperatures. The end-capped liquid crystal oligomers are stable for up to an hour in the melt phase. These properties make the end-capped liquid crystal oligomers highly processable by a variety of melt process shape forming and blending techniques including film extrusion, fiber spinning, reactive injection molding (RIM), resin transfer molding (RTM), resin film injection (RFI), powder molding, pultrusion, injection molding, blow molding, plasma spraying and thermo-forming. Once processed and shaped, the end- capped liquid crystal oligomers were heated to further polymerize and form liquid crystalline thermosets (LCT). The fully cured products are rubbers above their glass transition temperatures. The resulting thermosets display many properties that are superior to their non-end-capped high molecular weight analogs.

  17. Crystalline Oligo(ethylene sulfide) Domains Define Highly Stable Supramolecular Block Copolymer Assemblies.

    PubMed

    Brubaker, Carrie E; Velluto, Diana; Demurtas, Davide; Phelps, Edward A; Hubbell, Jeffrey A

    2015-07-28

    With proper control over copolymer design and solvation conditions, self-assembled materials display impressive morphological variety that encompasses nanoscale colloids as well as bulk three-dimensional architectures. Here we take advantage of both hydrophobicity and crystallinity to mediate supramolecular self-assembly of spherical micellar, linear fibrillar, or hydrogel structures by a family of highly asymmetric poly(ethylene glycol)-b-oligo(ethylene sulfide) (PEG-OES) copolymers. Assembly structural polymorphism was achieved with modification of PEG-OES topology (linear versus multiarm) and with precise, monomer-by-monomer control of OES length. Notably, all three morphologies were accessed utilizing OES oligomers with degrees of polymerization as short as three. These exceptionally small assembly forming blocks represent the first application of ethylene sulfide oligomers in supramolecular materials. While the assemblies demonstrated robust aqueous stability over time, oxidation by hydrogen peroxide progressively converted ethylene sulfide residues to increasingly hydrophilic and amorphous sulfoxides and sulfones, causing morphological changes and permanent disassembly. We utilized complementary microscopic and spectroscopic techniques to confirm this chemical stimulus-responsive behavior in self-assembled PEG-OES colloidal dispersions and physical gels. In addition to inherent stimulus-responsive behavior, fibrillar assemblies demonstrated biologically relevant molecular delivery, as confirmed by the dose-dependent activation of murine bone marrow-derived dendritic cells following fibril-mediated delivery of the immunological adjuvant monophosphoryl lipid A. In physical gels composed of either linear or multiarm PEG-OES precursors, rheologic analysis also identified mechanical stimulus-responsive shear thinning behavior. Thanks to the facile preparation, user-defined morphology, aqueous stability, carrier functionality, and stimuli-responsive behaviors of

  18. Blue phase liquid crystalline polymers and its application in manned spacecraft

    NASA Astrophysics Data System (ADS)

    Zhang, Dongpu; Xu, Fang; Li, Wangling; Guo, Weiguo

    2014-11-01

    As novel Liquid Crystal Display (LCD) materials, blue phase liquid crystalline polymers have attracted considerable attention and interests, mainly because of their unique properties, including wide angle of view, fast response times and selective reflection of light. Blue phases are mesophases usually exhibited by highly chiral materials and commonly occur in a narrow temperature range below the isotropic phase.They are optically active and non-birefringent, while exhibit Bragg diffraction of light in the visible wavelength. So they can improve and enhance the performances of liquid crystal display in manned spacecraft. The development and recent advances are reviewed with a brief introduction of the history of the blue phase studies. Some special properties are analyzed especially the frustration in the double twist molecular alignment. The application prospect of blue phase liquid crystalline polymers in manned spacecraft are discussed. Because of high resolution, high response speed, low power, low weight and small footprint, blue phase liquid crystal displays can meet the technique requirements on displays in our future manned spacecrafts, especially space station. Blue phase liquid crystalline polymers have more superior performances on viewing angle. Thus, blue phase LCD is a better choice to improve the viewing angle in manned spacecrafts.

  19. Electrophoretic Deposition for Cholesteric Liquid-Crystalline Devices with Memory and Modulation of Reflection Colors.

    PubMed

    Tokunaga, Shoichi; Itoh, Yoshimitsu; Yaguchi, Yuya; Tanaka, Hiroyuki; Araoka, Fumito; Takezoe, Hideo; Aida, Takuzo

    2016-06-01

    The first design strategy that allows both memorization and modulation of the liquid-crystalline reflection color is reported. Electrophoretic deposition of a tailored ionic chiral dopant is key to realizing this unprecedented function, which may pave the way for the development of full-color e-paper that can operate without the need of color filters. PMID:27027423

  20. Bundled Stack Discotic Columnar Liquid Crystalline Phase with Inter Stack Electronic Coupling

    SciTech Connect

    Wang, Bin; Sun, Runkun; Gunbas, Duygu; Zhang, Hao; Grozema, Ferdinand; Xiao, Kai; Jin, Shi

    2015-01-01

    The first compound capable of forming a bundled stack discotic columnar liquid crystalline (BSDCLC) phase was designed and synthesized. The unique perylene anhydride inter stack interaction was found to be the key to the formation of the BSDCLC structure and inter stack electronic coupling (ISEC).

  1. An electric-field-responsive discotic liquid-crystalline hexa-peri-hexabenzocoronene/oligothiophene hybrid.

    PubMed

    Hu, Nan; Shao, Renfan; Shen, Yongqiang; Chen, Dong; Clark, Noel A; Walba, David M

    2014-04-01

    A novel hexa-peri-hexabenzocoronene/oligothiophene hybrid is shown to self-assemble into a hexagonal columnar liquid crystalline phase, and respond to applied electric fields resulting in uniform homeotropic or parallel alignment depending upon the electrode structure. Furthermore, the columnar orientation can be maintained even after removal of the electric field unless the material is heated above the clearing temperature. PMID:24818257

  2. A bundled-stack discotic columnar liquid crystalline phase with inter-stack electronic coupling

    DOE PAGESBeta

    Wang, Bin; Sun, Runkun; Günbaş, Duygu D.; Zhang, Hao; Grozema, Ferdinand C.; Xiao, Kai; Jin, Shi

    2015-06-15

    The first compound proving to be capable of forming a bundled-stack discotic columnar liquid crystalline (BSDCLC) phase was designed and synthesized. Finally, the unique perylene anhydride inter-stack interaction was found to be the key to the formation of the BSDCLC structure and inter-stack electronic coupling (ISEC).

  3. Effect of Liquid-Crystalline Epoxy Backbone Structure on Thermal Conductivity of Epoxy-Alumina Composites

    NASA Astrophysics Data System (ADS)

    Giang, Thanhkieu; Kim, Jinhwan

    2016-06-01

    In a series of papers published recently, we clearly demonstrated that the most important factor governing the thermal conductivity of epoxy-Al2O3 composites is the backbone structure of the epoxy. In this study, three more epoxies based on diglycidyl ester-terminated liquid-crystalline epoxy (LCE) have been synthesized to draw conclusions regarding the effect of the epoxy backbone structure on the thermal conductivity of epoxy-alumina composites. The synthesized structures were characterized by proton nuclear magnetic resonance (1H-NMR) and Fourier-transform infrared (FT-IR) spectroscopy. Differential scanning calorimetry, thermogravimetric analysis, and optical microscopy were also employed to examine the thermal and optical properties of the synthesized LCEs and the cured composites. All three LCE resins exhibited typical liquid-crystalline behaviors: clear solid crystalline state below the melting temperature (T m), sharp crystalline melting at T m, and transition to nematic phase above T m with consequent isotropic phase above the isotropic temperature (T i). The LCE resins displayed distinct nematic liquid-crystalline phase over a wide temperature range and retained liquid-crystalline phase after curing, with high thermal conductivity of the resulting composite. The thermal conductivity values ranged from 3.09 W/m-K to 3.89 W/m-K for LCE-Al2O3 composites with 50 vol.% filler loading. The steric effect played a governing role in the difference. The neat epoxy resin thermal conductivity was obtained as 0.35 W/m-K to 0.49 W/m-K based on analysis using the Agari-Uno model. The results clearly support the objective of this study in that the thermal conductivity of the LCE-containing networks strongly depended on the epoxy backbone structure and the degree of ordering in the cured network.

  4. A liquid crystalline polymer microlens array with tunable focal intensity by the polarization control of a liquid crystal layer

    NASA Astrophysics Data System (ADS)

    Choi, Yoonseuk; Kim, Hak-Rin; Lee, Kwang-Ho; Lee, Yong-Min; Kim, Jae-Hoon

    2007-11-01

    We propose a focal intensity tunable microlens array by using a birefringent liquid crystalline polymer for lensing action. Due to the difference of effective refractive indices, it acts as a positive or negative microlens with respect to the polarization state. As we control the incident polarization by adding a liquid crystal layer, the focal intensity can be tuned by an applied voltage. Twisted nematic and bistable ferroelectric liquid crystal modes were applied to demonstrate the possibility of various driving features such as a continuously tunable focal intensity or fast switching with memory effect.

  5. Electrically Induced Twist in Smectic Liquid-Crystalline Elastomers.

    PubMed

    Spillmann, Christopher M; Naciri, Jawad; Ratna, B R; Selinger, Robin L B; Selinger, Jonathan V

    2016-07-01

    As an approach for electrically controllable actuators, we prepare elastomers of chiral smectic-A liquid crystals, which have an electroclinic effect, i.e., molecular tilt induced by an applied electric field. Surprisingly, our experiments find that an electric field causes a rapid and reversible twisting of the film out of the plane, with a helical sense that depends on the sign of the field. To explain this twist, we develop a continuum elastic theory based on an asymmetry between the front and back of the film. We further present finite-element simulations, which show the dynamic shape change. PMID:27096378

  6. Bacterial transport of colloids in liquid crystalline environments.

    PubMed

    Trivedi, Rishi R; Maeda, Rina; Abbott, Nicholas L; Spagnolie, Saverio E; Weibel, Douglas B

    2015-11-21

    We describe the controlled transport and delivery of non-motile eukaryotic cells and polymer microparticles by swimming bacteria suspended in nematic liquid crystals. The bacteria push reversibly attached cargo in a stable, unidirectional path (or along a complex patterned director field) over exceptionally long distances. Numerical simulations and analytical predictions for swimming speeds provide a mechanistic insight into the hydrodynamics of the system. This study lays the foundation for using cargo-carrying bacteria in engineering applications and for understanding interspecies interactions in polymicrobial communities. PMID:26382153

  7. Spontaneous dislocation of a crystalline lens to the anterior chamber with pupillary block glaucoma in Noonan Syndrome: a case report

    PubMed Central

    Mukhopadhyaya, Udayaditya; Chakraborti, Chandana; Mondal, Anindita; Pattyanayak, Ujjal; Agarwal, Rajesh Kumar; Tripathi, Partha

    2014-01-01

    We report a 13-year-old child with Noonan Syndrome who developed spontaneous dislocation of the crystalline lens in anterior chamber leading to pupillary block glaucoma in the left eye and subluxation of lens in right eye. Intracapsular extraction of the dislocated lens was done in the left eye. Prompt diagnosis and management is needed in such cases to avoid glaucoma and corneal endothelial cell damage. We could not find any such case after thorough Medline search. PMID:25374640

  8. Synchronization and liquid crystalline order in soft active fluids.

    PubMed

    Leoni, M; Liverpool, T B

    2014-04-11

    We introduce a phenomenological theory for a new class of soft active fluids with the ability to synchronize. Our theoretical framework describes the macroscopic behavior of a collection of interacting anisotropic elements with cyclic internal dynamics and a periodic phase variable. This system can (i) spontaneously undergo a transition to a state with macroscopic orientational order, with the elements aligned, a liquid crystal, (ii) attain another broken symmetry state characterized by synchronization of their phase variables, or (iii) a combination of both types of order. We derive the equations describing a spatially homogeneous system and also study the hydrodynamic fluctuations of the soft modes in some of the ordered states. We find that synchronization can promote or inhibit the transition to a state with orientational order, and vice versa. We provide an explicit microscopic realization: a suspension of microswimmers driven by cyclic strokes. PMID:24766022

  9. Nanoparticle-induced widening of the temperature range of liquid-crystalline blue phases

    NASA Astrophysics Data System (ADS)

    Karatairi, Eva; Rožič, Brigita; Kutnjak, Zdravko; Tzitzios, Vassilios; Nounesis, George; Cordoyiannis, George; Thoen, Jan; Glorieux, Christ; Kralj, Samo

    2010-04-01

    Liquid-crystalline blue phases exhibit exceptional properties for applications in the display and sensor industry. However, in single component systems, they are stable only for very narrow temperature range between the isotropic and the chiral nematic phase, a feature that severely hinders their applicability. Systematic high-resolution calorimetric studies reveal that blue phase III is effectively stabilized in a wide temperature range by mixing surface-functionalized nanoparticles with chiral liquid crystals. This effect is present for two liquid crystals, yielding a robust method to stabilize blue phases, especially blue phase III. Theoretical arguments show that the aggregation of nanoparticles at disclination lines is responsible for the observed effects.

  10. Bio-based ionic liquid crystalline quaternary ammonium salts: properties and applications.

    PubMed

    Sasi, Renjith; Rao, Talasila P; Devaki, Sudha J

    2014-03-26

    In the present work, we describe the preparation, properties, and applications of novel ionic liquid crystalline quaternary ammonium salts (QSs) of 3-pentadecylphenol, a bio-based low-cost material derived from cashew nut shell liquid. Amphotropic liquid crystalline phase formation in QSs was characterized using a combination of techniques, such as DSC, PLM, XRD, SEM, and rheology, which revealed the formation of one, two, and three dimensionally ordered mesophases in different length scales. On the basis of these results, a plausible mechanism for the formation of specific modes of packing in various mesophases was proposed. Observation of anisotropic ionic conductivity and electrochemical stability suggests their application as a solid electrolyte. PMID:24571658

  11. Optically Active Liquid Crystalline Polyoxometalates via Electrostatic Encapsulation with Cholesterol-Containing Amphiphile.

    PubMed

    Zhang, Jing; Li, Jingfang; Yuan, Hong; Zhang, Guohua; Li, Bao; Li, Wen; Wei, Xuehong; Duan, Xin-E; Wu, Lixin

    2016-07-20

    A novel cholesterol-containing amphiphile was designed and prepared in the study, which is a room-temperature ionic liquid crystal over a broad temperature range with pronounced chiroptical properties. Four types of inorganic polyoxometalates (PMs) with different numbers of charges were encapsulated by the chiral amphiphile. The incorporation of chiral organic cations triggers achiral PMs in the complexes to show induced chirality through intermolecular interactions, as demonstrated by circular dichroism spectroscopy. The electrostatic encapsulation with mesomorphic promoters provides the inorganic PMs with liquid crystalline behavior, characterized by differential scanning calorimetry, polarized optical microscopy, and X-ray diffraction. The strategy applied herein represents a unique example of liquid crystalline PM complexes with optical activity. PMID:27197844

  12. Lyotropic liquid crystalline L3 phase silicated nanoporous monolithic composites and their production

    DOEpatents

    McGrath, Kathryn M.; Dabbs, Daniel M.; Aksay, Ilhan A.; Gruner, Sol M.

    2003-10-28

    A mesoporous ceramic material is provided having a pore size diameter in the range of about 10-100 nanometers produced by templating with a ceramic precursor a lyotropic liquid crystalline L.sub.3 phase consisting of a three-dimensional, random, nonperiodic network packing of a multiple connected continuous membrane. A preferred process for producing the inesoporous ceramic material includes producing a template of a lyotropic liquid crystalline L.sub.3 phase by mixing a surfactant, a co-surfactant and hydrochloric acid, coating the template with an inorganic ceramic precursor by adding to the L.sub.3 phase tetramethoxysilane (TMOS) or tetraethoxysilane (TEOS) and then converting the coated template to a ceramic by removing any remaining liquids.

  13. Polarization axis-selective realignment of a photoreactive liquid crystalline composite with homogeneous alignment

    NASA Astrophysics Data System (ADS)

    Sasaki, Tomoyuki; Shoho, Takashi; Goto, Kohei; Sakamoto, Moritsugu; Noda, Kohei; Kawatsuki, Nobuhiro; Ono, Hiroshi

    2016-06-01

    We investigated the photoalignment properties of a liquid crystalline composite. The composite consisted of a low molecular weight nematic liquid crystal (LC) and a photoreactive liquid crystalline polymer containing 4-(4-methoxycinnamoyloxy)biphenyl side groups. Homogeneously aligned LC composite cells were fabricated using rubbed substrates and were then exposed to a linearly polarized (LP) ultraviolet (UV) laser beam. The alignment states of the LC composites were characterized using a LP visible laser beam. The LC composite in the cell was realigned by LP UV exposure and subsequent annealing. The direction of the realignment could be controlled by the polarization direction of the LP UV beam. The relationship between the realignment direction and the rubbing strength of the substrates was also investigated. A large realignment was induced in the LC composite cell when the azimuthal anchoring strength of the rubbed substrates was relatively weak.

  14. Nonionic diethanolamide amphiphiles with isoprenoid-type hydrocarbon chains: thermotropic and lyotropic liquid crystalline phase behaviour

    SciTech Connect

    Sagnella, Sharon M.; Conn, Charlotte E.; Krodkiewska, Irena; Drummond, Calum J.

    2014-09-24

    The thermotropic and lyotropic liquid crystalline phase behaviour of a series of diethanolamide amphiphiles with isoprenoid-type hydrocarbon chains (geranoyl, H-farnesoyl, and phytanoyl) has been investigated. When neat, both H-farnesoyl and phytanoyl diethanolamide form a smectic liquid crystalline structure at sub-zero temperatures. In addition, all three diethanolamides exhibit a glass transition temperature at around -73 C. Geranoyl diethanolamide forms a lamellar crystalline phase with a lattice parameter of 17.4 {angstrom} following long term storage accompanied by the loss of the glass transition. In the presence of water, H-farnesoyl and phytanoyl diethanolamide form lyotropic liquid crystalline phases, whilst geranoyl diethanolamide forms an L{sub 2} phase. H-farnesoyl diethanolamide forms a fluid lamellar phase (L{sub {alpha}}) at room temperature and up to {approx} 40 C. Phytanoyl diethanolamide displays a rich mesomorphism forming the inverse diamond (Q{sub II}{sup D}) and gyroid (Q{sub II}{sup G}) bicontinuous cubic phases in addition to an L{sub {alpha}} phase.

  15. Solution-based synthesis of crystalline silicon from liquid silane through laser and chemical annealing.

    PubMed

    Iyer, Ganjigunte R S; Hobbie, Erik K; Guruvenket, Srinivasan; Hoey, Justin M; Anderson, Kenneth J; Lovaasen, John; Gette, Cody; Schulz, Douglas L; Swenson, Orven F; Elangovan, Arumugasamy; Boudjouk, P

    2012-05-01

    We report a solution process for the synthesis of crystalline silicon from the liquid silane precursor cyclohexasilane (Si(6)H(12)). Polysilane films were crystallized through thermal and laser annealing, with plasma hydrogenation at atmospheric pressure generating further structural changes in the films. The evolution from amorphous to microcrystalline is characterized using scanning electron microscopy (SEM), atomic force microscopy (AFM), Raman spectroscopy and impedance spectroscopy. A four-decade enhancement in the electrical conductivity is attributed to a disorder-order transition in a bonded Si network. Our results demonstrate a potentially attractive approach that employs a solution process coupled with ambient postprocessing to produce crystalline silicon thin films. PMID:22545711

  16. Polycontinuous Lyotropic Liquid Crystalline Network Phases from Gemini Dicarboxylate Surfactants

    NASA Astrophysics Data System (ADS)

    Mahanthappa, Mahesh; Sorenson, Gregory; Schmitt, Adam

    2015-03-01

    Arising from the water concentration-dependent self-assembly of amphiphilic molecules, lyotropic liquid crystals (LLCs) form a wide variety of structurally periodic nanoscale morphologies including discontinuous micellar phases (I), hexagonally-packed cylinders (C), and lamellar (L) phases. In intermediate amphiphile concentration windows between the L and C phases, one typically observes three bicontinuous cubic network phases: gyroid (G), diamond (D), and primitive (P). Recent theoretical work has suggested the possible stability of a variety of non-cubic network phase LLCs, yet none of these phases have been previously observed. In this presentation, we describe the experimental discovery of the first triply periodic network phase LLC with 3D-hexagonal symmetry (space group #193) in binary mixtures of water with a simple gemini dicarboxylate surfactant based on dodecanoic acid. Using a combination of SAXS and rheological methods, we structurally characterize this new phase and show that it is comprised of three interpenetrating lipidic networks of 3-fold connectors in a matrix of water. This finding highlights the unusual aqueous phase behavior of gemini surfactants and suggests new methods for discovering and stabilizing new network phase LLCs beyond the gyroid.

  17. Design of Functional Materials based on Liquid Crystalline Droplets

    PubMed Central

    Miller, Daniel S.; Wang, Xiaoguang; Abbott, Nicholas L.

    2014-01-01

    This brief perspective focuses on recent advances in the design of functional soft materials that are based on confinement of low molecular weight liquid crystals (LCs) within micrometer-sized droplets. While the ordering of LCs within micrometer-sized domains has been explored extensively in polymer-dispersed LC materials, recent studies performed with LC domains with precisely defined size and interfacial chemistry have unmasked observations of confinement-induced ordering of LCs that do not follow previously reported theoretical predictions. These new findings, which are enabled in part by advances in the preparation of LCs encapsulated in polymeric shells, are opening up new opportunities for the design of soft responsive materials based on surface-induced ordering transitions. These materials are also providing new insights into the self-assembly of biomolecular and colloidal species at defects formed by LCs confined to micrometer-sized domains. The studies presented in this perspective serve additionally to highlight gaps in knowledge regarding the ordering of LCs in confined systems. PMID:24882944

  18. Three-dimensional colloidal crystals in liquid crystalline blue phases

    PubMed Central

    Ravnik, Miha; Alexander, Gareth P.; Yeomans, Julia M.; Žumer, Slobodan

    2011-01-01

    Applications for photonic crystals and metamaterials put stringent requirements on the characteristics of advanced optical materials, demanding tunability, high Q factors, applicability in visible range, and large-scale self-assembly. Exploiting the interplay between structural and optical properties, colloidal lattices embedded in liquid crystals (LCs) are promising candidates for such materials. Recently, stable two-dimensional colloidal configurations were demonstrated in nematic LCs. However, the question as to whether stable 3D colloidal structures can exist in an LC had remained unanswered. We show, by means of computer modeling, that colloidal particles can self-assemble into stable, 3D, periodic structures in blue phase LCs. The assembly is based on blue phases providing a 3D template of trapping sites for colloidal particles. The particle configuration is determined by the orientational order of the LC molecules: Specifically, face-centered cubic colloidal crystals form in type-I blue phases, whereas body-centered crystals form in type-II blue phases. For typical particle diameters (approximately 100 nm) the effective binding energy can reach up to a few 100 kBT, implying robustness against mechanical stress and temperature fluctuations. Moreover, the colloidal particles substantially increase the thermal stability range of the blue phases, for a factor of two and more. The LC-supported colloidal structure is one or two orders of magnitude stronger bound than, e.g., water-based colloidal crystals. PMID:21368186

  19. In situ polarized micro-Raman investigation of periodic structures realized in liquid-crystalline composite materials.

    PubMed

    Castriota, Marco; Fasanella, Angela; Cazzanelli, Enzo; De Sio, Luciano; Caputo, Roberto; Umeton, Cesare

    2011-05-23

    In situ polarized micro-Raman Spectroscopy has been utilized to determine the liquid crystal configuration inside a periodic liquid crystalline composite structure made of polymer slices alternated to films of liquid crystal. Liquid crystal, Norland Optical Adhesive (NOA-61) monomer and its polymerized form have been investigated separately. The main Raman features, used as markers for the molecular orientation estimation, have been identified. In situ polarized Raman spectra indicate that the orientation of the liquid crystal director inside the structure is perpendicular to its polymeric slices. Results show the usefulness of in situ polarized micro-Raman spectroscopy to investigate liquid crystalline composite structures. PMID:21643304

  20. A bicontinuous tetrahedral structure in a liquid-crystalline lipid

    NASA Astrophysics Data System (ADS)

    Longley, William; McIntosh, Thomas J.

    1983-06-01

    The structure of most lipid-water phases can be visualized as an ordered distribution of two liquid media, water and hydrocarbons, separated by a continuous surface covered by the polar groups of the lipid molecules1. In the cubic phases in particular, rod-like elements are linked into three-dimensional networks1,2. Two of these phases (space groups Ia3d and Pn3m) contain two such three-dimensional networks mutually inter-woven and unconnected. Under the constraints of energy minimization3, the interface between the components in certain of these `porous fluids' may well resemble one of the periodic minimal surface structures of the type described mathematically by Schwarz4,5. A structure of this sort has been proposed for the viscous isotropic (cubic) form of glycerol monooleate (GMO) by Larsson et al.6 who suggested that the X-ray diagrams of Lindblom et al.7 indicated a body-centred crystal structure in which lipid bilayers might be arranged as in Schwarz's octahedral surface4. We have now found that at high water contents, a primitive cubic lattice better fits the X-ray evidence with the material in the crystal arranged in a tetrahedral way. The lipid appears to form a single bilayer, continuous in three dimensions, separating two continuous interlinked networks of water. Each of the water networks has the symmetry of the diamond crystal structure and the bilayer lies in the space between them following a surface resembling Schwarz's tetrahedral surface4.

  1. Fluorescence and lasing in liquid crystalline photonic bandgap materials

    NASA Astrophysics Data System (ADS)

    Cao, Wenyi

    Cholesteric liquid crystals (CLCs) and cholesteric blue phases (BPs) are one-dimensional and three-dimensional photonic bandgap (PGB) materials. In this work, fluorescence and lasing are experimentally studied in dye-doped CLC films and BPs, together with the calculations of density of states rho in CLC films. The normal modes of light propagation in a CLC film in the direction along the helical axis have been obtained analytically, using transfer matrix method. Two normal modes are elliptically polarized and their rho differ greatly. The value and wavelength of the largest rho depend on the CLC film thickness. The fluorescence spectra of dye DCM in CLC films are greatly altered: suppressed in the stop band and enhanced at band edges with intensity oscillations. The altered fluorescence spectra are in good agreement with the calculated spectra from rho. The fluorescence lifetimes, however, have no measurable difference. At high dye concentration, the fluorescence intensity is quenched by the formation of dye excimers. Mirrorless lasing in CLC films has been studied systematically. The lasing wavelengths and thresholds are in good agreement with the calculated values from rho. The threshold is optimized over CLC film thickness and dye concentration. Lasing at defect modes has been observed in CLC composite structures. Photon-counting statistics confirms the transition from the incoherent fluorescence to coherent laser emission with increasing pump energy. The totally coherent emitting area is estimated from the diffraction pattern of the CLC laser emission. The structures of BPs are characterized through textures and reflection measurements. In BP I, the stimulated emission is due to the multiple reflection of the fluorescence by small BP I crystals. In large BP II single crystals, the fluorescence is altered and lasing occurs at edges of the reflection peak or at defect modes. Lasing in three dimensions has been observed for the first time in PGB materials, and

  2. X-ray diffraction study of thermotropic liquid crystalline polyesters and diester model compounds

    NASA Astrophysics Data System (ADS)

    Chin, H. H.; Azaroff, L. V.; Griffin, A. C.

    1987-10-01

    Two nematic liquid crystalline polyesters were examined by X-ray diffraction following quenching from the nematic temperature in a magnetic field of 15 tesla. It was not possible to quench an aligned nematic glass; instead a polycrystalline phase showing some preferred orientation or an unoriented nematic melt yielded monodomain nematic diffraction patterns with one resembling that of a fiber (crystalline) photograph while the other showed good nematic alignment which could be enhanced slightly by annealing. A series of Siamese-twin diester model compounds also examined at their respective nematic temperatures in a magnetic field of compounds also were examined at their crystalline phase at room temperature. All displayed well-aligned nematic monodomains above the crystallization point.

  3. Shear Flow Induced Transition from Liquid-Crystalline to Polymer Behavior in Side-Chain Liquid Crystal Polymers

    NASA Astrophysics Data System (ADS)

    Noirez, L.; Lapp, A.

    1997-01-01

    We determine the structure and conformation of side-chain liquid-crystalline polymers subjected to shear flow in the vicinity of the smectic phase by neutron scattering on the velocity gradient plane. Below the nematic-smectic transition we observe a typical liquid-crystal behavior; the smectic layers slide, leading to a main-chain elongation parallel to the velocity direction. In contrast, a shear applied above the transition induces a tilted main-chain conformation which is typical for polymer behavior.

  4. Single cell-gap transflective liquid crystal device created by controlling the pretilt angle using a liquid crystalline reactive monomer.

    PubMed

    Jeon, Eun-Young; Kim, Ki-Han; Lee, Ji-Hoon; Yoon, Tae-Hoon

    2011-12-01

    We present a single cell-gap transflective liquid crystal (LC) device using a homogeneous alignment polyimide (H-PI) mixed with a liquid crystalline reactive monomer that is able to vertically align the LC. We obtain two different pretilt angles in each pixel through the region by region control of the UV exposure time. The smaller pretilt angle is used to obtain a half-wave phase retardation for the transmissive part, whereas the larger pretilt angle is used to obtain a quarter-wave phase retardation for the reflective part. PMID:22273954

  5. Photogeneration and enhanced charge transport in aligned smectic liquid crystalline organic semiconductor

    NASA Astrophysics Data System (ADS)

    Paul, Sanjoy; Ellman, Brett; Tripathi, Suvagata; Twieg, Robert J.

    2015-10-01

    Liquid crystalline organic semiconductors are emerging candidates for applications in electronic and photonic devices. One of the most attractive aspects of such materials is the potential, in principle, to easily control and manipulate the molecular alignment of the semiconductor over large length scales. Here, we explore the consequences of alignment in a model smectic liquid crystalline semiconductor, and find that the photogeneration efficiency is a strong function of incident polarization in aligned samples. A straightforward theory shows that such behavior is a general feature of aligned materials, regardless of the details of photophysics. Furthermore, we uncover tentative evidence that the mobility of aligned samples is substantially enhanced. Both of these phenomena are of significant technological importance.

  6. Photogeneration and enhanced charge transport in aligned smectic liquid crystalline organic semiconductor

    SciTech Connect

    Paul, Sanjoy; Ellman, Brett; Tripathi, Suvagata; Twieg, Robert J.

    2015-10-07

    Liquid crystalline organic semiconductors are emerging candidates for applications in electronic and photonic devices. One of the most attractive aspects of such materials is the potential, in principle, to easily control and manipulate the molecular alignment of the semiconductor over large length scales. Here, we explore the consequences of alignment in a model smectic liquid crystalline semiconductor, and find that the photogeneration efficiency is a strong function of incident polarization in aligned samples. A straightforward theory shows that such behavior is a general feature of aligned materials, regardless of the details of photophysics. Furthermore, we uncover tentative evidence that the mobility of aligned samples is substantially enhanced. Both of these phenomena are of significant technological importance.

  7. Depolymerization of crystalline cellulose catalyzed by acidic ionic liquids grafted onto sponge-like nanoporous polymers.

    PubMed

    Liu, Fujian; Kamat, Ranjan K; Noshadi, Iman; Peck, Daniel; Parnas, Richard S; Zheng, Anmin; Qi, Chenze; Lin, Yao

    2013-10-01

    The acidic ionic liquid (IL) functionalized polymer (PDVB-SO3H-[C3vim][SO3CF3]) possesses abundant nanoporous structures, strong acid strength and unique capability for deconstruction of crystalline cellulose into sugars in ILs. The polymer shows much improved catalytic activities in comparison with mineral acids, homogeneous acidic ionic liquids and the acidic resins such as Amberlyst 15. The enhanced catalytic activity found in the polymer is attributed to synergistic effects between the strongly acidic group and the ILs grafted onto the polymer, which by itself is capable of breaking down the crystalline structures of cellulose. This study may help develop cost-effective and green routes for conversion of biomass to fuels. PMID:23958800

  8. Xanthan Gum-a lyotropic, liquid crystalline polymer and its properties as a suspending agent

    SciTech Connect

    Salamone, J.C.; Clough, S.B.; Jamison, D.E.; Reid, K.I.G.; Salamone, A.B.

    1982-08-01

    Studies a variety of xanthan solutions of various polymer concentrations in the presence and absence of various salts under a polarized light microscope (100X) in order to test xanthan gum for liquid crystalline order. Xanthan gum, a polysaccharide used in drilling fluids and in tertiary recovery, has relatively stable viscosity properties as a function of salt concentration, pH, temperature, and shear degradation. With solutions from 2 to 10% (wt/vol) xanthan gum in distilled water at room temperature, birefringent, ordered domains were observed at 10% concentration, with a decrease in birefringence as the polymer concentration decreased. When the xanthan solution is sheared between a glass slide and a cover slip, the optic axis (chain direction) aligns using the shear direction (as determined by the colors displayed using a first-order red plate). Examines liquid crystalline behavior of other naturally occurring polymers.

  9. Induced birefringence and dichroism in azo polymers. Comparison between amorphous and liquid crystalline polymers

    SciTech Connect

    Natansohn, A.; Brown, D.; Rochon, P.

    1993-12-31

    Macroscopic order can be induced in amorphous high-Tg azo polymers (usually containing electron-donor - electron-acceptor substituted azobenzene moieties) by exposure to polarized light. The phenomenon is based on a series of trans-cis-trans isomerization cycles and the induced birefringence is typically of 2x10{sup {minus}2}. The ordered domains can be returned to randomness ({open_quotes}erased{close_quotes}) using circularly polarized light. This paper will present a comparison between amorphous and liquid crystalline azo polymers. The most significant difference between these two types of polymers is that any other type of concert with the azo moiety. Consequently the dichroism and birefringence induced in the liquid crystalline polymers can be one order of magnitude higher than in the amorphous polymers. At the same time, however, the time required to achieve saturation also increases by at least one order of magnitude.

  10. REVIEWS OF TOPICAL PROBLEMS: Supermolecular liquid-crystalline structures in solutions of amphiphilic molecules

    NASA Astrophysics Data System (ADS)

    Vedenov, A. A.; Levchenko, E. B.

    1983-09-01

    This paper reviews the physical properties of liquid-crystalline phases arising in solutions containing molecules of amphiphilic substances. The basic characteristics of micelle formation in dilute solutions, models of sphere-disk or sphere-cylinder structural transformations, as well as phase transitions related to the appearance of lyotropic mesophases in the system, including nematic, lamellar, hexagonal, and others, are examined. The results of experimental and theoretical investigation of "solvation" forces acting between micelles in the solvent, as well as recently studied models of swelling of lamellar phases are presented. The phenomena occurring near the inversion point of microemulsions in amphiphile-oil-water systems are examined briefly. The role of liquid-crystalline ordering in some biological systems is discussed.

  11. Selective Sequence for the Peptide-Triggered Phase Transition of Lyotropic Liquid-Crystalline Structures.

    PubMed

    Liu, Qingtao; Dong, Yao-Da; Boyd, Ben J

    2016-05-24

    A novel concept of using mixed lipids to construct selective peptide-sequence-sensing lyotropic liquid-crystalline (LLC) dispersion systems was investigated. The LLC systems were constructed using a mixture of phytantriol, a lipid that forms lyotropic liquid-crystalline phases, and a novel synthesized peptide-lipid (peplipid) for sensing a target peptide with the RARAR sequence. The internal structure of the dispersed LLC particles was converted from the lamellar structure (liposomes) to the inverse bicontinuous cubic phase (cubosomes) in the presence of the target peptide. The addition of common human proteins did not induce any structural change, indicating a high selectivity of interaction with the target peptide. The concept has potential for the design of targeted controlled release drug delivery agents. PMID:27148806

  12. Shape-memory effect of nanocomposites based on liquid-crystalline elastomers

    NASA Astrophysics Data System (ADS)

    Marotta, A.; Lama, G. C.; Gentile, G.; Cerruti, P.; Carfagna, C.; Ambrogi, V.

    2016-05-01

    In this work, nanocomposites based on liquid crystalline (LC) elastomers were prepared and characterized in their shape memory properties. For the synthesis of materials, p-bis(2,3-epoxypropoxy)-α-methylstilbene (DOMS) was used as mesogenic epoxy monomer, sebacic acid (SA) as curing agent and multi-walled carbon nanotubes (MWCNT) and graphene oxide (GO) as fillers. First, an effective compatibilization methodology was set up to improve the interfacial adhesion between the matrix and the carbonaceous nanofillers, thus obtaining homogeneous distribution and dispersion of the nanofillers within the polymer phase. Then, the obtained nanocomposite films were characterized in their morphological and thermal properties. In particular, the effect of the addition of the nanofillers on liquid crystalline behavior, as well as on shape-memory properties of the realized materials was investigated. It was found that both fillers were able to enhance the thermomechanical response of the LC elastomers, making them good candidates as shape memory materials.

  13. Rheology of a viscoelastic emulsion with a liquid crystalline polymer dispersed phase

    SciTech Connect

    Lee, H.S.; Denn, M.M. |

    1999-11-01

    The steady-shear viscosity and first normal stress difference and the dynamic storage and loss moduli have been measured for a blend consisting of a thermotropic liquid crystalline polymer dispersed in a thermoplastic fluoropolymer matrix. The components are immiscible and nonreacting. Consistency with the Palierne emulsion theory for viscoelastic blends is possible if and only if the interfacial tension contribution is negligible for droplets that are comparable in size to a liquid crystalline domain or smaller, while retaining the effect for larger droplets. Steady shear results are approximately described by the scaling of the Doi{endash}Ohta theory, but there is a significant reduction in the excess shear stress over a finite shear-rate range for the lowest concentration, which contains the smallest droplets. {copyright} {ital 1999 Society of Rheology.}

  14. Tunable structures of mixtures of magnetic particles in liquid-crystalline matrices.

    PubMed

    Peroukidis, Stavros D; Lichtner, Ken; Klapp, Sabine H L

    2015-08-14

    We investigate the self-organization of a binary mixture of similar sized rods and dipolar soft spheres by means of Monte-Carlo simulations. We model interparticle interactions by employing anisotropic Gay-Berne, dipolar and soft-sphere interactions. In the limit of vanishing magnetic moments we obtain a variety of fully miscible liquid crystalline phases including nematic, smectic and lamellar phases. For the magnetic mixture, we find that the liquid crystalline matrix supports the formation of orientationally ordered ferromagnetic chains. Depending on the relative size of the species the chains align parallel or perpendicular to the director of the rods forming uniaxial or biaxial nematic, smectic and lamellar phases. As an exemplary external perturbation we apply a homogeneous magnetic field causing uniaxial or biaxial ordering to an otherwise isotropic state. PMID:26041553

  15. Investigations on the liquid crystalline phases of cation-induced condensed DNA

    NASA Astrophysics Data System (ADS)

    Pillai, C. K. S.; Sundaresan, Neethu; Radhakrishnan Pillai, M.; Thomas, T.; Thomas, T. J.

    2005-10-01

    Viral and nonviral condensing agents are used in gene therapy to compact oligonucleotides and plasmid DNA into nanostructures for their efficient transport through the cell membranes. Whereas viral vectors are best by the toxic effects on the immune system, most of the nonviral delivery vehicles are not effective for use in clinical system. Recent investigations indicate that the supramolecular organization of DNA in the condensed state is liquid crystalline. The present level of understanding of the liquid crystalline phase of DNA is inadequate and a thorough investigation is required to understand the nature, stability, texture and the influence of various environmental conditions on the structure of the phase. The present study is mainly concerned with the physico-chemical investigations on the liquid crystalline transitions during compaction of DNA by cationic species such as polyamines and metallic cations. As a preliminary to the above investigation, studies were conducted on the evolution of mesophase transitions of DNA with various cationic counterion species using polarized light microscopy. These studies indicated significant variations in the phase behaviour of DNA in the presence of Li and other ions. Apart from the neutralization of the charges on the DNA molecule, these ions are found to influence selectively the hydration sphere of DNA that in turn influences the induction and stabilization of the LC phases. The higher stability observed with the liquid crystalline phases of Li--DNA system could be useful in the production of nanostructured DNA. In the case of the polyamine, a structural specificity effect depending on the nature, charge and structure of the polyamine used has been found to be favoured in the crystallization of DNA.

  16. Electrooptical properties of hybrid liquid crystalline systems containing CdSe quantum dots

    SciTech Connect

    Dradrach, K. Bartkiewicz, S.; Miniewicz, A.

    2014-12-08

    In this paper, we present electrooptical properties of hybrid liquid crystalline systems, which contained CdSe quantum dots (QDs). We have shown by experiments of degenerated two-wave mixing and transverse conductivity measurements that liquid crystal cells filled with nematic and doped with semiconductor nanoparticles exhibit photorefractive effect associated with photoconductivity appearing in the system. We also present the mathematical model, which explains the relationship between the photoconductivity of the layer on which the QDs reside and the generation of holographic gratings. Our research may help to develop better understanding of processes observed in such systems and create more efficient materials for holographic data storage.

  17. Electrooptical properties of hybrid liquid crystalline systems containing CdSe quantum dots

    NASA Astrophysics Data System (ADS)

    Dradrach, K.; Bartkiewicz, S.; Miniewicz, A.

    2014-12-01

    In this paper, we present electrooptical properties of hybrid liquid crystalline systems, which contained CdSe quantum dots (QDs). We have shown by experiments of degenerated two-wave mixing and transverse conductivity measurements that liquid crystal cells filled with nematic and doped with semiconductor nanoparticles exhibit photorefractive effect associated with photoconductivity appearing in the system. We also present the mathematical model, which explains the relationship between the photoconductivity of the layer on which the QDs reside and the generation of holographic gratings. Our research may help to develop better understanding of processes observed in such systems and create more efficient materials for holographic data storage.

  18. Synthesis of a liquid-crystalline resin monomer with the property of low shrinkage polymerization.

    PubMed

    Liu, Wenwen; Chen, Su; Liu, Yiran; Ma, Yuanping; Wang, Na; Zhang, Zhenting; Yang, Yuzhe

    2013-01-01

    To reduce the polymerization shrinkage of the dental resin composites, a new liquid-crystalline resin monomer was developed. The acrylate liquid crystalline resin monomer (ALCRM), (4-3-(acryloyloxy)-2-hydroxypropoxy) phenyl 4-(3-(acryloyloxy)-2-hydroxypropoxy) benzoate, was synthesized by a three-step method. Using the ALCRM as the main monomer, the degree of conversion (DC) and the volume shrinkage of the resin matrix were compared with the traditional composite resin monomer (Bis-GMA), 2,2-bis[4-(2-hydroxy-3-methacryloyloxy-propoxy)-phenyl] propane. The new monomer showed liquid crystalline characteristics with a mesomorphic phasetransition temperature between 18ºC and 42ºC. When copolymerized with triethylene glycol dimethacrylate (TEGDMA) at a weight ratio of 7:3, the DC of ALCRM was higher and the volume shrinkage was 3.62±0.26%, which was less than that of the Bis-GMA. The ALCRM exhibits promising potential for the development of superior dental resins with low volume shrinkage. PMID:23903635

  19. High-Fidelity Replica Molding of Glassy Liquid Crystalline Polymer Microstructures.

    PubMed

    Zhao, Hangbo; Wie, Jeong Jae; Copic, Davor; Oliver, C Ryan; Orbaek White, Alvin; Kim, Sanha; Hart, A John

    2016-03-01

    Liquid crystalline polymers have recently been engineered to exhibit complex macroscopic shape adaptivity, including optically- and thermally driven bending, self-sustaining oscillation, torsional motion, and three-dimensional folding. Miniaturization of these novel materials is of great interest for both fundamental study of processing conditions and for the development of shape-changing microdevices. Here, we present a scalable method for high-fidelity replica molding of glassy liquid crystalline polymer networks (LCNs), by vacuum-assisted replica molding, along with magnetic field-induced control of the molecular alignment. We find that an oxygen-free environment is essential to establish high-fidelity molding with low surface roughness. Identical arrays of homeotropic and polydomain LCN microstructures are fabricated to assess the influence of molecular alignment on the elastic modulus (E = 1.48 GPa compared to E = 0.54 GPa), and side-view imaging is used to quantify the reversible thermal actuation of individual LCN micropillars by high-resolution tracking of edge motion. The methods and results from this study will be synergistic with future advances in liquid crystalline polymer chemistry, and could enable the scalable manufacturing of stimuli-responsive surfaces for applications including microfluidics, tunable optics, and surfaces with switchable wetting and adhesion. PMID:26943057

  20. Crystalline and liquid Si3 N4 characterization by first-principles molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Mauri, Aurelio; Celino, Massimo; Castellani, Niccoló; Erbetta, Davide

    2011-05-01

    Silicon nitride (Si3 N4) has a wide range of engineering applications where its mechanical and electronic properties can be effectively exploited. In particular, in the microelectronics field, the amorphous silicon nitride films are widely used as charge storage layer in metal-alumina-nitrideoxide nonvolatile memory devices. Atomic structure of amorphous silicon nitride is characterized by an high concentration of traps that control the electric behavior of the final device by the trappingde-trapping mechanism of the electrical charge occurring in its traps. In order to have a deep understanding of the material properties and, in particular, the nature of the electrical active traps a detailed numerical characterization of the crystalline and liquid phases is mandatory. For these reasons first-principles molecular dynamics simulations are extensively employed to simulate the crystalline Si3 N4 in its crystalline and liquid phases. Good agreement with experimental results is obtained in terms of density and formation entalpy. Detailed characterization of c-Si3 N4 electronic properties is performed in terms of band structure and band gap. Then constant temperature and constant volume first-principles molecular dynamics is used to disorder a stoichiometric sample of Si3 N4 . Extensive molecular dynamics simulations are performed to obtain a reliable liquid sample whose atomic structure does not depend on the starting atomic configuration. Detailed characterization of the atomic structure is achieved in terms of radial distribution functions and total structure factor.

  1. Side-Chain Liquid Crystalline Poly(meth)acrylates with Bent-Core Mesogens

    SciTech Connect

    Chen,X.; Tenneti, K.; Li, C.; Bai, Y.; Wan, X.; Fan, X.; Zhou, Q.; Rong, L.; Hsiao, B.

    2007-01-01

    We report the design, synthesis, and characterization of side-chain liquid crystalline (LC) poly(meth)acrylates with end-on bent-core liquid crystalline (BCLC) mesogens. Both conventional free radical polymerization and atom transfer radical polymerization have been used to synthesize these liquid crystalline polymers (LCP). The resulting polymers exhibit thermotropic LC behavior. Differential scanning calorimetry, thermopolarized light microscopy, wide-angle X-ray diffraction, and small-angle X-ray scattering were used to characterize the LC structure of both monomers and polymers. The electro-optic (EO) measurement was carried out by applying a triangular wave and measuring the LC EO response. SmCP (Smectic C indicates the LC molecules are tilted with respect to the layer normal; P denotes polar ordering) phases were observed for both monomers and polymers. In LC monomers, typical antiferroelectric switching was observed. In the ground state, SmCP{sub A} (A denotes antiferroelectric) was observed which switched to SmCP{sub F} (F denotes ferroelectric) upon applying an electric field. In the corresponding LCP, a unique bilayer structure was observed, which is different from the reported BCLC bilayer SmCG (G denotes generated) phase. Most of the LCPs did not switch upon applying electric field while weak AF switching was observed in a low molecular weight poly{l_brace}3'-[4-(4-n-dodecyloxybenzoyloxy)benzoyloxy]-4-(12-acryloyloxydodecyloxy)benzoyloxybiphenyl{r_brace} sample.

  2. Monodomain and polydomain helicoids in chiral liquid-crystalline phases and their biological analogues

    NASA Astrophysics Data System (ADS)

    de Luca, G.; Rey, A. D.

    2003-10-01

    Many natural composites exhibit an architecture known as twisted plywood which imparts to them a superior set of physical properties. The origin of this structure is complex and not yet understood. However, it is thought to involve a lyotropic chiral nematic liquid-crystalline mesophase. Indeed, striking structural similarities have been observed and reported between biological fibrous composites and ordered fluids. In this work, a mathematical model based on the Landau-de Gennes theory has been developed to investigate the role played by constraining surfaces in the structural development of a composite material that experiences a liquid-crystalline state during the early steps of its morphogenesis. The goal of this study is to verify the need for an initial constraining surface in the formation of monodomain twisted plywoods as hypothesized by Neville (Tissue & Cell 20, 133 (1988); Biology of Fibrous Composites (Cambridge University Press, 1993)). The numerical simulations qualitatively confirm this theory and highlight the important role that modelling of liquid-crystalline self-assembly plays in the study of tissue morphogenesis.

  3. Crystallization induced block copolymer assembly at curved liquid-liquid interface

    NASA Astrophysics Data System (ADS)

    Qi, Hao; Zhou, Tian; Zhou, Hao; Li, Christopher; Soft Materials Lab Team

    In a selected solvent, amphiphilic block copolymers can self-assemble into various micelle structures which find widespread applications in nanomedicine. Herein we report a directed assembly of poly (l-lactide acid)-b-poly (ethylene glycol) (PLLA-b-PEG) at curved oil/water interfaces. Oil droplets were dispersed in water phase upon sonication with amphiphilic PLLA-b-PEG as the surfactant. Subsequent crystallization of PLLA segments resulted in the formation of lamellasomes consisting of crystalline PLLA shell and densely-grafted (approx.1chain/nm2) PEG layer. The structure, morphology, and mechanical properties of these unique polymer ensembles were investigated using transmission electron microscopy and atomic force microscopy. Detailed formation mechanism will be discussed in detail.

  4. Disposition and association of the steric stabilizer Pluronic® F127 in lyotropic liquid crystalline nanostructured particle dispersions.

    PubMed

    Tilley, Adam J; Drummond, Calum J; Boyd, Ben J

    2013-02-15

    Liquid crystalline nanostructured particles, such as cubosomes and hexosomes, are most often colloidally stabilised using the tri-block co-polymer Pluronic® F127. Although the effect of F127 on the internal particle nanostructure has been well studied, the associative aspects of F127 with cubosomes and hexosomes are poorly understood. In this study the quantitative association of F127 with phytantriol-based cubosomes and hexosomes was investigated. The amount of free F127 in the dispersions was determined using pressure ultra-filtration. The percentage of F127 associated with the particles plateaued with increasing F127 concentration above the critical aggregation concentration. Hence the free concentration of F127 in the dispersion medium was proposed as a key factor governing association below the CMC, and partitioning of F127 between micelles and particles occurred above the CMC. The association of F127 with the particles was irreversible on dilution. The F127 associated with both the external and internal surfaces of the phytantriol cubosomes. The effects of lipid and F127 concentration, lipid type, dilution of the dispersions and internal nanostructure were also elucidated. A greater amount of F127 was associated with cubosomes comprised of glyceryl monooleate (GMO) than those prepared using phytantriol. Hexosomes prepared using a mixture of phytantriol and vitamin E acetate (vitEA) had a greater amount of F127 associated with them than phytantriol cubosomes. Hexosomes prepared using selachyl alcohol had less F127 associated with them than phytantriol:vitEA-based hexosomes and GMO-based cubosomes. This indicated that both the lipid from which the particles are composed and the particle internal nanostructure have an influence on the association of F127 with lyotropic liquid crystalline nanostructured particles. PMID:23137909

  5. Using dislocations to probe surface reconstruction in thick freely suspended liquid crystalline films

    NASA Astrophysics Data System (ADS)

    Collett, J. A.; Martinez Zambrano, Daniel

    2015-10-01

    Surface interactions can cause freely suspended thin liquid crystalline films to form phases different from the bulk material, but it is not known what happens at the surface of thick films. Edge dislocations can be used as a marker for the boundary between the bulk center and the reconstructed surface. We use noncontact mode atomic force microscopy to determine the depth of edge dislocations below the surface of freely suspended thick films of 4-n -heptyloxybenzylidene-4-n -heptylaniline (7O.7) in the crystalline B phase. Here, 3.0 ±0.1 nm high steps are found with a width that varies with temperature between 56 and 59 ∘C. Using a strain model for the profile of liquid crystalline layers above an edge dislocation to estimate the depth of the dislocation, we find that the number of reconstructed surface layers increases from 4 to 50 layers as the temperature decreases from 59 to 56 ∘C . This trend tracks the behavior of the phase boundary in the thickness dependent phase diagram of freely suspended films of 7O.7, suggesting that the surface may be reconstructed into a smectic F region.

  6. Crystalline monolayer surface of liquid Au-Cu-Si-Ag-Pd: Metallic glass former

    SciTech Connect

    Mechler, S; Yahel, E; Pershan, P S; Meron, M; Lin, B

    2012-02-06

    It is demonstrated by means of x-ray synchrotron reflectivity and diffraction that the surface of the liquid phase of the bulk metallic glass forming alloy Au49Cu26.9Si16.3Ag5.5Pd2.3 consists of a two-dimensional crystalline monolayer phase for temperatures of up to about 50 K above the eutectic temperature. The present alloy as well as glass forming Au82Si18 and Au-Si-Ge alloys containing small amounts of Ge are the only metallic liquids to exhibit surface freezing well above the melting temperature. This suggests that the phenomena of surface freezing in metallic liquids and glass forming ability are related and probably governed by similar physical properties.

  7. Quantitation of liquid-crystalline ordering in F-actin solutions.

    PubMed

    Coppin, C M; Leavis, P C

    1992-09-01

    Actin filaments (F-actin) are important determinants of cellular shape and motility. These functions depend on the collective organization of numerous filaments with respect to both position and orientation in the cytoplasm. Much of the orientational organization arises spontaneously through liquid crystal formation in concentrated F-actin solutions. In studying this phenomenon, we found that solutions of purified F-actin undergo a continuous phase transition, from the isotropic state to a liquid crystalline state, when either the mean filament length or the actin concentration is increased above its respective threshold value. The phase diagram representing the threshold filament lengths and concentrations at which the phase transition occurs is consistent with that predicted by Flory's theory on solutions of noninteracting, rigid cylinders (Flory, 1956b). However, in contrast to other predictions based on this model, we found no evidence for the coexistence of isotropic and anisotropic phases. Furthermore, the phase transition proved to be temperature dependent, which suggests the existence of orientation-dependent interfilament interactions or of a temperature-dependent filament flexibility. We developed a simple method for growing undistorted fluorescent acrylodan-labeled F-actin liquid crystals; and we derived a simple theoretical treatment by which polarization-of-fluorescence measurements could be used to quantitate, for the first time, the degree of spontaneous filament ordering (nematic order parameter) in these F-actin liquid crystals. This order parameter was found to increase monotonically with both filament length and concentration. Actin liquid crystals can readily become distorted by a process known as "texturing." Zigzaging and helicoidal liquid crystalline textures which persisted in the absence of ATP were observed through the polarizing microscope. Possible texturing mechanisms are discussed. PMID:1330036

  8. Solution-Based Synthesis of Crystalline Silicon from Liquid Silane through Laser and Chemical Annealing

    SciTech Connect

    Iyer, Ganjigunte R. S.; Hobbie, Erik K.; Guruvenket, Srinivasan; Hoey, Justin M.; Anderson, Kenneth J.; Lovaasen, John; Gette, Cody; Schulz, Douglas L.; Swenson, Orven F.; Elangovan, Arumugasamy; Boudjouk, P.

    2012-05-23

    We report a solution process for the synthesis of crystalline silicon from the liquid silane precursor cyclohexasilane (Si6H12). Polysilane films were crystallized through thermal and laser annealing, with plasma hydrogenation at atmospheric pressure generating further structural changes in the films. The evolution from amorphous to microcrystalline is characterized using scanning electron microscopy (SEM), atomic force microscopy (AFM), Raman spectroscopy and impedance spectroscopy. A four-decade enhancement in the electrical conductivity is attributed to a disorder-order transition in a bonded Si network. Lastly, our results demonstrate a potentially attractive approach that employs a solution process coupled with ambient post-processing to produce crystalline silicon thin films.

  9. Method for forming single phase, single crystalline 2122 BCSCO superconductor thin films by liquid phase epitaxy

    NASA Technical Reports Server (NTRS)

    Pandey, Raghvendra K. (Inventor); Raina, Kanwal (Inventor); Solayappan, Narayanan (Inventor)

    1994-01-01

    A substantially single phase, single crystalline, highly epitaxial film of Bi.sub.2 CaSr.sub.2 Cu.sub.2 O.sub.8 superconductor which has a T.sub.c (zero resistance) of 83 K is provided on a lattice-matched substrate with no intergrowth. This film is produced by a Liquid Phase Epitaxy method which includes the steps of forming a dilute supercooled molten solution of a single phase superconducting mixture of oxides of Bi, Ca, Sr, and Cu having an atomic ratio of about 2:1:2:2 in a nonreactive flux such as KCl, introducing the substrate, e.g., NdGaO.sub.3, into the molten solution at 850.degree. C., cooling the solution from 850.degree. C. to 830.degree. C. to grow the film and rapidly cooling the substrate to room temperature to maintain the desired single phase, single crystalline film structure.

  10. Low temperature Raman study of a liquid crystalline system 4-Decyloxy benzoic acid (4DBA)

    NASA Astrophysics Data System (ADS)

    Vikram, K.; Nandi, Rajib; Singh, Ranjan K.

    2013-08-01

    The Raman spectra of a liquid crystalline system, 4-Decyloxy benzoic acid (4DBA) have been recorded at different temperatures within the interval 300-78 K in order to identify the structural changes in crystalline state of a nematogen and to understand the molecular alignment therein. The earlier predicted dimer structure of 4DBA was optimized with DFT method and the theoretical Raman spectra of dimer as well as monomer have been calculated for comparison with the experimental spectra. The mode specific quartic coupling coefficient; Ai,ω and phonon frequency; ωi have been calculated using temperature dependent anharmonic perturbation theory. The precise band shape analysis of Raman bands at ˜807, ˜881, ˜1255, ˜1282, ˜1436, ˜1576, ˜1604, ˜2881 and ˜3081 cm-1 gives signature of temperature induced slow crystal modification. The structural changes leading to crystal modification have been discussed.

  11. Vitrified chiral-nematic liquid crystalline films for selective reflection and circular polarization

    SciTech Connect

    Katsis, D.; Chen, P.H.M.; Mastrangelo, J.C.; Chen, S.H.; Blanton, T.N.

    1999-06-01

    Nematic and left-handed chiral-nematic liquid crystals comprising methoxybiphenylbenzoate and (S)-(-)-1-phenylethylamine pendants to a cyclohexane core were synthesized and characterized. Although pristine samples were found to be polycrystalline, thermal quenching following heating to and annealing at elevated temperatures permitted the molecular orders characteristic of liquid crystalline mesomorphism to be frozen in the glassy state. Left at room temperature for 6 months, the vitrified liquid crystalline films showed no evidence of recrystallization. An orientational order parameter of 0.65 was determined with linear dichroism of a vitrified nematic film doped with Exalite 428 at a mole fraction of 0.0025. Birefringence dispersion of a blank vitrified nematic film was determined using a phase-difference method complemented by Abbe refractometry. A series of vitrified chiral-nematic films were prepared to demonstrate selective reflection and circular polarization with a spectral region tunable from blue to the infrared region by varying the chemical composition. The experimentally measured circular polarization spectra were found to agree with the Good-Karali theory in which all four system parameters were determined a priori: optical birefringence, average refractive index, selective reflection wavelength, and film thickness.

  12. A liquid crystalline supramolecular complex of C60 with a cyclotriveratrylene derivative

    PubMed

    Felder; Heinrich; Guillon; Nicoud; Nierengarten

    2000-10-01

    Cyclotriveratrylene (CTV) derivatives substituted with 9 (1) or 18 (2) long alkyl chains have been prepared. Whereas no liquid crystalline behavior has been observed for 1, the CTV derivative 2 has mesomorphic properties. Indeed, at room temperature compound 2 exhibits a nematic phase characterized by cybotactic groups with a local lamello-columnar order. Both CTV derivatives 1 and 2 are able to form supramolecular complexes with C60 in the solid state. In both cases, the 2:1 host-guest species have been obtained as brown compounds. No liquid crystalline behavior was observed for the supramolecular complex [C60 is included in (1)2]. In contrast, observation of the brown product obtained from C60 and the CTV derivative 2 directly after preparation by polarized optical microscopy revealed a fluid birefringent phase at room temperature. When the sample is heated above 70 degrees C, the birefringence of the texture under the microscope disappears and the X-ray diffraction pattern is transformed into a pattern characteristic of a cubic phase. For the first time in thermotropic liquid crystals, the space group of this cubic phase can be assigned as I4(1)32. PMID:11072814

  13. Dynamical Study of Guest-Host Orientational Interaction in LiquidCrystalline Materials

    SciTech Connect

    Truong, Thai Viet

    2005-12-20

    Guest-host interaction has long been a subject of interest in many disciplines. Emphasis is often on how a small amount of guest substance could significantly affect the properties of a host material. This thesis describe our work in studying a guest-host effect where dye-doping of liquid crystalline materials greatly enhances the optical Kerr nonlinearity of the material. The dye molecules, upon excitation and via intermolecular interaction, provides an extra torque to reorient the host molecules, leading to the enhanced optical Kerr nonlinearity. We carried out a comprehensive study on the dynamics of the photoexcited dye-doped liquid crystalline medium. Using various experimental techniques, we separately characterized the dynamical responses of the relevant molecular species present in the medium following photo-excitation, and thus were able to follow the transient process in which photo-excitation of the dye molecules exert through guest-host interaction a net torque on the host LC material, leading to the observed enhanced molecular reorientation. We also observed for the first time the enhanced reorientation in a pure liquid crystal system, where the guest population is created through photoexcitation of the host molecules themselves. Experimental results agree quantitatively with the time-dependent theory based on a mean-field model of the guest-host interaction.

  14. Self-Assembled Cubic Liquid Crystalline Nanoparticles for Transdermal Delivery of Paeonol

    PubMed Central

    Li, Jian-Chun; Zhu, Na; Zhu, Jin-Xiu; Zhang, Wen-Jing; Zhang, Hong-Min; Wang, Qing-Qing; Wu, Xiao-Xiang; Wang, Xiu; Zhang, Jin; Hao, Ji-Fu

    2015-01-01

    Background The aim of this study was to optimize the preparation method for self-assembled glyceryl monoolein-based cubosomes containing paeonol and to characterize the properties of this transdermal delivery system to improve the drug penetration ability in the skin. Material/Methods In this study, the cubic liquid crystalline nanoparticles loaded with paeonol were prepared by fragmentation of glyceryl monoolein (GMO)/poloxamer 407 bulk cubic gel by high-pressure homogenization. We evaluated the Zeta potential of these promising skin-targeting drug-delivery systems using the Malvern Zeta sizer examination, and various microscopies and differential scanning calorimetry were also used for property investigation. Stimulating studies were evaluated based on the skin irritation reaction score standard and the skin stimulus intensity evaluation standard for paeonol cubosomes when compared with commercial paeonol ointment. In vitro tests were performed on excised rat skins in an improved Franz diffusion apparatus. The amount of paeonol over time in the in vitro penetration and retention experiments both was determined quantitatively by HPLC. Results Stimulating studies were compared with the commercial ointment which indicated that the paeonol cubic liquid crystalline nanoparticles could reduce the irritation in the skin stimulating test. Thus, based on the attractive characteristics of the cubic crystal system of paeonol, we will further exploit the cosmetic features in the future studies. Conclusions The transdermal delivery system of paeonol with low-irritation based on the self-assembled cubic liquid crystalline nanoparticles prepared in this study might be a promising system of good tropical preparation for skin application. PMID:26517086

  15. Spatially resolved charge transport study in discotic liquid crystalline organic semiconductors

    NASA Astrophysics Data System (ADS)

    Paul, Sanjoy; Semyonov, Alexander; Dawson, Nathan J.; Singer, Kenneth D.; Twieg, Robert J.; Ellman, Brett

    Spatially resolved time-of-flight photogeneration and mobility have been measured on a discotic liquid crystalline organic semiconductor using scanning time-of-flight microscopy (STOFm). STOFm simultaneously obtains time-of-flight transients and polarized transmittance across the sample. Various shapes in time-of-flight transients were observed and extracted charge transport parameters such as photogeneration efficiency, mobility, and trapping show significant spatial variation. In some cases these can be linked to electrode surface inhomogeneities. Detailed measurement methodology, experimental results and challenges in their analysis will be discussed.

  16. Alignment engineering in liquid crystalline elastomers: Free-form microstructures with multiple functionalities

    SciTech Connect

    Zeng, Hao; Cerretti, Giacomo; Wiersma, Diederik S. E-mail: wiersma@lens.unifi.it; Wasylczyk, Piotr; Martella, Daniele; Parmeggiani, Camilla E-mail: wiersma@lens.unifi.it

    2015-03-16

    We report a method to fabricate polymer microstructures with local control over the molecular orientation. Alignment control is achieved on molecular level in a structure of arbitrary form that can be from 1 to 100 μm in size, by fixing the local boundary conditions with micro-grating patterns. The method makes use of two-photon polymerization (Direct Laser Writing) and is demonstrated specifically in liquid-crystalline elastomers. This concept allows for the realization of free-form polymeric structures with multiple functionalities which are not possible to realize with existing techniques and which can be locally controlled by light in the micrometer scale.

  17. Prediction and Observation of Sustained Oscillations in a Sheared Liquid Crystalline Polymer

    NASA Astrophysics Data System (ADS)

    Grosso, M.; Crescitelli, S.; Somma, E.; Vermant, J.; Moldenaers, P.; Maffettone, P. L.

    2003-03-01

    Experimental observations of sustained oscillations of both shear stress and first normal stress differences are reported in flowing liquid crystalline polymers in a limited range of shear rates. The results can be described by considering the response of a rigid-rod model. Depending on the initial conditions, the frequency spectrum of the stress signal contains either one or two characteristic frequencies. This can be explained by the occurrence of either pure “wagging” or the coexistence of wagging and “log-rolling” behavior of the director.

  18. Interferometric Sensor of Wavelength Detuning Using a Liquid Crystalline Polymer Waveplate.

    PubMed

    Wierzba, Paweł

    2016-01-01

    Operation of a polarization interferometer for measurement of the wavelength changes of a tunable semiconductor laser was investigated. A λ/8 waveplate made from liquid crystalline polymer is placed in one of interferometers' arms in order to generate two output signals in quadrature. Wavelength was measured with resolution of 2 pm in the wavelength range 628-635 nm. Drift of the interferometer, measured in the period of 500 s, was 8 nm, which corresponded to the change in the wavelength of 1.3 pm. If needed, wavelength-dependent Heydemann correction can be used to expand the range of operation of such interferometer. PMID:27171082

  19. Finite-difference time-domain analysis of light propagation in cholesteric liquid crystalline droplet array

    NASA Astrophysics Data System (ADS)

    Yamamoto, Kaho; Iwai, Yosuke; Uchida, Yoshiaki; Nishiyama, Norikazu

    2016-08-01

    We numerically analyzed the light propagation in cholesteric liquid crystalline (CLC) droplet array by the finite-difference time-domain (FDTD) method. The FDTD method successfully reproduced the experimental light path observed in the complicated photonic structure of the CLC droplet array more accurately than the analysis of CLC droplets by geometric optics with Bragg condition, and this method help us understand the polarization of the propagating light waves. The FDTD method holds great promise for the design of various photonic devices composed of curved photonic materials like CLC droplets and microcapsules.

  20. Photomobile polymer materials: photoresponsive behavior of cross-linked liquid-crystalline polymers with mesomorphic diarylethenes.

    PubMed

    Mamiya, Jun-ichi; Kuriyama, Akito; Yokota, Naoki; Yamada, Munenori; Ikeda, Tomiki

    2015-02-16

    Cross-linked liquid-crystalline (LC) polymers with a mesomorphic diarylethene were prepared to demonstrate a versatile strategy for cross-linked photochromic LC polymers as photomobile materials. Upon exposure to UV light to cause photocyclization of the diarylethene chromophore, the cross-linked polymer films bend toward an actinic light source. By irradiation with visible light to cause a closed-ring to open-ring isomerization, the bent films revert to the initial flat state. Without visible-light irradiation, the bent films remain bent even at 120 °C, indicating high thermal stability of the cross-linked diarylethene LC polymers. PMID:25581255

  1. Interferometric Sensor of Wavelength Detuning Using a Liquid Crystalline Polymer Waveplate

    PubMed Central

    Wierzba, Paweł

    2016-01-01

    Operation of a polarization interferometer for measurement of the wavelength changes of a tunable semiconductor laser was investigated. A λ/8 waveplate made from liquid crystalline polymer is placed in one of interferometers’ arms in order to generate two output signals in quadrature. Wavelength was measured with resolution of 2 pm in the wavelength range 628–635 nm. Drift of the interferometer, measured in the period of 500 s, was 8 nm, which corresponded to the change in the wavelength of 1.3 pm. If needed, wavelength-dependent Heydemann correction can be used to expand the range of operation of such interferometer. PMID:27171082

  2. Subwavelength modulation of surface relief and refractive index in preirradiated liquid-crystalline polymer films

    SciTech Connect

    Yu Haifeng; Shishido, Atsushi; Ikeda, Tomiki

    2008-03-10

    We present a simple method to record subwavelength gratings (SWGs) in an azobenzene (AZ)-containing liquid-crystalline polymer by preirradiation. Since the cooperative motions of mesogens are eliminated in a cis-AZ-rich isotropic phase by the pretreatment, the subwavelength modulation of surface relief and refractive index (RI) was obtained. The surface relief of less than 10 nm and the RI modulation were detected by atomic force microscopy. A large phase retardation and formed birefringence were obtained in the recorded SWGs in which a possible schematic illustration of AZ was proposed.

  3. Novel biaxial nematic phases of side-chain liquid crystalline polymers

    NASA Astrophysics Data System (ADS)

    Matsuyama, Akihiko

    2012-12-01

    We present a mean field theory to describe biaxial nematic phases of side-chain liquid crystalline polymers, in which rigid side-chains (mesogens) and rigid-backbone chains favor mutually perpendicular orientations. Taking into account both excluded volume and attractive interactions between rigid rods, novel biaxial nematic phases are theoretically predicted. We calculate uniaxial and biaxial orientational order parameters as a function of temperature and the length of backbone chains. We find a first-order biaxial-biaxial phase transition and a first (or second)-order uniaxial-biaxial one, depending on the length of mesogens and backbone chains.

  4. Highly polarized emission of the liquid crystalline conjugated polymer by controlling the surface anchoring energy

    NASA Astrophysics Data System (ADS)

    In Jo, Soo; Kim, Youngsik; Baek, Ji-Ho; Yu, Chang-Jae; Kim, Jae-Hoon

    2014-01-01

    We demonstrated a highly polarized organic light-emitting diode (OLED) through the enhancement of the orientational ordering of the emitting polymer with a nematic liquid crystalline (LC) phase. The highly ordered state of the conjugate polymer was obtained by thermal annealing at the nematic temperature and strong azimuthal anchoring energy of the underlying polyimide. The order parameter of the conjugate polymer was analyzed using a second-harmonic generation model and the dichroic ratio was measured to be 22 : 1. Also, we applied our optimized OLED with high optical polarizability to an effective light source for a twisted nematic LC display.

  5. Electronic structure and charge injection at interface between electrode and liquid-crystalline semiconductor

    NASA Astrophysics Data System (ADS)

    Toda, Tohru; Hanna, Jun-ichi; Tani, Tadaaki

    2007-01-01

    The measurement and analysis of the current-voltage characteristics of a liquid-crystalline organic semiconductor 2-(4'-octyphenyl)-6-dodecyloxynaphthalene (8-PNP-O12) in contact with electrodes of Pt, Au, ITO, Cr, and Al (in the order of work function) have revealed that the injection of holes from the electrodes of Pt, Au, and indium tin oxide to 8-PNP-O12 takes place according to the Richardson-Schottky model and that an electric double layer is formed at the interface between each of these electrodes and 8-PNP-O12, making it difficult to inject holes from the former to the latter.

  6. Preparation of ordered and crosslinked films from liquid crystalline vinyl ether monomers

    SciTech Connect

    Andersson, H.; Sahlen, F.; Gedde, U.W.; Hult, A.

    1993-12-31

    Highly ordered densely crosslinked liquid crystalline poly(vinyl ether) films have been prepared by in-situ photopolymerization of oriented bifunctional mesogenic vinyl ether monomers. Orientation was achieved either by a simple surface treatment, using an unidirectionally rubbed polyimide film or by a magnetic field. Polymerization from various monomer phases resulted in LC polymer network films with different molecular organizations. The films were analyzed with small-angle X-ray scattering, polarized light microscopy and infrared-dichroism measurements. It was shown that films with nematic, smectic A and smectic B structures were obtained, the latter having a very high degree of orientation.

  7. Crystalline Structure in Thin Films of DEH-PPV Homopolymer And PPV-B-PI Rod-Coil Block Copolymers

    SciTech Connect

    Olsen, B.D.; Alcazar, D.; Krikorian, V.; Toney, M.F.; Thomas, E.L.; Segalman, R.A.; /UC, Berkeley /LBL, Berkeley /MIT /SLAC, SSRL

    2009-04-30

    The rod orientation and crystalline packing of a model semiconducting rodlike polymer, poly(2,5-di(2{prime}-ethylhexyloxy)-1,4-phenylenevinylene) (DEH-PPV), is shown to affect the self-assembly of weakly segregated rod-coil block copolymers. The in-plane packing of DEH-PPV rods in lamellar poly(2,5-di(2{prime}-ethylhexyloxy)-1,4-phenylenevinylene-b-isoprene) (DEH-PPV-b-PI) diblock copolymers is nearly identical to that observed in DEH-PPV homopolymers for compositions ranging from 0.42 to 0.82 vol % coil block. The crystal structure of DEH-PPV, characterized by grazing incidence X-ray diffraction and electron diffraction, consists of a tetragonal unit cell having c = 0.665 nm with a = b = 1.348 nm. The polymer chain axis is aligned along the [001] direction, and the nearest neighbor rod-rod spacing along 110 is 1.0 nm. As-cast thin films of DEH-PPV homopolymer demonstrate chain alignment primarily perpendicular to the substrate in 5100 g/mol homopolymer, while for 3500 g/mol homopolymer the chains align both perpendicular and parallel to the substrate. For the DEH-PPV-b-PI block copolymers, a sharper 001 reflection is observed due to the effect of microphase separation, improving alignment and stacking of the rods. The lamellar phases have a smectic A-like packing structure with the rods oriented parallel to the lamellar normal regardless of coil fraction; however, at coil fractions above about 0.8 the crystalline lattice of the rods becomes rapidly disordered as evidenced by loss of all but the two strongest Bragg reflections. This suggests that the constraints of packing into the unit cell outweigh the chain stretching and segment-segment repulsion energies that are predicted to lead to a transition from normal (smectic A) to tilted (smectic C) rod orientation within the lamellae at high coil fraction; increasing coil fraction breaks apart the crystalline lattice rather than distorting it into a tilted polymorph.

  8. Ab initio calculations of the optical properties of crystalline and liquid InSb

    NASA Astrophysics Data System (ADS)

    Sano, Haruyuki; Mizutani, Goro

    2015-11-01

    Ab initio calculations of the electronic and optical properties of InSb were performed for both the crystalline and liquid states. Two sets of atomic structure models for liquid InSb at 900 K were obtained by ab initio molecular dynamics simulations. To reduce the effect of structural peculiarities in the liquid models, an averaging of the two sets of the calculated electronic and optical properties corresponding to the two liquid models was performed. The calculated results indicate that, owing to the phase transition from crystal to liquid, the density of states around the Fermi level increases. As a result, the energy band gap opening near the Fermi level disappears. Consequently, the optical properties change from semiconductor to metallic behavior. Namely, owing to the melting of InSb, the interband transition peaks disappear and a Drude-like dispersion is observed in the optical dielectric functions. The optical absorption at a photon energy of 3.06 eV, which is used in Blu-ray Disc systems, increases owing to the melting of InSb. This increase in optical absorption is proposed to result from the increased optical transitions below 2 eV.

  9. Ab initio calculations of the optical properties of crystalline and liquid InSb

    SciTech Connect

    Sano, Haruyuki; Mizutani, Goro

    2015-11-15

    Ab initio calculations of the electronic and optical properties of InSb were performed for both the crystalline and liquid states. Two sets of atomic structure models for liquid InSb at 900 K were obtained by ab initio molecular dynamics simulations. To reduce the effect of structural peculiarities in the liquid models, an averaging of the two sets of the calculated electronic and optical properties corresponding to the two liquid models was performed. The calculated results indicate that, owing to the phase transition from crystal to liquid, the density of states around the Fermi level increases. As a result, the energy band gap opening near the Fermi level disappears. Consequently, the optical properties change from semiconductor to metallic behavior. Namely, owing to the melting of InSb, the interband transition peaks disappear and a Drude-like dispersion is observed in the optical dielectric functions. The optical absorption at a photon energy of 3.06 eV, which is used in Blu-ray Disc systems, increases owing to the melting of InSb. This increase in optical absorption is proposed to result from the increased optical transitions below 2 eV.

  10. A liquid-crystalline hexagonal columnar phase in highly-dilute suspensions of imogolite nanotubes

    PubMed Central

    Paineau, Erwan; Krapf, Marie-Eve M.; Amara, Mohamed-Salah; Matskova, Natalia V.; Dozov, Ivan; Rouzière, Stéphan; Thill, Antoine; Launois, Pascale; Davidson, Patrick

    2016-01-01

    Liquid crystals have found wide applications in many fields ranging from detergents to information displays and they are also increasingly being used in the ‘bottom-up' self-assembly approach of material nano-structuration. Moreover, liquid-crystalline organizations are frequently observed by biologists. Here we show that one of the four major lyotropic liquid-crystal phases, the columnar one, is much more stable on dilution than reported so far in literature. Indeed, aqueous suspensions of imogolite nanotubes, at low ionic strength, display the columnar liquid-crystal phase at volume fractions as low as ∼0.2%. Consequently, due to its low visco-elasticity, this columnar phase is easily aligned in an alternating current electric field, in contrast with usual columnar liquid-crystal phases. These findings should have important implications for the statistical physics of the suspensions of charged rods and could also be exploited in materials science to prepare ordered nanocomposites and in biophysics to better understand solutions of rod-like biopolymers. PMID:26728415

  11. A liquid-crystalline hexagonal columnar phase in highly-dilute suspensions of imogolite nanotubes

    NASA Astrophysics Data System (ADS)

    Paineau, Erwan; Krapf, Marie-Eve M.; Amara, Mohamed-Salah; Matskova, Natalia V.; Dozov, Ivan; Rouzière, Stéphan; Thill, Antoine; Launois, Pascale; Davidson, Patrick

    2016-01-01

    Liquid crystals have found wide applications in many fields ranging from detergents to information displays and they are also increasingly being used in the `bottom-up' self-assembly approach of material nano-structuration. Moreover, liquid-crystalline organizations are frequently observed by biologists. Here we show that one of the four major lyotropic liquid-crystal phases, the columnar one, is much more stable on dilution than reported so far in literature. Indeed, aqueous suspensions of imogolite nanotubes, at low ionic strength, display the columnar liquid-crystal phase at volume fractions as low as ~0.2%. Consequently, due to its low visco-elasticity, this columnar phase is easily aligned in an alternating current electric field, in contrast with usual columnar liquid-crystal phases. These findings should have important implications for the statistical physics of the suspensions of charged rods and could also be exploited in materials science to prepare ordered nanocomposites and in biophysics to better understand solutions of rod-like biopolymers.

  12. Nature-inspired light-harvesting liquid crystalline porphyrins for organic photovoltaics

    SciTech Connect

    Li, Lanfang; Kang, Shin-Woong; Harden, John; Sun, Qingjiang; Zhou, Xiaoli; Dai, Liming; Jakli, Antal; Kumar, Satyendra; Li, Quan

    2008-12-22

    A new class of nanoscale light-harvesting discotic liquid crystalline porphyrins, with the same basic structure of the best photoreceptor in nature (chlorophyll), was synthesized. These materials can be exceptionally aligned into a highly ordered architecture in which the columns formed by intermolecular {pi}-{pi} stacking are spontaneously perpendicular to the substrate. The homeotropic alignment, well confirmed by synchrotron X-ray diffraction, could not only provide the most efficient pathway for hole conduction along the columnar axis crossing the device thickness, but also offer the largest area to the incident light for optimized light harvesting. Their preliminary photocurrent generation and photovoltaic performances were also demonstrated. The results provide new and efficient pathways to the development of organic photovoltaics by using homeotropically aligned liquid crystal thin films.

  13. Towards photo-induced swimming: actuation of liquid crystalline elastomer in water

    NASA Astrophysics Data System (ADS)

    Cerretti, Giacomo; Martella, Daniele; Zeng, Hao; Parmeggiani, Camilla; Palagi, Stefano; Mark, Andrew G.; Melde, Kai; Qiu, Tian; Fischer, Peer; Wiersma, Diederik S.

    2016-04-01

    Liquid Crystalline Elastomers (LCEs) are very promising smart materials that can be made sensitive to different external stimuli, such as heat, pH, humidity and light, by changing their chemical composition. In this paper we report the implementation of a nematically aligned LCE actuator able to undergo large light-induced deformations. We prove that this property is still present even when the actuator is submerged in fresh water. Thanks to the presence of azo-dye moieties, capable of going through a reversible trans-cis photo-isomerization, and by applying light with two different wavelengths we managed to control the bending of such actuator in the liquid environment. The reported results represent the first step towards swimming microdevices powered by light.

  14. Carrier transport simulation in a model liquid crystalline system with the biaxial Gay-Berne potential.

    PubMed

    Goto, Masanao; Takezoe, Hideo; Ishikawa, Ken

    2010-02-01

    In this paper, we performed carrier transport simulation to understand the unusual temperature dependence of the carrier mobility observed in nematic liquid crystals. For this purpose, we made a model liquid crystalline system consisting of biaxial Gay-Berne particles, and then we simulated hopping transport between these particles. The hopping rate was formulated suitably for the biaxial Gay-Berne particles based on the investigation of the electronic overlaps between actual aromatic molecules. The carrier transport simulation was performed by master equation method on the model system prepared by N-P-T ensemble Monte Carlo simulation. We reproduced gradual mobility increase in the nematic phase as a result of the change in the short range molecular order. PMID:20136321

  15. Carrier transport simulation in a model liquid crystalline system with the biaxial Gay-Berne potential

    NASA Astrophysics Data System (ADS)

    Goto, Masanao; Takezoe, Hideo; Ishikawa, Ken

    2010-02-01

    In this paper, we performed carrier transport simulation to understand the unusual temperature dependence of the carrier mobility observed in nematic liquid crystals. For this purpose, we made a model liquid crystalline system consisting of biaxial Gay-Berne particles, and then we simulated hopping transport between these particles. The hopping rate was formulated suitably for the biaxial Gay-Berne particles based on the investigation of the electronic overlaps between actual aromatic molecules. The carrier transport simulation was performed by master equation method on the model system prepared by N-P-T ensemble Monte Carlo simulation. We reproduced gradual mobility increase in the nematic phase as a result of the change in the short range molecular order.

  16. More than one way to spin a crystallite: multiple trajectories through liquid crystallinity to solid silk.

    PubMed

    Walker, Andrew A; Holland, Chris; Sutherland, Tara D

    2015-06-22

    Arthropods face several key challenges in processing concentrated feedstocks of proteins (silk dope) into solid, semi-crystalline silk fibres. Strikingly, independently evolved lineages of silk-producing organisms have converged on the use of liquid crystal intermediates (mesophases) to reduce the viscosity of silk dope and assist the formation of supramolecular structure. However, the exact nature of the liquid-crystal-forming-units (mesogens) in silk dope, and the relationship between liquid crystallinity, protein structure and silk processing is yet to be fully elucidated. In this review, we focus on emerging differences in this area between the canonical silks containing extended-β-sheets made by silkworms and spiders, and 'non-canonical' silks made by other insect taxa in which the final crystallites are coiled-coils, collagen helices or cross-β-sheets. We compared the amino acid sequences and processing of natural, regenerated and recombinant silk proteins, finding that canonical and non-canonical silk proteins show marked differences in length, architecture, amino acid content and protein folding. Canonical silk proteins are long, flexible in solution and amphipathic; these features allow them both to form large, micelle-like mesogens in solution, and to transition to a crystallite-containing form due to mechanical deformation near the liquid-solid transition. By contrast, non-canonical silk proteins are short and have rod or lath-like structures that are well suited to act both as mesogens and as crystallites without a major intervening phase transition. Given many non-canonical silk proteins can be produced at high yield in E. coli, and that mesophase formation is a versatile way to direct numerous kinds of supramolecular structure, further elucidation of the natural processing of non-canonical silk proteins may to lead to new developments in the production of advanced protein materials. PMID:26041350

  17. Effects of temperature on the alignment and electrooptical responses of a nematic nanoscale liquid crystalline film.

    PubMed

    Lee, Lay Min; Kwon, Hye J; Nuzzo, Ralph G; Schweizer, Ken S

    2006-08-17

    The surface-induced alignment and electrooptical (EO) dynamics of a 50-nm-thick liquid crystalline (4-n-pentyl-4'-cyanobiphenyl; 5CB) film were studied at three temperatures: 25 and 33 degrees C (near the crystalline-nematic and nematic-isotropic transition temperatures, respectively) and 29 degrees C (a median temperature in the stability region of the nematic phase). The ZnSe surfaces that entrap the liquid crystal (LC) film have been polished unidirectionally to produce a grooved surface presenting nanometer-scale corrugations, a structure that induces a planar and homogeneous orientation in the nematic phase. The present work attempts to understand the influences of temperature on the surface-induced alignment and corresponding EO dynamics of the material. Step-scan time-resolved spectroscopy measurements were made to determine the rate constants for the electric-field-induced orientation and thermal relaxation of the 5CB film. The field-driven orientation rates vary sensitively with temperature across a range that spans the stability limits of the nematic phase; the relaxation rates, however, vary very little across this same temperature range. We propose that these differences in LC behavior arise as consequence of the interplay of the temperature dependence of the elastic constants, viscosity, and degree of orientational order of the LC medium. A simple theoretical model provides some understanding of these behaviors. PMID:16898726

  18. Polarization-Sensitive Two-Photon Microscopy Study of the Organization of Liquid-Crystalline DNA

    PubMed Central

    Mojzisova, Halina; Olesiak, Joanna; Zielinski, Marcin; Matczyszyn, Katarzyna; Chauvat, Dominique; Zyss, Joseph

    2009-01-01

    Abstract Highly concentrated DNA solutions exhibit self-ordering properties such as the generation of liquid-crystalline phases. Such organized domains may play an important role in the global chromatin topology but can also be used as a simple model for the study of more complex 3D DNA structures. In this work, using polarized two-photon fluorescence microscopy, we report on the orientation of DNA molecules in liquid-crystalline phases. For this purpose, we analyze the signal emitted by fluorophores that are noncovalently bound to DNA strands. In nonlinear processes, excitation occurs exclusively in the focal volume, which offers advantages such as the reduction of photobleaching of out-of-focus molecules and intrinsic 3D sectioning capability. Propidium iodide and Hoechst, two fluorophores with different DNA binding modes, have been considered. Polarimetric measurements show that the dyes follow the alignment with respect to the DNA strands and allow the determination of the angles between the emission dipoles and the longitudinal axis of the DNA double strand. These results provide a useful starting point toward the application of two-photon polarimetry techniques to determine the local orientation of condensed DNA in physiological conditions. PMID:19843467

  19. Thermomyces lanuginosus lipase-catalyzed hydrolysis of the lipid cubic liquid crystalline nanoparticles.

    PubMed

    Barauskas, Justas; Anderberg, Hanna; Svendsen, Allan; Nylander, Tommy

    2016-01-01

    In this study well-ordered glycerol monooleate (GMO)-based cubic liquid crystalline nanoparticles (LCNPs) have been used as substrates for Thermomyces lanuginosus lipase in order to establish the relation between the catalytic activity, measured by pH-stat titration, and the change in morphology and nanostructure determined by cryogenic transmission electron microscopy and synchrotron small angle X-ray diffraction. The initial lipase catalyzed LCNP hydrolysis rate is approximately 25% higher for large 350nm nanoparticles compared to the small 190nm particles, which is attributed to the increased number of structural defects on the particle surface. At pH 8.0 and 8.4 bicontinuous Im3m cubic LCNPs transform into "sponge"-like assemblies and disordered multilamellar onion-like structures upon exposure to lipase. At pH 6.5 and 7.5 lipolysis induced phase transitions of the inner core of the particles, following the sequence Im3m cubic → reversed hexagonal → reversed micellar Fd3m cubic → reversed micelles. These transitions to the liquid crystalline phases with higher negative curvature of the lipid/water interface were found to trigger protonation of the oleic acid produced during lipase catalyzed reaction. The increase curvature of the reversed discrete micellar cubic phase was suggested to cause an increase in the oleic acid pKa to a larger value observed by pH-stat titration. PMID:26047576

  20. Surface and liquid-crystalline properties of FmHnFm triblock semifluorinated n-alkanes.

    PubMed

    Chachaj-Brekiesz, Anna; Górska, Natalia; Osiecka, Natalia; Makyła-Juzak, Katarzyna; Dynarowicz-Łątka, Patrycja

    2016-05-01

    A series of triblock semifluorinated n-alkanes of the general formula: F(CF2)m(CH2)n(CF2)mF, (in short FmHnFm), where m=10, 12, and n=6, 8, and 12 have been synthesized and employed for liquid crystalline studies and Langmuir monolayer characterization. Differential scanning calorimetry (DSC) measurements together with texture observation with polarizing microscope (POM) revealed the presence of liquid crystalline smectic phases for all the investigated homologs. The behavior of the studied molecules spread at the free water surface has also been investigated. Our results show for the first time that these unusual film-forming materials, which are completely hydrophobic in nature and do not possess any polar group in their structure, are surface active and form insoluble (Langmuir) monolayers at the air/water interface. Due to the fact that these molecules are chemically inert and, similar to the semifluorinated diblocks, are not toxic, they may be destined for biomedical uses as gas carriers and contrast agents, as well as in drug delivery systems. PMID:26952494

  1. Synthesis, characterization, and gelation and development of liquid crystalline order during isothermal cure of rigid rod epoxy

    NASA Astrophysics Data System (ADS)

    Cho, Seunghyun

    The liquid crystalline thermoset monomers 4,4'-diglycidyloxy-alpha-methylstilbene (DOMS) and D2A1 that resulted from reaction between DOMS and aniline were synthesized. The monomers were characterized with cross-polarized optical microscopy, differential scanning calorimetry (DSC) and dynamic thermogravimetric analysis (TGA). DOMS showed monotropic liquid crystalline mesophase and D2A1 showed smectic phase even at room temperature and turned into nematic then cleared upon heating. DOMS was cured with sulfanilamide (SAA) and D2A1 was cured with catalytic curing agent, 1-methyl imidazole (MI). Thermal stability tests of DOMS-SAA, D2A1-MI and commercial nonliquid crystalline epoxy, diglycidyl ether of bisphenol A (DGEBA) SAA system via dynamic TGA shows that the factor that most influences thermal stability is the molecular structure of the material itself rather than liquid crystalline phases. The %conversion data were determined from dynamic DSC scan to examine the applicability of Flory's gelation theory. The results reveal that even though the amount of reaction that occurs in the liquid crystalline phase is different at different cure temperatures, the isoconversion theory of gelation fits quite well. The actual average value of the conversion at the gel point is 0.677, which is slightly higher than the calculated theoretical value of 0.577 because of the failed assumptions of this theory. That is, there might be reactivity differences among the same types of functional groups and intramolecular connections are possible. The phase transitions do not show isoconversion behavior in contrast to gelation. Instead, the conversion where phase changes from isotropic to a liquid crystalline phase tends to increase with temperature because the critical length of the molecules needed for the liquid crystallinity increases with temperature.

  2. Silica nanoparticle stabilization of liquid crystalline lipid dispersions: impact on enzymatic digestion and drug solubilization.

    PubMed

    Bhatt, Achal B; Barnes, Timothy J; Prestidge, Clive A

    2015-01-01

    The high internal surface area and drug solubilizing capacity of liquid crystal lipids makes them promising oral drug delivery systems. Pluronic F127 is typically used to disperse highly viscous cubic liquid crystal lipids into cubosomes; however, such copolymers alter the internal structure and provide little control over enzymatic digestion. This study aimed to use hydrophilic silica nanoparticles to stabilize glyceryl monooleate (GMO) cubosomes prepared by ultrasonication. We investigate the influence of silica nanoparticles size and concentration on the physical (colloidal) and chemical (enzymatic digestion) stability, as well as in vitro solubilization of cinnarizine as a poorly soluble model drug. Silica stabilized nanostructured liquid crystal dispersions (120 nm to150 nm in diameter and zeta potentials of-30 mV to -60 mV) were successfully prepared with excellent long-term stability (<10% size change after 30 days). Silica stabilized GMO cubosomes demonstrated reduced enzymatic digestion compared to pluronic F127 stabilized cubosomes. This reduced digestion was attributed to a combination of adsorbed silica nanoparticles acting as a physical barrier and excess dispersed silica adsorbing/scavenging the lipase enzyme. Under simulated intestinal digestion conditions, silica stabilized GMO cubosomes showed a greater solubilization capacity for cinnarizine, which precipitated in non-crystalline form, in comparison to pure drug suspensions or pluronic F127 stabilized GMO cubosomes. Silica nanoparticle stabilized GMO liquid crystal dispersions are a promising oral delivery vehicle. PMID:25176029

  3. On the molecular anisotropy of liquid crystalline and flexible polymer systems

    NASA Astrophysics Data System (ADS)

    van Horn, Brett L.

    The demand for products of ever increasing quality or for novel applications has required increasing attention to or manipulation of the anisotropy of manufactured parts. Oriented plastics are used everywhere from recording film to automotive body parts to monofilament fishing line. Liquid crystals are also used in a wide array of applications including their dominance in the flat panel display industry, color changing temperature sensors, and woven bullet resistant fabrics. Anisotropy can also be detrimental, for instance sometimes leading to poor fracture resistance or low yield stress along specific directions. Controlling and measuring anisotropy of materials has become increasingly important, but doing so is wrought with challenges. Measuring physical properties of isotropic liquids, such as water or most oils can be done in a straightforward fashion. Their viscosities and densities, for example, have unique values under a given set of conditions. With anisotropic fluids, like liquid crystals, the viscosity, for instance, will not only depend upon temperature, concentration, etc. but also upon the direction of observation, degree of anisotropy, source of anisotropy, and so forth. This added degree of complexity complicates our ability to define the state of the material at which the measurements are made and generally necessitates the use of more sophisticated measurement strategies or techniques. This work presents techniques and tools for investigating anisotropy in liquid crystalline and stretched polymeric systems. Included are the use of conoscopy for the determination of birefringence and orientation of nematic liquid crystals and stretched polymers, the shear response of flow aligning nematic liquid crystal monodomains, and the design of a novel linear rheometer that allows for in situ optical or scattering investigations.

  4. More than one way to spin a crystallite: multiple trajectories through liquid crystallinity to solid silk

    PubMed Central

    Walker, Andrew A.; Holland, Chris; Sutherland, Tara D.

    2015-01-01

    Arthropods face several key challenges in processing concentrated feedstocks of proteins (silk dope) into solid, semi-crystalline silk fibres. Strikingly, independently evolved lineages of silk-producing organisms have converged on the use of liquid crystal intermediates (mesophases) to reduce the viscosity of silk dope and assist the formation of supramolecular structure. However, the exact nature of the liquid-crystal-forming-units (mesogens) in silk dope, and the relationship between liquid crystallinity, protein structure and silk processing is yet to be fully elucidated. In this review, we focus on emerging differences in this area between the canonical silks containing extended-β-sheets made by silkworms and spiders, and ‘non-canonical’ silks made by other insect taxa in which the final crystallites are coiled-coils, collagen helices or cross-β-sheets. We compared the amino acid sequences and processing of natural, regenerated and recombinant silk proteins, finding that canonical and non-canonical silk proteins show marked differences in length, architecture, amino acid content and protein folding. Canonical silk proteins are long, flexible in solution and amphipathic; these features allow them both to form large, micelle-like mesogens in solution, and to transition to a crystallite-containing form due to mechanical deformation near the liquid–solid transition. By contrast, non-canonical silk proteins are short and have rod or lath-like structures that are well suited to act both as mesogens and as crystallites without a major intervening phase transition. Given many non-canonical silk proteins can be produced at high yield in E. coli, and that mesophase formation is a versatile way to direct numerous kinds of supramolecular structure, further elucidation of the natural processing of non-canonical silk proteins may to lead to new developments in the production of advanced protein materials. PMID:26041350

  5. Novel spiropyran amphiphiles and their application as light-responsive liquid crystalline components.

    PubMed

    Tangso, Kristian J; Fong, Wye-Khay; Darwish, Tamim; Kirby, Nigel; Boyd, Ben J; Hanley, Tracey L

    2013-09-01

    Light-responsive materials formed by liquid crystalline lipids in water have potential application to drug delivery through inclusion of photochromic additives such as spiropyran. A series of novel analogues of spiropyran (SP) have been synthesized with an SP headgroup that possess a C8 (SP-OC), C12 (SP-L), and C16 (SP-P) tail to probe the influence of the length of the hydrophobic tail on their physicochemical properties and effect on behavior in liquid crystal matrices with a view to application as stimulus-responsive elements on ultraviolet irradiation. In addition, compounds possessing an oleyl (SP-OL) and phytanyl (SP-PHYT) tail, to mimic those of the "parent" reverse bicontinuous cubic (V2) phase forming lipids, glyceryl monooleate (GMO) and phytantriol, were also prepared. The photochromic compounds were characterized by their melting points and photophysical behavior in solution using techniques including hot stage microscopy (HSM), differential scanning calorimetry (DSC), and UV-visible spectroscopy. Their effect on the equilibrium nanostructure of bulk V2 phases and phase-switching kinetics after exposure to UV light was assessed using small-angle X-ray scattering (SAXS). The melting point of the SP derivatives decreased linearly with increasing chain length, which suggests that interactions between the head groups governed their melting point, rather than the van der Waals interactions between the tails. Changing the R group did not influence the equilibrium rate constants for the isomerization of SP. Phase transition temperatures of liquid crystalline (LC) matrices were influenced significantly by incorporation of the SP derivatives and were greatest when the photochromic compound possessed an intermediate tail length substituent compared to the short alkyl or bulkier moieties. The level of disruption of lipid packing, and hence phase structure, were dependent on the duration of UV exposure. PMID:23909814

  6. Tea Flavanols Block Advanced Glycation of Lens Crystallins Induced by Dehydroascorbic Acid.

    PubMed

    Zhu, Yingdong; Zhao, Yantao; Wang, Pei; Ahmedna, Mohamed; Ho, Chi-Tang; Sang, Shengmin

    2015-01-20

    Growing evidence has shown that ascorbic acid (ASA) can contribute to protein glycation and the formation of advanced glycation end products (AGEs), especially in the lens. The mechanism by which ascorbic acid can cause protein glycation probably originates from its oxidized form, dehydroascorbic acid (DASA), which is a reactive dicarbonyl species. In the present study, we demonstrated for the first time that four tea flavanols, (-)-epigallocatechin 3-O-gallate (EGCG), (-)-epigallocatechin (EGC), (-)-epicatechin 3-O-gallate (ECG), and (-)-epicatechin (EC), could significantly trap DASA and consequently form 6C- or 8C-ascorbyl conjugates. Among these four flavanols, EGCG exerted the strongest trapping efficacy by capturing approximate 80% of DASA within 60 min. We successfully purified and identified seven 6C- or 8C-ascorbyl conjugates of flavanols from the chemical reaction between tea flavanols and DASA under slightly basic conditions. Of which, five ascorbyl conjugates, EGCGDASA-2, EGCDASA-2, ECGDASA-1, ECGDASA-2 and ECDASA-1, were recognized as novel compounds. The NMR data showed that positions 6 and 8 of the ring A of flavanols were the major active sites for trapping DASA. We further demonstrated that tea flavanols could effectively inhibit the formation of DASA-induced AGEs via trapping DASA in the bovine lens crystallin-DASA assay. In this assay, 8C-ascorbyl conjugates of flavanols were detected as the major adducts using LC-MS. This study suggests that daily consumption of beverages containing tea flavanols may prevent protein glycation in the lens induced by ascorbic acid and its oxidized products. PMID:25437149

  7. Building a nano-crystalline α-alumina layer at a liquid metal/sapphire interface by ultrasound.

    PubMed

    Cui, Wei; Yan, Jiuchun; Dai, Yan; Li, Dandan

    2015-01-01

    Transitional layers at the metal/ceramic interface play an very important role in ceramic joining. In this study, sapphire blocks were ultrasonically dipped in liquid Sn-Zn-Al alloy. It is found that the ultrasound promoted rapid oxidation reaction of aluminum at the Sn-Zn-Al/sapphire interface at 230°C in the ambient atmosphere, resulting in the formation of a nano-crystalline α-Al2O3 layer (NCAL). In a ∼2nm boundary layer of the NCAL, the lattice matches the sapphire substrate well. Thus, a smooth transition of the lattice from sapphire to metal was formed through the NCAL. Ultrasonically soldered sapphire joints were made with Sn-Zn-Al as the filler alloy. Compressive shear strength of the joints reached 43-48MPa, which is relatively high comparing to other Al2O3 joints made of Sn alloys doped with Ti or Rear Earth elements. Thus, a new mechanism of ultrasonic soldering, i.e. building an oxide transitional layer on the surface of the solid, was revealed. We expect this sonochemical process to be applicable to other metal/oxide systems. PMID:24882591

  8. Peptide KSL-W-Loaded Mucoadhesive Liquid Crystalline Vehicle as an Alternative Treatment for Multispecies Oral Biofilm.

    PubMed

    Bernegossi, Jéssica; Calixto, Giovana Maria Fioramonti; Sanches, Paulo Ricardo da Silva; Fontana, Carla Raquel; Cilli, Eduardo Maffud; Garrido, Saulo Santesso; Chorilli, Marlus

    2015-01-01

    Decapeptide KSL-W shows antibacterial activities and can be used in the oral cavity, however, it is easily degraded in aqueous solution and eliminated. Therefore, we aimed to develop liquid crystalline systems (F1 and F2) for KSL-W buccal administration to treat multispecies oral biofilms. The systems were prepared with oleic acid, polyoxypropylene (5) polyoxyethylene (20) cetyl alcohol (PPG-5-CETETH-20), and a 1% poloxamer 407 dispersion as the oil phase (OP), surfactant (S), and aqueous phase (AP), respectively. We characterized them using polarized light microscopy (PLM), small-angle X-ray scattering (SAXS), rheology, and in vitro bioadhesion, and performed in vitro biological analysis. PLM showed isotropy (F1) or anisotropy with lamellar mesophases (F2), confirmed by peak ratio quantification using SAXS. Rheological tests demonstrated that F1 exhibited Newtonian behavior but not F2, which showed a structured AP concentration-dependent system. Bioadhesion studies revealed an AP concentration-dependent increase in the system's bioadhesiveness (F2 = 15.50 ± 1.00 mN·s) to bovine teeth blocks. Antimicrobial testing revealed 100% inhibition of multispecies oral biofilm growth after KSL-W administration, which was incorporated in the F2 aqueous phase at a concentration of 1 mg/mL. Our results suggest that this system could serve as a potential vehicle for buccal administration of antibiofilm peptides. PMID:26712726

  9. Formulation of an oral dosage form utilizing the properties of cubic liquid crystalline phases of glyceryl monooleate.

    PubMed

    Sallam, Al-Sayed; Khalil, Enam; Ibrahim, Hussain; Freij, Ibtisam

    2002-05-01

    Glyceryl monooleate is a Food and Drug Administration-approved food additive which has the ability to form various liquid crystalline phases in the presence of various amounts of water. The unique properties of the cubic liquid crystalline phase that result upon the presence of excess body fluids at body temperature were utilized to formulate an oral dosage form containing furosemide as the model drug. The aim was to develop a formula, which has both bioadhesive and sustained release properties of the resultant cubic phase, so that increasing gastric residence time to improve bioavailability of the drug and at the same time obtaining a sustained action. The system was found to be affected by the limited solubility of furosemide in both the carrier system and the pH of surrounding medium. As a consequence, the addition of some solubility modifiers was investigated in order to obtain the desired properties of the expected liquid crystalline system. PMID:11976023

  10. Hierarchically structured free-standing hydrogels with liquid crystalline domains and magnetic nanoparticles as dual physical cross-linkers.

    PubMed

    Zhou, Yuxiang; Sharma, Nitin; Deshmukh, Prashant; Lakhman, Rubinder Kaur; Jain, Menka; Kasi, Rajeswari M

    2012-01-25

    Here we report a modular strategy for preparing physically cross-linked and mechanically robust free-standing hydrogels comprising unique thermotropic liquid crystalline (LC) domains and magnetic nanoparticles both of which serve as the physical cross-linkers resulting in hydrogels that can be used as magnetically responsive soft actuators. A series of amphiphilic LC pentablock copolymers of poly(acrylic acid) (PAA), poly(5-cholesteryloxypentyl methacrylate) (PC5MA), and poly(ethylene oxide) (PEO) blocks in the sequence of PAA-PC5MA-PEO-PC5MA-PAA were prepared using reversible addition-fragmentation chain transfer polymerization. These pentablock copolymers served as macromolecular ligands to template Fe(3)O(4) magnetic nanoparticles (MNPs), which were directly anchored to the polymer chains through the coordination bonds with the carboxyl groups of PAA blocks. The resulting polymer/MNP nanocomposites comprised a complicated hierarchical structure in which polymer-coated MNP clusters were dispersed in a microsegregated pentablock copolymer matrix that further contained LC ordering. Upon swelling, the hierarchical structure was disrupted and converted to a network structure, in which MNP clusters were anchored to the polymer chains and LC domains stayed intact to connect solvated PEO and PAA blocks, leading to a free-standing LC magnetic hydrogel (LC ferrogel). By varying the PAA weight fraction (f(AA)) in the pentablock copolymers, the swelling degrees (Q) of the resulting LC ferrogels were tailored. Rheological experiments showed that these physically cross-linked free-standing LC ferrogels exhibit good mechanical strength with storage moduli G' of around 10(4)-10(5) Pa, similar to that of natural tissues. Furthermore, application of a magnetic field induced bending actuation of the LC ferrogels. Therefore, these physically cross-linked and mechanically robust LC ferrogels can be used as soft actuators and artificial muscles. Moreover, this design strategy is a