Oil and drug control the release rate from lyotropic liquid crystals.

PubMed

Martiel, Isabelle; Baumann, Nicole; Vallooran, Jijo J; Bergfreund, Jotam; Sagalowicz, Laurent; Mezzenga, Raffaele

2015-04-28

The control of the diffusion coefficient by the dimensionality d of the structure appears as a most promising lever to efficiently tune the release rate from lyotropic liquid crystalline (LLC) phases and dispersed particles towards sustained, controlled and targeted release. By using phosphatidylcholine (PC)- and monolinoleine (MLO)-based mesophases with various apolar structural modifiers and water-soluble drugs, we present a comprehensive study of the dimensional structural control of hydrophilic drug release, including 3-d bicontinuous cubic, 2-d lamellar, 1-d hexagonal and 0-d micellar cubic phases in excess water. We investigate how the surfactant, the oil properties and the drug hydrophilicity mitigate or even cancel the effect of structure variation on the drug release rate. Unexpectedly, the observed behavior cannot be fully explained by the thermodynamic partition of the drug into the lipid matrix, which points out to previously overlooked kinetic effects. We therefore interpret our results by discussing the mechanism of structural control of the diffusion rate in terms of drug permeation through the lipid membrane, which includes exchange kinetics. A wide range of implications follow regarding formulation and future developments, both for dispersed LLC delivery systems and topical applications in bulk phase. Copyright © 2015 Elsevier B.V. All rights reserved.

Control of Partial Coalescence of Self-Assembled Metal Nano-Particles across Lyotropic Liquid Crystals Templates towards Long Range Meso-Porous Metal Frameworks Design

PubMed Central

Dumée, Ludovic F.; Lemoine, Jean-Baptiste; Ancel, Alice; Hameed, Nishar; He, Li; Kong, Lingxue

2015-01-01

The formation of purely metallic meso-porous metal thin films by partial interface coalescence of self-assembled metal nano-particles across aqueous solutions of Pluronics triblock lyotropic liquid crystals is demonstrated for the first time. Small angle X-ray scattering was used to study the influence of the thin film composition and processing conditions on the ordered structures. The structural characteristics of the meso-structures formed demonstrated to primarily rely on the lyotropic liquid crystal properties while the nature of the metal nano-particles used as well as the their diameters were found to affect the ordered structure formation. The impact of the annealing temperature on the nano-particle coalescence and efficiency at removing the templating lyotropic liquid crystals was also analysed. It is demonstrated that the lyotropic liquid crystal is rendered slightly less thermally stable, upon mixing with metal nano-particles and that low annealing temperatures are sufficient to form purely metallic frameworks with average pore size distributions smaller than 500 nm and porosity around 45% with potential application in sensing, catalysis, nanoscale heat exchange, and molecular separation. PMID:28347094

Nanoparticle guests in lyotropic liquid crystals

NASA Astrophysics Data System (ADS)

Dölle, Sarah; Park, Ji Hyun; Schymura, Stefan; Jo, Hyeran; Scalia, Giusy; Lagerwall, Jan P. F.

In this chapter we discuss the benefits, peculiarities and main challenges related to nanoparticle templating in lyotropic liquid crystals. We first give a brief bird's-eye view of the field, discussing different nanoparticles as well as different lyotropic hosts that have been explored, but then quickly focus on the dispersion of carbon nanotubes in surfactant-based lyotropic nematic phases. We discuss in some detail how the transfer of orientational order from liquid crystal host to nanoparticle guest can be verified and which degree of ordering can be expected, as well as the importance of choosing the right surfactant and its concentration for the stability of the nanoparticle suspension. We introduce a method for dispersing nanoparticles with an absolute minimum of stabilizing surfactant, based on dispersion below the Krafft temperature, and we discuss the peculiar phenomenon of filament formation in lyotropic nematic phases with a sufficient concentration of well-dispersed carbon nanotubes. Finally, we describe how the total surfactant concentration in micellar nematics can be greatly reduced by combining cat- and anionic surfactants, and we discuss how nanotubes can help in inducing the liquid crystal phase close to the isotropic-nematic boundary.

Interactions of biomacromolecules with reverse hexagonal liquid crystals: drug delivery and crystallization applications.

PubMed

Libster, Dima; Aserin, Abraham; Garti, Nissim

2011-04-15

Recently, self-assembled lyotropic liquid crystals (LLCs) of lipids and water have attracted the attention of both scientific and applied research communities, due to their remarkable structural complexity and practical potential in diverse applications. The phase behavior of mixtures of glycerol monooleate (monoolein, GMO) was particularly well studied due to the potential utilization of these systems in drug delivery systems, food products, and encapsulation and crystallization of proteins. Among the studied lyotropic mesophases, reverse hexagonal LLC (H(II)) of monoolein/water were not widely subjected to practical applications since these were stable only at elevated temperatures. Lately, we obtained stable H(II) mesophases at room temperature by incorporating triacylglycerol (TAG) molecules into the GMO/water mixtures and explored the physical properties of these structures. The present feature article summarizes recent systematic efforts in our laboratory to utilize the H(II) mesophases for solubilization, and potential release and crystallization of biomacromolecules. Such a concept was demonstrated in the case of two therapeutic peptides-cyclosporin A (CSA) and desmopressin, as well as RALA peptide, which is a model skin penetration enhancer, and eventually a larger macromolecule-lysozyme (LSZ). In the course of the study we tried to elucidate relationships between the different levels of organization of LLCs (from the microstructural level, through mesoscale, to macroscopic level) and find feasible correlations between them. Since the structural properties of the mesophase systems are a key factor in drug release applications, we investigated the effects of these guest molecules on their conformations and the way these molecules partition within the domains of the mesophases. The examined H(II) mesophases exhibited great potential as transdermal delivery vehicles for bioactive peptides, enabling tuning the release properties according to their chemical composition and physical properties. Furthermore, we showed a promising opportunity for crystallization of CSA and LSZ in single crystal form as model biomacromolecules for crystallographic structure determination. The main outcomes of our research demonstrated that control of the physical properties of hexagonal LLC on different length scales is key for rational design of these systems as delivery vehicles and crystallization medium for biomacromolecules. Copyright © 2011 Elsevier Inc. All rights reserved.

Aqueous Lyotropic Liquid Crystalline Frank-Kasper Mesophases

NASA Astrophysics Data System (ADS)

Mahanthappa, Mahesh; Kim, Sung A.; Jeong, Kyeong-Jun; Yethiraj, Arun

Amphiphilic molecules undergo water concentration-dependent self-assembly to form lyotropic liquid crystal (LLC) mesophases. LLC morphology selection is directed by cooperative optimization of preferred molecular packing arrangements, which stem from a subtle balance of local, non-covalent interactions. We recently discovered a class of amphiphiles that form a progression of discontinuous micellar LLCs, including two tetrahedrally-closest packed Frank-Kasper phases that exhibit exceptional long range order. This discovery complements recent reports of their formation in thermotropic liquid crystals, neat diblock and tetrablock polymers, and in lyotropic mesophases of block polymers in ionic liquids. Using a combination of MD simulations and experiments, we provide new insights into the mechanisms of formation for these low symmetry micelle phases.

Solvation Dynamics in Different Phases of the Lyotropic Liquid Crystalline System.

PubMed

Roy, Bibhisan; Satpathi, Sagar; Gavvala, Krishna; Koninti, Raj Kumar; Hazra, Partha

2015-09-03

Reverse hexagonal (HII) liquid crystalline material based on glycerol monooleate (GMO) is considered as a potential carrier for drugs and other important biomolecules due to its thermotropic phase change and excellent morphology. In this work, the dynamics of encapsulated water, which plays important role in stabilization and formation of reverse hexagonal mesophase, has been investigated by time dependent Stokes shift method using Coumarin-343 as a solvation probe. The formation of the reverse hexagonal mesophase (HII) and transformation to the L2 phase have been monitored using small-angle X-ray scattering and polarized light microscopy experiments. REES studies suggest the existence of different polar regions in both HII and L2 systems. The solvation dynamics study inside the reverse hexagonal (HII) phase reveals the existence of two different types of water molecules exhibiting dynamics on a 120-900 ps time scale. The estimated diffusion coefficients of both types of water molecules obtained from the observed dynamics are in good agreement with the measured diffusion coefficient collected from the NMR study. The calculated activation energy is found to be 2.05 kcal/mol, which is associated with coupled rotational-translational water relaxation dynamics upon the transition from "bound" to "quasi-free" state. The observed ∼2 ns faster dynamics of the L2 phase compared to the HII phase may be associated with both the phase transformation as well as thermotropic effect on the relaxation process. Microviscosities calculated from time-resolved anisotropy studies infer that the interface is almost ∼22 times higher viscous than the central part of the cylinder. Overall, our results reveal the unique dynamical features of water inside the cylinder of reverse hexagonal and inverse micellar phases.

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.

Technical Report: Understanding Functional Lyotropic Liquid Crystal Network Phase Self-Assembly and the Properties of Nanoconfined Water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mahanthappa, Mahesh K; Yethiraj, Arun

Through the synergistic interplay of molecular dynamics (MD) simulations, chemical synthesis, and materials characterization by X-ray and neutron scattering techniques, this project investigated the phase behaviors of new classes of aqueous lyotropic liquid crystals (LLCs) and the properties of water nanoconfined within their pores. A portion of our studies focused on the synthesis of new classes of alkylsulfonic acid and alkylphosphonate amphiphiles, which were shown to undergo water-induced self-assembly to form a wide variety of nanostructured morphologies with unusually high degrees of long-range translational order observed by small- angle X-ray scattering (SAXS). Sample LLC morphologies that were observed include themore » lamellar (L!), tricontinuous double gyroid (G), hexagonally-packed cylinders (H), and low symmetry discontinuous micellar (I) Frank-Kasper phases. Since the G and H phases are the most promising for the development of selective ion transporting membranes for energy applications, we sought the characterize the structure and dynamics of water confined within the sub-3 nm pores of these LLCs using wide-angle neutron diffraction (WAND) and quasielastic neutron scattering (QENS) experiments performed at the Spallation Neutron Source at Oak Ridge National Laboratory. Using molecular dynamics (MD) simulations, we validated models for analyzing this QENS data to obtain water self-diffusion coefficients in LLC G and H phases of carboxylate and sulfonate surfactant LLCs as a function of the identities of their charge compensating counterions.« less

Myelin structures formed by thermotropic smectic liquid crystals

NASA Astrophysics Data System (ADS)

Peddireddy, Karthik Reddy; Kumar, Pramoda; Thutupalli, Shashi; Herminghaus, Stephan; Bahr, Christian

2014-03-01

We report on transient structures, formed by thermotropic smectic-A liquid crystals, resembling the myelin figures of lyotropic lamellar liquid crystals. The thermotropic myelin structures form during the solubilization of a smectic-A droplet in an aqueous phase containing a cationic surfactant at concentrations above the critical micelle concentration. Similar to the lyotropic myelin figures, the thermotropic myelins appear in an optical microscope as flexible tube-like structures growing at the smectic/aqueous interface. Polarizing microscopy and confocal fluorescence microscopy show that the smectic layers are parallel to the tube surface and form a cylindrically bent arrangement around a central line defect in the tube. We study the growth behavior of this new type of myelins and discuss similarities and differences to the classical lyotropic myelin figures.

Magnetic self-orientation of lyotropic hexagonal phases based on long chain alkanoic (fatty) acids.

PubMed

Douliez, Jean-Paul

2010-07-06

It is presently shown that long chain (C14, C16, and C18) alkanoic (saturated fatty) acids can form magnetically oriented hexagonal phases in aqueous concentrated solutions in mixtures with tetrabutylammonium (TBAOH) as the counterion. The hexagonal phase occurred for a molar ratio, alkanoic acid/TBAOH, higher than 1, i.e., for an excess of fatty acid. The hexagonal phase melted to an isotropic phase (micelles) upon heating at a given temperature depending on the alkyl chain length. The self-orientation of the hexagonal phase occurred upon cooling from the "high-temperature" isotropic phase within the magnetic field. The long axis of the hexagonal phase was shown to self-orient parallel to the magnetic field as evidenced by deuterium solid-state NMR. This finding is expected to be of interest in the field of structural biology and materials chemistry for the synthesis of oriented materials.

Lyotropic liquid crystal preconcentrates for the treatment of periodontal disease.

PubMed

Fehér, A; Urbán, E; Eros, I; Szabó-Révész, P; Csányi, E

2008-06-24

The aim of our study was to develop water-free lyotropic liquid crystalline preconcentrates, which consist of oils and surfactants with good physiological tolerance and spontaneously form lyotropic liquid crystalline phase in aqueous environment. In this way these preconcentrates having low viscosity can be injected into the periodontal pocket, where they are transformed into highly viscous liquid crystalline phase, so that the preparation is prevented from flowing out of the pocket due to its great viscosity, while drug release is controlled by the liquid crystalline texture. In order to follow the structure alteration upon water absorption polarization microscopical and rheological examinations were performed. The water absorption mechanism of the samples was examined by the Enslin-method. Metronidazole-benzoate was used as active agent the release of which was characterized via in vitro investigations performed by means of modified Kirby-Bauer disk diffusion method. On the grounds of the results it can be stated that the 4:1 mixture of the investigated surfactants (Cremophor EL, Cremophor RH40) and oil (Miglyol 810) formed lyotopic liquid crystalline phases upon water addition. Polarization microscopic examinations showed that samples with 10-40% water content possessed anisotropic properties. On the basis of water absorption, rheological and drug release studies it can be concluded that the amount of absorbed water and stiffness of lyotropic structure influenced by the chemical entity of the surfactant exerted major effect on the drug release.

Geometrical aspects of the frustration in the cubic phases of lyotropic liquid crystals.

PubMed Central

Anderson, D M; Gruner, S M; Leibler, S

1988-01-01

Bicontinuous cubic phases, composed of bilayers arranged in the geometries of periodic minimal surfaces, are found in a variety of different lipid/water systems. It has been suggested recently that these cubic structures arrive as the result of competition between two free-energy terms: the curvature energy of each monolayer and the stretching energy of the lipid chains. This scenario, closely analogous to the one that explains the origin of the hexagonal phases, is investigated here by means of simple geometrical calculations. It is first assumed that the lipid bilayer is of constant thickness and the distribution of the (local) mean curvature of the phospholipid-water interfaces is calculated. Then, assuming the mean curvature of these interfaces is constant, the distribution of the bilayer's thickness is calculated. Both calculations quantify the fact that the two energy terms are frustrated and cannot be satisfied simultaneously. However, the amount of the frustration can be smaller for the cubic phase than for the lamellar and hexagonal structures. Therefore, this phase can appear in the phase diagram between the other two, as observed in many recent experiments. PMID:3399497

Nematic DNA Thermotropic Liquid Crystals with Photoresponsive Mechanical Properties.

PubMed

Zhang, Lei; Maity, Sourav; Liu, Kai; Liu, Qing; Göstl, Robert; Portale, Giuseppe; Roos, Wouter H; Herrmann, Andreas

2017-09-01

Over the last decades, water-based lyotropic liquid crystals of nucleic acids have been extensively investigated because of their important role in biology. Alongside, solvent-free thermotropic liquid crystals (TLCs) from DNA are gaining great interest, owing to their relevance to DNA-inspired optoelectronic applications. Up to now, however, only the smectic phase of DNA TLCs has been reported. The development of new mesophases including nematic, hexagonal, and cubic structures for DNA TLCs remains a significant challenge, which thus limits their technological applications considerably. In this work, a new type of DNA TLC that is formed by electrostatic complexation of anionic oligonucleotides and cationic surfactants containing an azobenzene (AZO) moiety is demonstrated. DNA-AZO complexes form a stable nematic mesophase over a temperature range from -7 to 110 °C and retain double-stranded DNA structure at ambient temperature. Photoisomerization of the AZO moieties from the E- to the Z-form alters the stiffness of the DNA-AZO hybrid materials opening a pathway toward the development of DNA TLCs as stimuli-responsive biomaterials. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sagnella, Sharon M.; Conn, Charlotte E.; Krodkiewska, Irena

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 anmore » 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.« less

Molecularly Imprinted Microrods via Mesophase Polymerization.

PubMed

Parisi, Ortensia Ilaria; Scrivano, Luca; Candamano, Sebastiano; Ruffo, Mariarosa; Vattimo, Anna Francesca; Spanedda, Maria Vittoria; Puoci, Francesco

2017-12-28

The aim of the present research work was the synthesis of molecularly imprinted polymers (MIPs) with a rod-like geometry via "mesophase polymerization". The ternary lyotropic system consisting of sodium dodecyl sulfate (SDS), water, and decanol was chosen to prepare a hexagonal mesophase to direct the morphology of the synthesized imprinted polymers using theophylline, methacrylic acid, and ethylene glycol dimethacrylate as a drug model template, a functional monomer, and a crosslinker, respectively. The obtained molecularly imprinted microrods (MIMs) were assessed by performing binding experiments and in vitro release studies, and the obtained results highlighted good selective recognition abilities and sustained release properties. In conclusion, the adopted synthetic strategy involving a lyotropic mesophase system allows for the preparation of effective MIPs characterized by a rod-like morphology.

Swollen hexagonal liquid crystals as smart nanoreactors: implementation in materials chemistry for energy applications.

PubMed

Ghosh, Srabanti; Ramos, Laurence; Remita, Hynd

2018-03-29

Materials are the key roadblocks for the commercialization of energy conversion devices in fuel cells and solar cells. Significant research has focused on tuning the intrinsic properties of materials at the nanometer scale. The soft template mediated controlled fabrication of advanced nanostructured materials is attracting considerable interest due to the promising applications of these materials in catalysis and electrocatalysis. Swollen hexagonal lyotropic liquid crystals (SLCs) consist of oil-swollen surfactant-stabilized 1D, 2D or 3D nanometric assemblies regularly arranged in an aqueous solvent. Interestingly, the characteristic size of the SLCs can be controlled by adjusting the volume ratio of oil to water. The non-polar and/or polar compartments of the SLCs can be doped with guest molecules and used as nanoreactors for the synthesis of various metals (Pt, Pd, Au, etc.), conducting polymers and composite nanostructures with controlled size and shape. 1D, 2D and 3D mono- and bimetallic nanostructures of controlled composition and porosity can also be fabricated. These materials have demonstrated impressive enhancements of their electrochemical properties as compared to their bulk counterparts and have been identified as promising for further implementation in energy harvesting applications. In this review article, recent research materials are described regarding the development of functional materials with much improved performances for catalysis applications. This review addresses a brief overview of swollen hexagonal mesophases as nanoreactors, describes examples of nanostructured materials synthesized in these nanoreactors, shows several examples of the energy conversion applications in solar light harvesting, fuel cells etc. and also summarizes the associated reaction mechanisms developed in the recent literature for enhanced catalytic activity.

A micromachined calorimetric gas sensor: an application of electrodeposited nanostructured palladium for the detection of combustible gases.

PubMed

Bartlett, Philip N; Guerin, Samuel

2003-01-01

Palladium films with regular nanoarchitectures were electrochemically deposited from the hexagonal (H1) lyotropic liquid crystalline phase of the nonionic surfactant octaethyleneglycol monohexadecyl ether (C16EO8) onto micromachined silicon hotplate structures. The H1-e Pd films were shown to have high surface areas (approximately 28 m2 g(-1)) and to act as effective and stable catalysts for the detection of methane in air on heating to 500 degrees C. The response of the H1-e Pd-coated planar pellistors was found to be linearly proportional to the concentration of methane between 0 and 2.5% in air with a detection limit below 0.125%. Our results show that the electrochemical deposition of nanostructured metal films offers a promising approach to the fabrication of micromachined calorimetric gas sensors for combustible gases.

Synthesis and high catalytic properties of mesoporous Pt nanowire array by novel conjunct template method

NASA Astrophysics Data System (ADS)

Zhong, Yi; Xu, Cai-Ling; Kong, Ling-Bin; Li, Hu-Lin

2008-12-01

A novel conjunct template method for fabricating mesoporous Pt nanowire array through direct current (DC) electrodeposition of Pt into the pores of anodic aluminum oxide (AAO) template on Ti/Si substrate from hexagonal structured lyotropic liquid crystalline phase is demonstrated in this paper. The morphology and structure of as-prepared Pt nanowire array are characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). The electrocatalytic properties of Pt nanowire array for methanol are also investigated in detail. The results indicate that Pt nanowire array has the unique mesoporous structure of approximate 40-50 nm in diameter, which resulted in the high surface area and greatly improved electrocatalytic activity for methanol. The mesoporous Pt nanowire array synthesized by the new conjunct template method has a very promising application in portable fuel cell power sources.

Chelating DTPA amphiphiles: ion-tunable self-assembly structures and gadolinium complexes.

PubMed

Moghaddam, Minoo J; de Campo, Liliana; Kirby, Nigel; Drummond, Calum J

2012-10-05

A series of chelating amphiphiles and their gadolinium (Gd(III)) metal complexes have been synthesized and studied with respect to their neat and lyotropic liquid crystalline phase behavior. These amphiphiles have the ability to form ion-tunable self-assembly nanostructures and their associated Gd(III) complexes have potential as magnetic resonance imaging (MRI) contrast enhancement agents. The amphiphiles are composed of diethylenetriaminepentaacetic acid (DTPA) chelates conjugated to one or two oleyl chain(s) (DTPA-MO and DTPA-BO), or isoprenoid-type chain(s) of phytanyl (DTPA-MP and DTPA-BP). The thermal phase behavior of the neat amphiphiles was examined by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and cross polarizing optical microscopy (POM). Self-assembly of neat amphiphiles and their associated Gd complexes, as well as their lyotropic phase behavior in water and sodium acetate solutions of different ionic strengths, were examined by POM and small and wide angle X-ray scattering (SWAXS). All neat amphiphiles exhibited lamellar structures. The non-complexed amphiphiles showed a variety of lyotropic phases depending on the number and nature of the hydrophobic chain in addition to the ionic state of the hydration. Upon hydration with increased Na-acetate concentration and the subtle changes in the effective headgroup size, the interfacial curvature of the amphiphile increased, altering the lyotropic liquid crystalline structures towards higher order mesophases such as the gyroid (Ia3d) bicontinuous cubic phase. The chelation of Gd with the DTPA amphiphiles resulted in lamellar crystalline structures for all the neat amphiphiles. Upon hydration with water, the Gd-complexed mono-conjugates formed micellar or vesicular self-assemblies, whilst the bis-conjugates transformed only partially into lyotropic liquid crystalline mesophases.

Process for separating and recovering an anionic dye from an aqueous solution

DOEpatents

Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.

1998-01-01

A solid/liquid phase process for the separation and recovery of an anionic dye from an aqueous solution is disclosed. The solid phase comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the anionic dye molecules are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt. After contact between the aqueous solution and separation particles, the anionic dye is bound to the particles. The bound anionic dye molecules are freed from the separation particles by contacting the anionic dye-bound particles with an aqueous solution that does not contain a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt to form an aqueous anionic dye solution whose anionic dye concentration is preferably higher than that of the initial dye-containing solution.

Process for separating and recovering an anionic dye from an aqueous solution

DOEpatents

Rogers, R.; Horwitz, E.P.; Bond, A.H.

1998-01-13

A solid/liquid phase process for the separation and recovery of an anionic dye from an aqueous solution is disclosed. The solid phase comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the anionic dye molecules are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt. After contact between the aqueous solution and separation particles, the anionic dye is bound to the particles. The bound anionic dye molecules are freed from the separation particles by contacting the anionic dye-bound particles with an aqueous solution that does not contain a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt to form an aqueous anionic dye solution whose anionic dye concentration is preferably higher than that of the initial dye-containing solution. 7 figs.

Shear rheology and in-vitro release kinetic study of apigenin from lyotropic liquid crystal.

PubMed

Fan, Jun; Liu, Feng; Wang, Zhongni

2016-01-30

Apigenin is a flavonoid compound with diverse pharmacological functions which could develop health benefit products, but its formulation is hampered by its poor water solubility and bioavailability. In this paper, in order to overcome these difficulties, apigenin was encapsulated in LLC formed by polyoxyethylene-10-oleyl ether (Brij 97) and sodium deoxycholate (NaDC) mixtures. The hexagonal liquid crystalline phase (H) and the cubic liquid crystalline phase (C) were found in this system. The shear rheology was used to study the structure change with temperature. It was shown that C3 (Brij 97-NaDC/IPM-PEG400/H2O=36:9:55) was C at low temperature. But above 35.6°C, the matrix of C3 completely transformed to polymer solution. The matrix of H3 was H (Brij 97-NaDC:IPM-PEG 400:H2O=50:9:41) below 50°C, but the structural strength change was obvious. Vitro release experiment was used to study drug release kinetics. It was indicated that apigenin encapsulated in LLC conformed to the concentration diffusion model, and cumulative percentage of apigenin released from C3 and H3 had corresponding relationship with the shear rheology at different temperatures. Copyright © 2015. Published by Elsevier B.V.

Chem I Supplement: Liquid Crystals--The Chameleon Chemicals.

ERIC Educational Resources Information Center

Brown, Glenn H.

1983-01-01

Presents information relevant to everyday life so as to stimulate student interest in the properties of the two basic types of liquid crystals: thermotropic and lyotropic. Describes the applications of liquid crystals to electronics, biomedicine, and polymer science and appraises the future of liquid crystal research. (JM)

Chiral amplification and sensing of chirality with lyotropic chromonic liquid crystals

NASA Astrophysics Data System (ADS)

Srinivasarao, Mohan; Park, Jung Ok; Fu, Jinxin; Nayani, Karthik; Chang, Rui

Due to the anisotropic elastic properties of lyotropic chromonic liquid crystals (LCLCs), a spontaneously twisted chiral structure has been reported in the achiral LCLCs system under cylindrical confinement. It is found that the handedness of chirality could be biased with a minute amount of a chiral additive. The entire system becomes ``homochiral'' and takes on the handedness of the additive. When 1% by weight of L-glutamic acid was added to LCLCs in a cylinder, the LCLC sbecomes homochiral and possesses giant optical rotation. We explore the mechanism for this based on the ``sergeants-and-soldiers'' and the ``majority-rule'' principles known for organic molecular systems.

Electroclinic effect in the chiral lamellar α phase of a lyotropic liquid crystal

NASA Astrophysics Data System (ADS)

Harjung, Marc D.; Giesselmann, Frank

2018-03-01

In thermotropic chiral Sm -A* phases, an electric field along the smectic layers breaks the D∞ symmetry of the Sm -A* phase and induces a tilt of the liquid crystal director. This so-called electroclinic effect (ECE) was first reported by Garoff and Meyer in 1977 and attracted substantial scientific and technological interest due to its linear and submicrosecond electro-optic response [S. Garoff and R. B. Meyer, Phys. Rev. A 19, 338 (1979), 10.1103/PhysRevA.19.338]. We now report the observation of an ECE in the pretransitional regime from a lyotropic chiral lamellar Lα* phase into a lyo-Sm -C* phase, the lyotropic analog to the thermotropic Sm -C* phase which was recently discovered by Bruckner et al. [Angew. Chem. Int. Ed. 52, 8934 (2013), 10.1002/anie.201303344]. We further show that the observed ECE has all signatures of its thermotropic counterpart, namely (i) the effect is chiral in nature and vanishes in the racemic Lα phase, (ii) the effect is essentially linear in the sign and magnitude of the electric field, and (iii) the magnitude of the effect diverges hyperbolically as the temperature approaches the critical temperature of the second order tilting transition. Specific deviations between the ECEs in chiral lamellar and chiral smectic phases are related to the internal field screening effect of electric double layers formed by inevitable ionic impurities in lyotropic phases.

Polymorphism and mesomorphism of oligomeric surfactants: effect of the degree of oligomerization.

PubMed

Jurašin, D; Pustak, A; Habuš, I; Šmit, I; Filipović-Vinceković, N

2011-12-06

A series of cationic oligomeric surfactants (quaternary dodecyldimethylammonium ions with two, three, or four chains connected by an ethylene spacer at the headgroup level, abbreviated as dimer, trimer, and tetramer) were synthesized and characterized. The influence of the degree of oligomerization on their polymorphic and mesomorphic properties was investigated by means of X-ray diffraction, polarizing optical microscopy, thermogravimetry, and differential scanning calorimetry. All compounds display layered arrangements with interdigitated dodecyl chains. The increase in the degree of oligomerization increases the interlayer distance and decreases the ordering in the solid phase; whereas the dimer sample is fully crystalline with well-developed 3D ordering and the trimer and tetramer crystallize as highly ordered crystal smectic phases. The number of thermal phase transitions and sequence of phases are markedly affected by the number of dodecyl chains. Anhydrous samples exhibit polymorphism and thermotropic mesomorphism of the smectic type, with the exception of the tetramer that displays only transitions at higher temperature associated with decomposition and melting. All hydrated compounds form lyotropic mesophases showing reversible phase transitions upon heating and cooling. The sequence of liquid-crystalline phases for the dimer, typical of concentrated ionic surfactant systems, comprises a hexagonal phase at lower temperatures and a smectic phase at higher temperatures. In contrast, the trimer and tetramer reveal textures of the hexagonal phase. © 2011 American Chemical Society

Shape-dependent dispersion and alignment of nonaggregating plasmonic gold nanoparticles in lyotropic and thermotropic liquid crystals.

PubMed

Liu, Qingkun; Tang, Jianwei; Zhang, Yuan; Martinez, Angel; Wang, Shaowei; He, Sailing; White, Timothy J; Smalyukh, Ivan I

2014-05-01

We use both lyotropic liquid crystals composed of prolate micelles and thermotropic liquid crystals made of rod-like molecules to uniformly disperse and unidirectionally align relatively large gold nanorods and other complex-shaped nanoparticles at high concentrations. We show that some of these ensuing self-assembled orientationally ordered soft matter systems exhibit polarization-dependent plasmonic properties with strongly pronounced molar extinction exceeding that previously achieved in self-assembled composites. The long-range unidirectional alignment of gold nanorods is mediated mainly by anisotropic surface anchoring interactions at the surfaces of gold nanoparticles. Polarization-sensitive absorption, scattering, and extinction are used to characterize orientations of nanorods and other nanoparticles. The experimentally measured unique optical properties of these composites, which stem from the collective plasmonic effect of the gold nanorods with long-range order in a liquid crystal matrix, are reproduced in computer simulations. A simple phenomenological model based on anisotropic surface interaction explains the alignment of gold nanorods dispersed in liquid crystals and the physical underpinnings behind our observations.

Confinement effects on lyotropic nematic liquid crystal phases of graphene oxide dispersions

NASA Astrophysics Data System (ADS)

Al-Zangana, Shakhawan; Iliut, Maria; Turner, Michael; Vijayaraghavan, Aravind; Dierking, Ingo

2017-12-01

Graphene oxide (GO) forms well ordered liquid crystal (LC) phases in polar solvents. Here, we map the lyotropic phase diagram of GO as a function of the lateral dimensions of the GO flakes, their concentration, geometrical confinement configuration and solvent polarity. GO flakes were prepared in water and transferred into other polar solvents. Polarising optical microscopy (POM) was used to determine the phase evolution through the isotropic-biphasic-nematic transitions of the GO LC. We report that the confinement volume and geometry relative to the particle size is critical for the observation of the lyotropic phase, specifically, this determines the low-end concentration limit for the detection of the GO LC. Additionally, a solvent with higher polarisability stabilises the LC phases at lower concentrations and smaller flake sizes. GO LCs have been proposed for a range of applications from display technologies to conductive fibres, and the behaviour of LC phase formation under confinement imposes a limit on miniaturisation of the dimensions of such GO LC systems which could significantly impact on their potential applications.

Ultrasonic Resonance Spectrometry with Fourier Synthesized Pseudorandom Noise Excitation and Its Application to a Lyotropiec Liquid Crystal

NASA Astrophysics Data System (ADS)

Nakamura, Haruki; Naito, Yasushi; Tsuboi, Yukitoshi; Mitaku, Shigeki; Okano, Koji

1982-11-01

Time domain measurement to obtain ultrasonic resonance spectra was made using Fourier Synthesized Pseudorandom Noise (FSPN) excitation in order to observe the viscoelastic property of a lyotropic liquid crystal. The FSPN with multiple frequency components was amplitude-modulated by a carrier signal with a much higher single frequency component, and a quadrature detection technique was used to obtain a shear ultrasonic resonance spectrum produced between two transducers. A reflection method was applied to observe mechanical impedance of viscous and elastic materials at about 3 MHz. The viscosities obtained for standard viscous materials agreed well with literature values, and the rigidity and viscosity of a lyotropic liquid crystal of Sodium Lauryl Sulfate with water were measured; they were ˜ 106 dyn/cm2 and ˜0.1 P, respectively.

Influence of chain length and double bond on the aqueous behavior of choline carboxylate soaps.

PubMed

Rengstl, Doris; Diat, Olivier; Klein, Regina; Kunz, Werner

2013-02-26

In preceding studies, we demonstrated that choline carboxylates ChC(m) with alkyl chain lengths of m = 12 - 18 are highly water-soluble (for m = 12, soluble up to 93 wt % soap and 0 °C). In addition, choline soaps are featured by an extraordinary lyotropic phase behavior. With decreasing water concentration, the following phases were found: micellar phase (L(1)), discontinuous cubic phase (I(1)' and I(1)"), hexagonal phase (H(1)), bicontinuous cubic phase (V(1)), and lamellar phase (L(α)). The present work is also focused on the lyotropic phase behavior of choline soaps but with shorter alkyl chains or different alkyl chain properties. We have investigated the aqueous phase behavior of choline soaps with C(8) and C(10) chain-lengths (choline octanoate and choline decanoate) and with a C(18) chain-length with a cis-double bond (choline oleate). We found that choline decanoate follows the lyotropic phase behavior of the longer-chain homologues mentioned above. Choline octanoate in water shows no discontinuous cubic phases, but an extended, isotropic micellar solution phase. In addition, choline octanoate is at the limit between a surfactant and a hydrotrope. The double bond in choline oleate leads also to a better solubility in water and a decrease of the solubilization temperature. It also influences the Gaussian curvature of the aggregates which results in a loss of discontinuous cubic phases in the binary phase diagram. The different lyotropic mesophases were identified by the penetration scan technique with polarizing light microscope and visual observations. To clarify the structural behavior small (SAXS) and wide (WAXS) angle X-ray scattering were performed. To further characterize the extended, isotropic micellar solution phase in the binary phase diagram of choline octanoate viscosity and conductivity measurements were also carried out.

PEG-nanotube liquid crystals as templates for construction of surfactant-free gold nanorods.

PubMed

Kameta, Naohiro; Shiroishi, Hidenobu

2018-05-03

Lyotropic liquid crystals, in which nanotubes coated with polyethylene glycol were aligned side-by-side in aqueous dispersions, acted as templates for the construction of surfactant-free gold nanorods with controllable diameters, functionalizable surfaces, and tunable optical properties.

Noncovalent Polymerization of Mesogens Crystallizes Lysozyme: Correlation between Nonamphiphilic Lyotropic Liquid Crystal Phase and Protein Crystal Formation

PubMed Central

Simon, Karen A.; Shetye, Gauri S.; Englich, Ulrich; Wu, Lei; Luk, Yan-Yeung

2011-01-01

Crystallization of proteins is important for fundamental studies and biopharmaceutical development but remains largely an empirical science. Here, we report the use of organic salts that can form a class of unusual non-amphiphilic lyotropic liquid crystals to crystallize the protein lysozyme. Certain non-amphiphilic organic molecules with fused aromatic rings and two charges can assemble into stable thread-like noncovalent polymers that may further form liquid crystal phases in water, traditionally termed chromonic liquid crystals. Using five of these mesogenic molecules as additives to induce protein crystallization, we discover that molecules that can form liquid crystal phases in water are highly effective at inducing the crystal formation of lysozyme, even at concentrations significantly lower than that required for forming liquid crystal phases. This result reveals an example of inducing protein crystallization by the molecular assembly of the additives, and is consistent with a new mechanism by which the strong hydration of an assembly process provides a gradual means to compete for the water molecules to enable solvated proteins to form crystals. PMID:21786812

Spectroscopic characterizations of a mixed surfactant mesophase and its application in materials synthesis

NASA Astrophysics Data System (ADS)

Liu, Limin

A viscous lyotropic crystalline mesophase containing bis (2-ethylhexyl) sodium sulfosuccinate (AOT), alpha-phosphatidylcholine (lecithin), with comparable volume fractions of isooctane and water was characterized by Fourier-transform 31P and 1H nuclear magnetic resonance (NMR) spectroscopy. Shear alignment on the reverse hexagonal mesophase was reflected through both 31P NMR and 1H NMR spectra. A complicated 31P spectrum was observed as a result of superposition of chemical shifts according to the distribution of crystalline domains prior to shear. The initially disordered samples with polydomain structures became macroscopically aligned after Couette shear and the alignment retained for a long period of time. 31P NMR chemical shift anisotropy characteristics were used to elucidate orientation of the hexagonal phase. Interestingly, 1H NMR of the water, methyl and methylene groups exhibited spectral changes upon shear alignment closely corresponding with that of 31P NMR spectra. A reverse hexagonal to lamellar phase transition was manifested as an expanding of the expressed 31P NMR chemical shift anisotropy and an apparent reversal of the powder pattern with increasing water content and/or temperature. Correspondingly, 1H NMR spectra also experienced a spectral pattern transition as the water content or temperature was increased. These observations complement the findings of mesophase alignment obtained using small angle neutron scattering (SANS) and imply that 31P and 1H NMR spectroscopy can be used as probes to define microstructure and monitor orientation changes in this binary surfactant system. This is especially beneficial if these mesophases are used as templates for materials synthesis. The mesophase retains its alignment for extended periods allowing materials synthesis to be decoupled from the application of shear. Highly aligned string-like silica nanostructures were obtained through templated synthesis in the columnar hexagonal structure of the viscous lyotropic crystalline mesophase. A two-step procedure was used to first shear-align the surfactant mesophase, and then conduct synthesis under quiescent conditions in the mesophase. Polystyrene was post-grafted to the silica surface without disturbing its nanostring morphology. The coupling of materials synthesis in surfactant mesophases with processing techniques (e.g. extrusion) may result in functional materials, such as new catalyst support and membrane nanoarchitectures.

Surfactant induced stabilization of nano liquid crystalline (dodecane-phytantriol) droplet

NASA Astrophysics Data System (ADS)

Abbas, S.; Saha, Debasish; Kumar, Sugam; Aswal, V. K.; Kohlbrecher, J.

2018-04-01

The study of formation and stabilization of dodecane-phytantriol (DPT) microemulsions using ionic and nonionic surfactants are investigated. Small Angle Neutron Scattering (SANS) and Dynamic Light Scattering (DLS) techniques have been employed to study the resulting structures of the micro emulsion droplets. We show the formation of stable microemulsion droplets with absence of lyotropic liquid crystalline phase on addition of nonionic surfactant C12E10. The oil to surfactant ratio plays the crucial role in formation of stable droplet and its size. The dense presence of C12E10 molecules between microemulsion droplets protect them from coalescence while less number of C12E10 between the surface of droplets easily triggers the coalescence process. The interaction with both anionic (SDS) as well as cationic (DTAB) surfactants with DPT phase leads to formation of microemulsion droplets with lyotropic liquid crystalline phase.

Brownian Dynamics of Colloidal Particles in Lyotropic Chromonic Liquid Crystals

NASA Astrophysics Data System (ADS)

Martinez, Angel; Collings, Peter J.; Yodh, Arjun G.

We employ video microscopy to study the Brownian dynamics of colloidal particles in the nematic phase of lyotropic chromonic liquid crystals (LCLCs). These LCLCs (in this case, DSCG) are water soluble, and their nematic phases are characterized by an unusually large elastic anisotropy. Our preliminary measurements of particle mean-square displacement for polystyrene colloidal particles (~5 micron-diameter) show diffusive and sub-diffusive behaviors moving parallel and perpendicular to the nematic director, respectively. In order to understand these motions, we are developing models that incorporate the relaxation of elastic distortions of the surrounding nematic field. Further experiments to confirm these preliminary results and to determine the origin of these deviations compared to simple diffusion theory are ongoing; our results will also be compared to previous diffusion experiments in nematic liquid crystals. We gratefully acknowledge financial support through NSF DMR12-05463, MRSEC DMR11-20901, and NASA NNX08AO0G.

Electrostatic Interactions Govern "Odd/Even" Effects in Water-Induced Gemini Surfactant Self-Assembly.

PubMed

Mantha, Sriteja; McDaniel, Jesse G; Perroni, Dominic V; Mahanthappa, Mahesh K; Yethiraj, Arun

2017-01-26

Gemini surfactants comprise two single-tailed surfactants connected by a linker at or near the hydrophilic headgroup. They display a variety of water-concentration-dependent lyotropic liquid crystal morphologies that are sensitive to surfactant molecular structure and the nature of the headgroups and counterions. Recently, an interesting dependence of the aqueous-phase behavior on the length of the linker has been discovered; odd-numbered linker length surfactants exhibit characteristically different phase diagrams than even-numbered linker surfactants. In this work, we investigate this "odd/even effect" using computer simulations, focusing on experimentally studied gemini dicarboxylates with Na + counterions, seven nonterminal carbon atoms in the tails, and either three, four, five, or six carbon atoms in the linker (denoted Na-73, Na-74, Na-75, and Na-76, respectively). We find that the relative electrostatic repulsion between headgroups in the different morphologies is correlated with the qualitative features of the experimental phase diagrams, predicting destabilization of hexagonal phases as the cylinders pack close together at low water content. Significant differences in the relative headgroup orientations of Na-74 and Na-76 compared to those of Na-73 and Na-75 surfactants lead to differences in linker-linker packing and long-range headgroup-headgroup electrostatic repulsion, which affects the delicate electrostatic balance between the hexagonal and gyroid phases. Much of the fundamental insight presented in this work is enabled by the ability to computationally construct and analyze metastable phases that are not observable in experiments.

Triply Periodic Multiply Continuous Lyotropic Liquid Crystals Derived from Gemini Surfactants

NASA Astrophysics Data System (ADS)

Sorenson, Gregory P.

A subtle balance of non-covalent interactions directs the self-assembly of small molecule amphiphiles in aqueous media into supramolecular assemblies known as aqueous lyotropic liquid crystals (LLCs). Aqueous LLCs form many intricate, ordered nanoscale morphologies comprising distinct and structurally periodic hydrophobic and hydrophilic domains. Triply periodic multiply continuous (TPMC) LLC morphologies, which exhibit continuous hydrophobic and aqueous domains that percolate in three-dimensions, are of particular interest by virtue of their potentially wide ranging technological applications including advanced membranes for electrical energy storage and utilization, therapeutic delivery, and templates for new organic and inorganic mesoporous materials. However, robust molecular design criteria for amphiphiles that readily form TMPC morphologies are notably lacking in the literature. Recent reports have described the increased propensity for quaternary ammonium and phosphonium gemini surfactants, derived from dimerization of traditional single-tail surfactants at or near the hydrophilic headgroups through a hydrophobic linker, to stabilize TMPC mesophases. The generality of this surfactant design strategy remains untested in other amphiphiles classes bearing different headgroup chemistries. In this thesis, we describe the unusual aqueous LLC phase behavior of series of gemini dicarboxylate amphiphiles as a function of the alkyl tail length, hydrophobic linker length, and the charge-compensating counterion. These dicarboxylate surfactants unexpectedly exhibit a strong propensity to form TPMC LLCs over amphiphile concentration windows as wide as 20 wt% over a temperature range T = 25--100 °C. Through systematic modifications of the length of the hydrophobic linker and alkyl tails, we use small-angle X-ray scattering to demonstrate that these surfactants adopt new LLC mesophases including the first report of a single-gyroid phase (I4132 symmetry) and a new, tetracontinuous hexagonal network phase ( P63/mcm symmetry). Additionally, we probe the role of the linker position in the surfactant architecture. These data taken together indicate the sensitive dependence of the LLC phase behavior on counterion-headgroup correlations. Based on these molecular design criteria, we demonstrate the synthesis of a polymerizable gemini surfactant that may be self-assembled into a TPMC LLC phase and covalently fixed by a crosslinking photopolymerization. Comprised of aqueous nanochannels lined with metal carboxylates, the resulting LLC membranes exhibit high ionic conductivities.

A Simple Experiment Illustrating the Structure of Association Colloids.

ERIC Educational Resources Information Center

Friberg, Stig. E.; Bendiksen, Beverly

1979-01-01

The experiment described is intended to illustrate the intermolecular phenomena involved in association colloids. These are normal and inverse micelles and lyotropic liquid crystals. Solubilization, microemulsion and emulsion are discussed. (Author/SA)

Perylene bisimide hydrogels and lyotropic liquid crystals with temperature-responsive color change.

PubMed

Görl, Daniel; Soberats, Bartolome; Herbst, Stefanie; Stepanenko, Vladimir; Würthner, Frank

2016-11-01

The self-assembly of perylene bisimide (PBI) dyes bearing oligo ethylene glycol (OEG) units in water affords responsive functional nanostructures characterized by their lower critical solution temperature (LCST). Tuning of the LCST is realized by a supramolecular approach that relies on two structurally closely related PBI-OEG molecules. The two PBIs socially co-assemble in water and the resulting nanostructures exhibit a single LCST in between the transition temperatures of the aggregates formed by single components. This permits to precisely tune the transition from a hydrogel to a lyotropic liquid crystal state at temperatures between 26 and 51 °C by adjusting the molar fraction of the two PBIs. Owing to concomitant changes in PBI-PBI interactions this phase transition affords a pronounced color change with "fluorescence-on" response that can be utilized as a smart temperature sensory system.

Development of New Supramolecular Lyotropic Liquid Crystals and Their Application as Alignment Media for Organic Compounds.

PubMed

Leyendecker, Martin; Meyer, Nils-Christopher; Thiele, Christina M

2017-09-11

Most alignment media for the residual dipolar coupling (RDC) based molecular structure determination of small organic compounds consist of rod-like polymers dissolved in organic solvents or of swollen cross-linked polymer gels. Thus far, the synthesis of polymer-based alignment media has been a challenging process, which is often followed by a time-consuming sample preparation. We herein propose the use of non-polymeric alignment media based on benzenetricarboxamides (BTAs), which self-assemble into rod-like supramolecules. Our newly found supramolecular lyotropic liquid crystals (LLCs) are studied in terms of their LLC properties and their suitability as alignment media in NMR spectroscopy. Scalable enantiodifferentiating properties are introduced through a sergeant-and-soldier principle by blending achiral with chiral substituted BTAs. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Free-standing mesoporous silica films with tunable chiral nematic structures.

PubMed

Shopsowitz, Kevin E; Qi, Hao; Hamad, Wadood Y; Maclachlan, Mark J

2010-11-18

Chirality at the molecular level is found in diverse biological structures, such as polysaccharides, proteins and DNA, and is responsible for many of their unique properties. Introducing chirality into porous inorganic solids may produce new types of materials that could be useful for chiral separation, stereospecific catalysis, chiral recognition (sensing) and photonic materials. Template synthesis of inorganic solids using the self-assembly of lyotropic liquid crystals offers access to materials with well-defined porous structures, but only recently has chirality been introduced into hexagonal mesostructures through the use of a chiral surfactant. Efforts to impart chirality at a larger length scale using self-assembly are almost unknown. Here we describe the development of a photonic mesoporous inorganic solid that is a cast of a chiral nematic liquid crystal formed from nanocrystalline cellulose. These materials may be obtained as free-standing films with high surface area. The peak reflected wavelength of the films can be varied across the entire visible spectrum and into the near-infrared through simple changes in the synthetic conditions. To the best of our knowledge these are the first materials to combine mesoporosity with long-range chiral ordering that produces photonic properties. Our findings could lead to the development of new materials for applications in, for example, tuneable reflective filters and sensors. In addition, this type of material could be used as a hard template to generate other new materials with chiral nematic structures.

Electrostatic Interactions Govern “Odd/Even” Effects in Water-Induced Gemini Surfactant Self-Assembly

DOE PAGES

Mantha, Sriteja; McDaniel, Jesse G.; Perroni, Dominic V.; ...

2016-12-27

Gemini surfactants comprise two single-tailed surfactants connected by a linker at or near the hydrophilic headgroup. They display a variety of water concentration-dependent lyotropic liquid crystal (LLC) morphologies that are sensitive to surfactant molecular structure, and na- ture of the headgroups and counterions. Recently, an interesting dependence of the aqueous phase behavior on the length of the linker has been discovered; odd-numbered linker length surfactants exhibit characteristically different phase diagrams than even-numbered linker sur- factants. In this work, we investigate this “odd/even effect” using computer simulations, focusing on experimentally studied gemini dicarboxylates with Na + counterions, 7 non-terminal carbon atomsmore » in the tails, and either 3, 4, 5, or 6 carbon atoms in the linker (denoted Na-73, Na-74, Na-75, and Na-76 respectively). We find that the relative electrostatic repulsion be- tween headgroups in the different morphologies is correlated with qualitative features of the experimental phase diagrams, predicting destabilization of hexagonal phases as the cylinders pack close together at low water content. Significant differences in the relative headgroup ori- entations of Na-74 and Na-76 compared to Na-73 and Na-75 surfactants lead to differences in linker-linker packing, and long-range headgroup/headgroup electrostatic repulsion, which affects the delicate electrostatic balance between hexagonal and gyroid phases. Finally, much of the fundamental insight presented in this work is enabled by the ability to computationally construct and analyze metastable phases that are not observable in experiments.« less

Prediction of EPR Spectra of Lyotropic Liquid Crystals using a Combination of Molecular Dynamics Simulations and the Model-Free Approach.

PubMed

Prior, Christopher; Oganesyan, Vasily S

2017-09-21

We report the first application of fully atomistic molecular dynamics (MD) simulations to the prediction of the motional electron paramagnetic resonance (EPR) spectra of lyotropic liquid crystals in different aggregation states doped with a paramagnetic spin probe. The purpose of this study is twofold. First, given that EPR spectra are highly sensitive to the motions and order of the spin probes doped within lyotropic aggregates, simulation of EPR line shapes from the results of MD modelling provides an ultimate test bed for the force fields currently employed to model such systems. Second, the EPR line shapes are simulated using the motional parameters extracted from MD trajectories using the Model-Free (MF) approach. Thus a combined MD-EPR methodology allowed us to test directly the validity of the application of the MF approach to systems with multi-component molecular motions. All-atom MD simulations using the General AMBER Force Field (GAFF) have been performed on sodium dodecyl sulfate (SDS) and dodecyltrimethylammonium chloride (DTAC) liquid crystals. The resulting MD trajectories were used to predict and interpret the EPR spectra of pre-micellar, micellar, rod and lamellar aggregates. The predicted EPR spectra demonstrate good agreement with most of experimental line shapes thus confirming the validity of both the force fields employed and the MF approach for the studied systems. At the same time simulation results confirm that GAFF tends to overestimate the packing and the order of the carbonyl chains of the surfactant molecules. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Non-linear optical measurement of the twist elastic constant in thermotropic and DNA lyotropic chiral nematics.

PubMed

Lucchetti, Liana; Fraccia, Tommaso P; Ciciulla, Fabrizio; Bellini, Tommaso

2017-07-10

Throughout the whole history of liquid crystals science, the balancing of intrinsic elasticity with coupling to external forces has been the key strategy for most application and investigation. While the coupling of the optical field to the nematic director is at the base of a wealth of thoroughly described optical effects, a significant variety of geometries and materials have not been considered yet. Here we show that by adopting a simple cell geometry and measuring the optically induced birefringence, we can readily extract the twist elastic coefficient K 22 of thermotropic and lyotropic chiral nematics (N*). The value of K 22 we obtain for chiral doped 5CB thermotropic N* well matches those reported in the literature. With this same strategy, we could determine for the first time K 22 of the N* phase of concentrated aqueous solutions of DNA oligomers, bypassing the limitations that so far prevented measuring the elastic constants of this class of liquid crystalline materials. The present study also enlightens the significant nonlinear optical response of DNA liquid crystals.

Process for recovering chaotropic anions from an aqueous solution also containing other ions

DOEpatents

Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.

1999-01-01

A solid/liquid process for the separation and recovery of chaotropic anions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the chaotropic anions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt (lyotrope). A solid/liquid phase admixture of separation particles containing bound chaotropic anions in such an aqueous solution is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture.

Process for recovering chaotropic anions from an aqueous solution also containing other ions

DOEpatents

Rogers, R.; Horwitz, E.P.; Bond, A.H.

1999-03-30

A solid/liquid process for the separation and recovery of chaotropic anions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the chaotropic anions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt (lyotrope). A solid/liquid phase admixture of separation particles containing bound chaotropic anions in such an aqueous solution is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture. 19 figs.

Anisamide-Anchored Lyotropic Nano-Liquid Crystalline Particles with AIE Effect: A Smart Optical Beacon for Tumor Imaging and Therapy.

PubMed

Urandur, Sandeep; Banala, Venkatesh Teja; Shukla, Ravi Prakash; Mittapelly, Naresh; Pandey, Gitu; Kalleti, Navodayam; Mitra, Kalyan; Rath, Srikanta Kumar; Trivedi, Ritu; Ramarao, Pratibha; Mishra, Prabhat Ranjan

2018-04-18

The prospective design of nanocarriers for personalized oncotherapy should be an ensemble of targeting, imaging, and noninvasive therapeutic capabilities. Herein, we report the development of the inverse hexagonal nano-liquid crystalline (NLC) particles that are able to host formononetin (FMN), a phytoestrogen with known anticancer activity, and tetraphenylethene (TPE), an iconic optical beacon with aggregation-induced emission (AIE) signature, simultaneously. Ordered three-dimensional mesoporous internal structure and high-lipid-volume fraction of NLC nanoparticles (NLC NPs) frame the outer compartment for the better settlement of payloads. Embellishment of these nanoparticles by anisamide (AA), a novel sigma receptor targeting ligand using carbodiimide coupling chemistry ensured NLC's as an outstanding vehicle for possible utility in surveillance of tumor location as well as the FMN delivery through active AIE imaging. The size and structural integrity of nanoparticles were evaluated by quasi-elastic light scattering, cryo field emission scanning electron microscopy small-angle X-ray scattering. The existence of AIE effect in the nanoparticles was evidenced through the photophysical studies that advocate the application of NLC NPs in fluorescence-based bioimaging. Moreover, confocal microscopy illustrated the single living cell imaging ability endowed by the NLC NPs. In vitro and in vivo studies supported the enhanced efficacy of targeted nanoparticles (AA-NLC-TF) in comparison to nontargeted nanoparticles (NLC-TF) and free drug. Apparently, this critically designed multimodal NLC NPs may establish a promising platform for targeted and image-guided chemotherapy for breast cancer.

Exploring the Phase Behavior of Monoolein/Oleic Acid/Water Systems for Enhanced Donezepil Administration for Alzheimer Disease Treatment.

PubMed

Ruela, André Luís Morais; Carvalho, Flávia Chiva; Pereira, Gislaine Ribeiro

2016-01-01

Donepezil is a drug usually administered by oral route for Alzheimer disease treatment, but several gastric side effects have been reported as diarrhea, nausea, and anorexia. We explored the phase behavior of lyotropic liquid crystalline (LLC) mesophases composed by monoolein/oleic acid/water for enhanced administration of donepezil. Polarized light microscopy suggested that these systems ranged from isotropic inverse micellar solutions (L2) to viscous and birefringent reverse hexagonal (HII) mesophases according to the amount of water in the ternary systems. Phase transition was observed from a L2 phase to HII mesophase after swelling studies, an interesting property to be explored as a precursor of LLC mesophases for mucosal administration that increases its viscosity in situ. Mucoadhesive properties of LLC mesophases were characterized using a texture analyzer indicating that these systems can have an increased residence time in the site of absorption. Donepezil-free base was incorporated in the evaluated formulations, and their in vitro release was controlled up to 24 h. The phase behavior of the systems demonstrated a great potential for enhanced donepezil administration once these mucoadhesive-controlled release formulations can incorporate the drug and prolong its release, possibly reducing its side effects. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Dual-modality NIRF-MRI cubosomes and hexosomes: High throughput formulation and in vivo biodistribution.

PubMed

Tran, Nhiem; Bye, Nicole; Moffat, Bradford A; Wright, David K; Cuddihy, Andrew; Hinton, Tracey M; Hawley, Adrian M; Reynolds, Nicholas P; Waddington, Lynne J; Mulet, Xavier; Turnley, Ann M; Morganti-Kossmann, M Cristina; Muir, Benjamin W

2017-02-01

Engineered nanoparticles with multiple complementary imaging modalities are of great benefit to the rapid treatment and diagnosis of disease in various organs. Herein, we report the formulation of cubosomes and hexosomes that carry multiple amphiphilic imaging contrast agents in their self-assembled lipid bilayers. This is the first report of the use of both near infrared fluorescent (NIRF) imaging and gadolinium lipid based magnetic resonance (MR) imaging modalities in cubosomes and hexosomes. High-throughput screening was used to rapidly optimize formulations with desirable nano-architectures and low in vitro cytotoxicity. The dual-modal imaging nanoparticles in vivo biodistribution and organ specific contrast enhancement were then studied. The NIRF in vivo imaging results indicated accumulation of both cubosomes and hexosomes in the liver and spleen of mice up to 20h post-injection. Remarkably, the biodistribution of the nanoparticle formulations was affected by the mesophase (i.e. cubic or hexagonal), a finding of significant importance for the future use of these compounds, with hexosomes showing higher accumulation in the spleen than the liver compared to cubosomes. Furthermore, in vivo MRI data of animals injected with either type of lyotropic liquid crystal nanoparticle displayed enhanced contrast in the liver and spleen. Copyright © 2016 Elsevier B.V. All rights reserved.

Electrochemical synthesis of mesoporous Pt-Au binary alloys with tunable compositions for enhancement of electrochemical performance.

PubMed

Yamauchi, Yusuke; Tonegawa, Akihisa; Komatsu, Masaki; Wang, Hongjing; Wang, Liang; Nemoto, Yoshihiro; Suzuki, Norihiro; Kuroda, Kazuyuki

2012-03-21

Mesoporous Pt-Au binary alloys were electrochemically synthesized from lyotropic liquid crystals (LLCs) containing corresponding metal species. Two-dimensional exagonally ordered LLC templates were prepared on conductive substrates from diluted surfactant solutions including water, a nonionic surfactant, ethanol, and metal species by drop-coating. Electrochemical synthesis using such LLC templates enabled the preparation of ordered mesoporous Pt-Au binary alloys without phase segregation. The framework composition in the mesoporous Pt-Au alloy was controlled simply by changing the compositional ratios in the precursor solution. Mesoporous Pt-Au alloys with low Au content exhibited well-ordered 2D hexagonal mesostructures, reflecting those of the original templates. With increasing Au content, however, the mesostructural order gradually decreased, thereby reducing the electrochemically active surface area. Wide-angle X-ray diffraction profiles, X-ray photoelectron spectra, and elemental mapping showed that both Pt and Au were atomically distributed in the frameworks. The electrochemical stability of mesoporous Pt-Au alloys toward methanol oxidation was highly improved relative to that of nonporous Pt and mesoporous Pt films, suggesting that mesoporous Pt-Au alloy films are potentially applicable as electrocatalysts for direct methanol fuel cells. Also, mesoporous Pt-Au alloy electrodes showed a highly sensitive amperometric response for glucose molecules, which will be useful in next-generation enzyme-free glucose sensors.

Self-assembled block copolymer-nanoparticle hybrids: interplay between enthalpy and entropy.

PubMed

Sarkar, Biswajit; Alexandridis, Paschalis

2012-11-13

The dispersion of nanoparticles in ordered block copolymer nanostructures can provide control over particle location and orientation, and pave the way for engineered nanomaterials that have enhanced mechanical, electrical, or optical properties. Fundamental questions pertaining to the role of enthalpic and entropic particle-polymer interactions remain open and motivate the present work. We consider here a system of 10.6 nm silica nanoparticles (NPs) dispersed in ordered cylinders formed by hydrated poly(ethylene oxide)-poly(propylene oxide) block copolymers (Pluronic P105: EO(37)PO(56)EO(37)). Protonation of silica was used to vary the NP-polymer enthalpic interactions, while polar organic solvents (glycerol, DMSO, ethanol, and DMF) were used to modulate the NP-polymer entropic interactions. The introduction of deprotonated NPs in the place of an equal mass of water did not affect the lattice parameter of the PEO-PPO-PEO block copolymer hexagonal lyotropic liquid crystalline structures. However, the dispersion of protonated NPs led to an increase in the lattice parameter, which was attributed to stronger NP-polymer hydrogen bonding (enthalpic) interactions. Dispersion of protonated NPs into cylindrical structures formed by Pluronic P105 in 80/20 water/organic solvents does not influence the lattice parameter, different from the case of protonated NP in plain water. Organic solvents appear to screen the NP-polymer hydrogen bonding interactions.

Rational design of mesoporous metals and related nanomaterials by a soft-template approach.

PubMed

Yamauchi, Yusuke; Kuroda, Kazuyuki

2008-04-07

We review recent developments in the preparation of mesoporous metals and related metal-based nanomaterials. Among the many types of mesoporous materials, mesoporous metals hold promise for a wide range of potential applications, such as in electronic devices, magnetic recording media, and metal catalysts, owing to their metallic frameworks. Mesoporous metals with highly ordered networks and narrow pore-size distributions have traditionally been produced by using mesoporous silica as a hard template. This method involves the formation of an original template followed by deposition of metals within the mesopores and subsequent removal of the template. Another synthetic method is the direct-template approach from lyotropic liquid crystals (LLCs) made of nonionic surfactants at high concentrations. Direct-template synthesis creates a novel avenue for the production of mesoporous metals as well as related metal-based nanomaterials. Many mesoporous metals have been prepared by the chemical or electrochemical reduction of metal salts dissolved in aqueous LLC domains. As a soft template, LLCs are more versatile and therefore more advantageous than hard templates. It is possible to produce various nanostructures (e.g., lamellar, 2D hexagonal (p6mm), and 3D cubic (Ia\\3d)), nanoparticles, and nanotubes simply by controlling the composition of the reaction bath.

Transitions induced by solubilized fat into reverse hexagonal mesophases.

PubMed

Amar-Yuli, Idit; Garti, Nissim

2005-06-25

Lyotropic liquid crystals of glycerol monooleate (GMO) and water binary mixtures have been extensively studied and their resemblance to human membranes has intrigued many scientists. Biological systems as well as food mixtures are composed of lipids and fat components including triacylglycerols (TAGs, triglycerides) that can affect the nature of the assembly of the mesophase. The present study examines the effect of TAGs of different chain lengths (C(2)-C(18)) at various water/GMO compositions, on phase transitions from lamellar or cubic to reverse hexagonal (L(alpha)-H(II) and Q-H(II)). The ability of the triglycerides to promote the formation of an H(II) mesophase is chain length-dependent. It was found that TAG molecules with very short acyl chains (triacetin) can hydrate the head groups of the lipid and do not affect the critical packing parameter (CPP) of the amphiphile; therefore, they do not affect the self-assembly of the GMO in water, and the mesophase remains lamellar or cubic. However, TAGs with medium chain fatty acids will solvate the tails of the lipid, and will affect the CPP of the GMO, and transform the lamellar or cubic phases into hexagonal mesophase. TAGs with long chain fatty acids are very bulky, not very miscible with the GMO, and therefore, kinetically are very slow to solvate the lipid tails of the amphiphile and are difficult to accommodate into the lipophilic parts of the GMO. Their effect on the transitions from a lamellar or cubic phase to hexagonal is detected only after months of equilibration. In order to enhance the effect of the TAG on the phase transitions in the GMO/triglyceride/water systems, temperature and electrolytes effects were examined. In the presence of short and medium chain triglycerides, increasing temperature caused a transition from lamellar or hexagonal to L(2) phase (highest CPP value). However, in the presence of long chain TAGs, increasing temperature to ca. 40 degrees C caused a formation of H(II) mesophase. In addition, it was found that in tricaprylin/GMO/water systems, the increase in temperature caused a decrease in the lattice parameter. The effect of NaCl on the H(II) mesophase revealed interesting results. At low concentration of tricaprylin (5 wt%), the addition of only 0.1 wt% of NaCl was sufficient to cause the formation of well-defined H(II) mesophase, while further addition of electrolyte increased the hexagonal lattice parameters. At higher TAGs concentrations (10 wt%), addition of electrolyte resulted in the formation of H(II) with modifications of the lattice parameter. All the examined effects were more pronounced with increasing water content.

Perylene bisimide hydrogels and lyotropic liquid crystals with temperature-responsive color change† †Electronic supplementary information (ESI) available: Detailed procedures and results for all reported experiments, along with synthetic details for PBI 1. See DOI: 10.1039/c6sc02249a Click here for additional data file.

PubMed Central

Görl, Daniel; Soberats, Bartolome; Herbst, Stefanie; Stepanenko, Vladimir

2016-01-01

The self-assembly of perylene bisimide (PBI) dyes bearing oligo ethylene glycol (OEG) units in water affords responsive functional nanostructures characterized by their lower critical solution temperature (LCST). Tuning of the LCST is realized by a supramolecular approach that relies on two structurally closely related PBI–OEG molecules. The two PBIs socially co-assemble in water and the resulting nanostructures exhibit a single LCST in between the transition temperatures of the aggregates formed by single components. This permits to precisely tune the transition from a hydrogel to a lyotropic liquid crystal state at temperatures between 26 and 51 °C by adjusting the molar fraction of the two PBIs. Owing to concomitant changes in PBI–PBI interactions this phase transition affords a pronounced color change with “fluorescence-on” response that can be utilized as a smart temperature sensory system. PMID:28451124

Lyotropic liquid crystal engineering moving beyond binary compositional space - ordered nanostructured amphiphile self-assembly materials by design.

PubMed

van 't Hag, Leonie; Gras, Sally L; Conn, Charlotte E; Drummond, Calum J

2017-05-22

Ordered amphiphile self-assembly materials with a tunable three-dimensional (3D) nanostructure are of fundamental interest, and crucial for progressing several biological and biomedical applications, including in meso membrane protein crystallization, as drug and medical contrast agent delivery vehicles, and as biosensors and biofuel cells. In binary systems consisting of an amphiphile and a solvent, the ability to tune the 3D cubic phase nanostructure, lipid bilayer properties and the lipid mesophase is limited. A move beyond the binary compositional space is therefore required for efficient engineering of the required material properties. In this critical review, the phase transitions upon encapsulation of more than 130 amphiphilic and soluble additives into the bicontinuous lipidic cubic phase under excess hydration are summarized. The data are interpreted using geometric considerations, interfacial curvature, electrostatic interactions, partition coefficients and miscibility of the alkyl chains. The obtained lyotropic liquid crystal engineering design rules can be used to enhance the formulation of self-assembly materials and provides a large library of these materials for use in biomedical applications (242 references).

Ordered Nanostructured Amphiphile Self-Assembly Materials from Endogenous Nonionic Unsaturated Monoethanolamide Lipids in Water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sagnella, Sharon M.; Conn, Charlotte E.; Krodkiewska, Irena

2010-08-23

The self-assembly, solid state and lyotropic liquid crystalline phase behavior of a series of endogenous n-acylethanolamides (NAEs) with differing degrees of unsaturation, viz., oleoyl monoethanolamide, linoleoyl monoethanolamide, and linolenoyl monoethanolamide, have been examined. The studied molecules are known to possess inherent biological function. Both the monoethanolamide headgroup and the unsaturated hydrophobe are found to be important in dictating the self-assembly behavior of these molecules. In addition, all three molecules form lyotropic liquid crystalline phases in water, including the inverse bicontinuous cubic diamond (Q{sub II}{sup D}) and gyroid (Q{sub II}{sup G}) phases. The ability of the NAE's to form inverse cubicmore » phases and to be dispersed into ordered nanostructured colloidal particles, cubosomes, in excess water, combined with their endogenous nature and natural medicinal properties, makes this new class of soft mesoporous amphiphile self-assembly materials suitable candidates for investigation in a variety of advanced multifunctional applications, including encapsulation and controlled release of therapeutic agents and incorporation of medical imaging agents.« less

Control of Nanomaterial Self-Assembly in Ultrasonically Levitated Droplets.

PubMed

Seddon, Annela M; Richardson, Sam J; Rastogi, Kunal; Plivelic, Tomás S; Squires, Adam M; Pfrang, Christian

2016-04-07

We demonstrate that acoustic trapping can be used to levitate and manipulate droplets of soft matter, in particular, lyotropic mesophases formed from self-assembly of different surfactants and lipids, which can be analyzed in a contact-less manner by X-ray scattering in a controlled gas-phase environment. On the macroscopic length scale, the dimensions and the orientation of the particle are shaped by the ultrasonic field, while on the microscopic length scale the nanostructure can be controlled by varying the humidity of the atmosphere around the droplet. We demonstrate levitation and in situ phase transitions of micellar, hexagonal, bicontinuous cubic, and lamellar phases. The technique opens up a wide range of new experimental approaches of fundamental importance for environmental, biological, and chemical research.

Liquid Crystalline Behavior and Related Properties of Colloidal Systems of Inorganic Oxide Nanosheets

PubMed Central

Nakato, Teruyuki; Miyamoto, Nobuyoshi

2009-01-01

Inorganic layered crystals exemplified by clay minerals can be exfoliated in solvents to form colloidal dispersions of extremely thin inorganic layers that are called nanosheets. The obtained “nanosheet colloids” form lyotropic liquid crystals because of the highly anisotropic shape of the nanosheets. This system is a rare example of liquid crystals consisting of inorganic crystalline mesogens. Nanosheet colloids of photocatalytically active semiconducting oxides can exhibit unusual photoresponses that are not observed for organic liquid crystals. This review summarizes experimental work on the phase behavior of the nanosheet colloids as well as photochemical reactions observed in the clay and semiconducting nanosheets system.

Ionic Liquid Crystals: Versatile Materials.

PubMed

Goossens, Karel; Lava, Kathleen; Bielawski, Christopher W; Binnemans, Koen

2016-04-27

This Review covers the recent developments (2005-2015) in the design, synthesis, characterization, and application of thermotropic ionic liquid crystals. It was designed to give a comprehensive overview of the "state-of-the-art" in the field. The discussion is focused on low molar mass and dendrimeric thermotropic ionic mesogens, as well as selected metal-containing compounds (metallomesogens), but some references to polymeric and/or lyotropic ionic liquid crystals and particularly to ionic liquids will also be provided. Although zwitterionic and mesoionic mesogens are also treated to some extent, emphasis will be directed toward liquid-crystalline materials consisting of organic cations and organic/inorganic anions that are not covalently bound but interact via electrostatic and other noncovalent interactions.

Direct Visualisation of the Structural Transformation between the Lyotropic Liquid Crystalline Lamellar and Bicontinuous Cubic Mesophase.

PubMed

Tran, Nhiem; Zhai, Jiali; Conn, Charlotte E; Mulet, Xavier; Waddington, Lynne J; Drummond, Calum J

2018-05-29

The transition between the lyotropic liquid crystalline lamellar and the bicontinuous cubic mesophase drives multiple fundamental cellular processes involving changes in cell membrane topology including endocytosis and membrane budding. While several theoretical models have been proposed to explain this dynamic transformation, experimental validation of these models has been challenging due to the short lived nature of the intermediates present during the phase transition. Herein, we report the direct observation of a lamellar to bicontinuous cubic phase transition in nanoscale dispersions using a combination of cryogenic transmission electron microscopy and static small angle X-ray scattering. The results represent the first experimental confirmation of a theoretical model which proposed that the bicontinuous cubic phase originates from the centre of a lamellar vesicle, then propagates outward via the formation of inter-lamellar attachments and stalks. The observation was possible due to the precise control of the lipid composition to place the dispersion systems at the phase boundary of a lamellar and a cubic phase, allowing for the creation of long-lived structural intermediates. By surveying the nanoparticles using cryogenic transmission electron microscopy, a complete phase transition sequence was established.

Smectic phase in suspensions of gapped DNA duplexes

DOE PAGES

Salamonczyk, Miroslaw; Zhang, Jing; Portale, Giuseppe; ...

2016-11-15

Smectic ordering in aqueous solutions of monodisperse stiff double-stranded DNA fragments is known not to occur, in spite of the fact that these systems exhibit both chiral nematic and columnar mesophases. Here, we show, unambiguously, that a smectic-A type of phase is formed by increasing the DNA's flexibility through the introduction of an unpaired single-stranded DNA spacer in the middle of each duplex. This is unusual for a lyotropic system, where flexibility typically destabilizes the smectic phase. We also report on simulations suggesting that the gapped duplexes (resembling chain-sticks) attain a folded conformation in the smectic layers, and argue thatmore » this layer structure, which we designate as smectic-fA phase, is thermodynamically stabilized by both entropic and energetic contributions to the system's free energy. These results demonstrate that DNA as a building block offers an exquisitely tunable means to engineer a potentially rich assortment of lyotropic liquid crystals.« less

Low-symmetry sphere packings of simple surfactant micelles induced by ionic sphericity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Sung A.; Jeong, Kyeong-Jun; Yethiraj, Arun

We report the discovery of an ionic small molecule surfactant that undergoes water-drive self- assembly into quasispherical micelles, which pack into the first lyotropic liquid crystalline Frank–Kasper σ phase. Small-angle X-ray scattering studies indicate that this unexpected, low-symmetry phase is characterized by a tetragonal unit cell, in which 30 sub-2 nm micelles of five discrete types are arranged into a tetrahedral close packing with exceptional translational order. Varying the relative amounts of surfactant and water in these lyotropic phases enables formation of a Frank–Kasper A15 sphere packing and a more common body-centered cubic structure. MD simulations reveal that the symmetrymore » breaking that drives the selection of the σ and A15 phases arises from a delicate interplay between the drive to maintain local spherical particle symmetry and the maximization of electrostatic cohesion between the soft micellar particles.« less

Low-symmetry sphere packings of simple surfactant micelles induced by ionic sphericity

DOE PAGES

Kim, Sung A.; Jeong, Kyeong-Jun; Yethiraj, Arun; ...

2017-04-03

We report the discovery of an ionic small molecule surfactant that undergoes water-drive self- assembly into quasispherical micelles, which pack into the first lyotropic liquid crystalline Frank–Kasper σ phase. Small-angle X-ray scattering studies indicate that this unexpected, low-symmetry phase is characterized by a tetragonal unit cell, in which 30 sub-2 nm micelles of five discrete types are arranged into a tetrahedral close packing with exceptional translational order. Varying the relative amounts of surfactant and water in these lyotropic phases enables formation of a Frank–Kasper A15 sphere packing and a more common body-centered cubic structure. MD simulations reveal that the symmetrymore » breaking that drives the selection of the σ and A15 phases arises from a delicate interplay between the drive to maintain local spherical particle symmetry and the maximization of electrostatic cohesion between the soft micellar particles.« less

Manipulating the Ordered Nanostructure of Self-Assembled Monoolein and Phytantriol Nanoparticles with Unsaturated Fatty Acids.

PubMed

Tran, Nhiem; Mulet, Xavier; Hawley, Adrian M; Fong, Celesta; Zhai, Jiali; Le, Tu C; Ratcliffe, Julian; Drummond, Calum J

2018-02-27

Mesophase structures of self-assembled lyotropic liquid crystalline nanoparticles are important factors that directly influence their ability to encapsulate and release drugs and their biological activities. However, it is difficult to predict and precisely control the mesophase behavior of these materials, especially in complex systems with several components. In this study, we report the controlled manipulation of mesophase structures of monoolein (MO) and phytantriol (PHYT) nanoparticles by adding unsaturated fatty acids (FAs). By using high throughput formulation and small-angle X-ray scattering characterization methods, the effects of FAs chain length, cis-trans isomerism, double bond location, and level of chain unsaturation on self-assembled systems are determined. Additionally, the influence of temperature on the phase behavior of these nanoparticles is analyzed. We found that in general, the addition of unsaturated FAs to MO and PHYT induces the formation of mesophases with higher Gaussian surface curvatures. As a result, a rich variety of lipid polymorphs are found to correspond with the increasing amounts of FAs. These phases include inverse bicontinuous cubic, inverse hexagonal, and discrete micellar cubic phases and microemulsion. However, there are substantial differences between the phase behavior of nanoparticles with trans FA, cis FAs with one double bond, and cis FAs with multiple double bonds. Therefore, the material library produced in this study will assist the selection and development of nanoparticle-based drug delivery systems with desired mesophase.

Nonionic amphiphile nanoarchitectonics: self-assembly into micelles and lyotropic liquid crystals

NASA Astrophysics Data System (ADS)

Shrestha, Lok Kumar; Strzelczyk, Karolina Maria; Goswami Shrestha, Rekha; Ichikawa, Kotoko; Aramaki, Kenji; Hill, Jonathan P.; Ariga, Katsuhiko

2015-05-01

Amphiphiles, molecules that possess both hydrophilic and hydrophobic moieties, are architecturally simple molecules that can spontaneously self-assemble into complex hierarchical structures from lower to higher dimensions either in the bulk phase or at an interface. Recent developments in multifunctional nanostructure design using the advanced concept of nanoarchitectonics utilize this simple process of assembly. Amphiphilic self-assemblies involving lipids or proteins mimic the structure of biological systems, thus highlighting the necessity of a fundamental physical understanding of amphiphilic self-assembly towards a realization of the complex mechanisms operating in nature. Herein, we describe self-assembled microstructures of biocompatible and biodegradable tetraglycerol lauryl ether (C12G4) nonionic surfactant in an aqueous solvent system. Temperature-composition analyses of equilibrium phases identified by using small-angle x-ray scattering (SAXS) provide strong evidence of various spontaneously self-assembled mesostructures, such as normal micelles (Wm), hexagonal liquid crystal (H1), and reverse micelles (Om). In contrast to conventional poly(oxyethylene) nonionic surfactants, C12G4 did not exhibit the clouding phenomenon at higher temperatures (phase separation was not observed up to 100 °C), demonstrating the greater thermal stability of the self-assembled mesophases. Generalized indirect Fourier transformation (GIFT) evaluation of the SAXS data confirmed the formation of core-shell-type spherical micelles with a maximum dimension ca. 8.7 nm. The shape and size of the C12G4 micelles remained apparently unchanged over a wide range of concentrations (up to 20%), but intermicellar interactions increased and could be described by the Percus-Yevick (PY) theory (after Carnahan and Starling), which provides a very accurate analytical expression for the osmotic pressure of a monodisperse hard sphere.

Self-organization of a wedge-shaped surfactant in monolayers and multilayers.

PubMed

Cain, Nicholas; Van Bogaert, Josh; Gin, Douglas L; Hammond, Scott R; Schwartz, Daniel K

2007-01-16

The self-organization behavior of a wedge-shaped surfactant, disodium-3,4,5-tris(dodecyloxy)phenylmethylphosphonate, was studied in Langmuir monolayers (at the air-water interface), Langmuir-Blodgett (LB) monolayers and multilayers, and films adsorbed spontaneously from isooctane solution onto a mica substrate (self-assembled films). This compound forms an inverted hexagonal lyotropic liquid crystal phase in the bulk and in thick adsorbed films. Surface pressure isotherm and Brewster angle microscope (BAM) studies of Langmuir monolayers revealed three phases: gas (G), liquid expanded (LE), and liquid condensed (LC). The surface pressure-temperature phase diagram was determined in detail; a triple point was found at approximately 10 degrees C. Atomic force microscope (AFM) images of LB monolayers transferred from various regions of the phase diagram were consistent with the BAM images and indicated that the LE regions are approximately 0.5 nm thinner than the LC regions. AFM images were also obtained of self-assembled films after various adsorption times. For short adsorption times, when monolayer self-assembly was incomplete, the film topography indicated the coexistence of two distinct monolayer phases. The height difference between these two phases was again 0.5 nm, suggesting a correspondence with the LE/LC coexistence observed in the Langmuir monolayers. For longer immersion times, adsorbed multilayers assembled into highly organized periodic arrays of inverse cylindrical micelles. Similar periodic structures, with the same repeat distance of 4.5 nm, were also observed in three-layer LB films. However, the regions of organized periodic structure were much smaller and more poorly correlated in the LB multilayers than in the films adsorbed from solution. Collectively, these observations indicate a high degree of similarity between the molecular organization in Langmuir layers/LB films and adsorbed self-assembled films. In both cases, monolayers progress through an LE phase, into LE/LC coexistence, and finally into LC phase as surface density increases. Following the deposition of an additional bilayer, the film reorganizes to form an array of inverted cylindrical micelles.

Self-assembled ordered structures in thin films of HAT5 discotic liquid crystal.

PubMed

Morales, Piero; Lagerwall, Jan; Vacca, Paolo; Laschat, Sabine; Scalia, Giusy

2010-05-20

Thin films of the discotic liquid crystal hexapentyloxytriphenylene (HAT5), prepared from solution via casting or spin-coating, were investigated by atomic force microscopy and polarizing optical microscopy, revealing large-scale ordered structures substantially different from those typically observed in standard samples of the same material. Thin and very long fibrils of planar-aligned liquid crystal were found, possibly formed as a result of an intermediate lyotropic nematic state arising during the solvent evaporation process. Moreover, in sufficiently thin films the crystallization seems to be suppressed, extending the uniform order of the liquid crystal phase down to room temperature. This should be compared to the bulk situation, where the same material crystallizes into a polymorphic structure at 68 °C.

Nuclear magnetic resonance of liquid crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Emsley, J.W.

1984-01-01

The phenomenon of liquid crystallinity has been known for 100 years, but it is only in recent years that our modern methods have yielded an understanding of this fascinating and important subject in terms of molecular behavior. The great improvements in NMR spectrometers have led to a rapid growth in the study of liquid crystalline systems; concurrently, the increased use of these systems in electro-optic displays, in soaps and membranes, have all focused increased attention on liquid crystallinity. The emphasis is placed first on giving an account of the theory of both the spectroscopy and the liquid crystalline state. Thismore » is followed by descriptions of experiments and their application to thermotropic phases, including discotics, to lyotropics, and finally to the very complex biological membranes.« less

Chromonic liquid crystalline nematic phase exhibited in binary mixture of two liquid crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Govindaiah, T. N., E-mail: tngovi.phy@gmail.com; Sreepad, H. R.; Sridhar, K. N.

2015-06-24

A binary mixture of abietic acid and orthophosphoric acid (H{sub 3}PO{sub 4}) exhibits co-existence of biphasic region of Nematic+Isotropic (N+I), lyotropic Nematic (ND) and Smectic-G (SmG) phases. The mixture exhibits N+I, N and SmG phases at different concentrations and at different temperatures. Mixtures with all concentrations of abietic acid exhibit I→N+I→N→SmG phases sequentially when the specimen is cooled from its isotropic melt. These phases have been characterized by using differential scanning calorimetric, X-ray diffraction, and optical texture studies.

Protein Stabilization and Enzyme Activation in Ionic Liquids: Specific Ion Effects

PubMed Central

Zhao, Hua

2015-01-01

There are still debates on whether the hydration of ions perturbs the water structure, and what is the degree of such disturbance; therefore, the origin of Hofmeister effect on protein stabilization continues being questioned. For this reason, it is suggested to use the ‘specific ion effect’ instead of other misleading terms such as Hofmeister effect, Hofmeister series, lyotropic effect, and lyotropic series. In this review, we firstly discuss the controversial aspect of inorganic ion effects on water structures, and several possible contributors to the specific ion effect of protein stability. Due to recent overwhelming attraction of ionic liquids (ILs) as benign solvents in many enzymatic reactions, we further evaluate the structural properties and molecular-level interactions in neat ILs and their aqueous solutions. Next, we systematically compare the specific ion effects of ILs on enzyme stability and activity, and conclude that (a) the specificity of many enzymatic systems in diluted aqueous IL solutions is roughly in line with the traditional Hofmeister series albeit some exceptions; (b) however, the specificity follows a different track in concentrated or neat ILs because other factors (such as hydrogen-bond basicity, nucelophilicity, and hydrophobicity, etc) are playing leading roles. In addition, we demonstrate some examples of biocatalytic reactions in IL systems that are guided by the empirical specificity rule. PMID:26949281

Formation of a 1,8-octanedithiol self-assembled monolayer on Au(111) prepared in a lyotropic liquid-crystalline medium.

PubMed

García Raya, Daniel; Madueño, Rafael; Blázquez, Manuel; Pineda, Teresa

2010-07-20

A characterization of the 1,8-octanedithiol (ODT) self-assembled monolayer (SAM) formed from a Triton X-100 lyotropic medium has been conducted by electrochemical techniques. It is found that an ODT layer of standing-up molecules is obtained at short modification time without removing oxygen from the medium. The electrochemical study shows that the ODT layer formed after 15 min of modification time has similar electron-transfer blocking properties to the layers formed from organic solvents at much longer modification times. On the basis of XPS data, it is demonstrated that the inability to bind gold nanoparticles (AuNPs) is due to the presence of extra ODT molecules either interdigited or on top of the layer. Treatment consisting of an acid washing step following the formation of the ODT-Au(111) SAM produces a layer that is able to attach AuNPs as demonstrated by electrochemical techniques and atomic force microscopy (AFM) images.

Chiral lyotropic chromonic liquid crystals composed of disodium cromoglycate doped with water-soluble chiral additives.

PubMed

Shirai, Tatsuya; Shuai, Min; Nakamura, Keita; Yamaguchi, Akihiro; Naka, Yumiko; Sasaki, Takeo; Clark, Noel A; Le, Khoa V

2018-02-28

We investigated the pitches of cholesteric liquid crystals prepared by mixing disodium cromoglycate (DSCG) in water with 5 different water-soluble chiral additives. The measurements are based on the Grandjean-Cano wedge cell method. Overall, the twisting effect is weak, and the shortest pitch of 2.9 ± 0.2 μm is obtained using trans-4-hydroxy-l-proline, by which the cholesteric sample is iridescent at certain viewing angles. Freeze-fracture transmission electron microscopy (FFTEM) was also performed for the first time on both the nematic and cholesteric phases, revealing that stacked chromonic aggregates are very long, up to a few hundred nm, which explains why cholesteric chromonic liquid crystals hardly have pitches in the visible wavelength region.

Periodic assembly of nanoparticle arrays in disclinations of cholesteric liquid crystals.

PubMed

Li, Yunfeng; Prince, Elisabeth; Cho, Sangho; Salari, Alinaghi; Mosaddeghian Golestani, Youssef; Lavrentovich, Oleg D; Kumacheva, Eugenia

2017-02-28

An important goal of the modern soft matter science is to discover new self-assembly modalities to precisely control the placement of small particles in space. Spatial inhomogeneity of liquid crystals offers the capability to organize colloids in certain regions such as the cores of the topological defects. Here we report two self-assembly modes of nanoparticles in linear defects-disclinations in a lyotropic colloidal cholesteric liquid crystal: a continuous helicoidal thread and a periodic array of discrete beads. The beads form one-dimensional arrays with a periodicity that matches half a pitch of the cholesteric phase. The periodic assembly is governed by the anisotropic surface tension and elasticity at the interface of beads with the liquid crystal. This mode of self-assembly of nanoparticles in disclinations expands our ability to use topological defects in liquid crystals as templates for the organization of nanocolloids.

Investigations of the local environment and macroscopic alignment behavior of novel polymerizeable lyotropic liquid crystals using nuclear magnetic resonance

NASA Astrophysics Data System (ADS)

Juang, Elizabeth

In this dissertation, a variety of NMR techniques were used to explore the local environment of novel polymerizeable lyotropic liquid crystals (LLC). The LLC monomers examined in this study self-assemble in the presence of a small amount of water to form uniform, nanometer-scale tubes with aqueous interiors. The phase architecture is retained upon photopolymerization to yield the resulting nanoporous material. By dissolving reactive precursors into the aqueous phase, well- structured nancomposite materials have also been formed. Proposed uses for these novel polymerizeable LLCs are as porous water filtration membranes, as heterogeneous organic catalysts, and as nanocomposite materials for load bearing and optical applications. In order to better exploit these polymerizeable LLCs for materials development, the local environment must be examined. In addition, the macroscopic orientation of these materials remains an important step in their advancement. Various NMR studies were conducted on these novel LLCs. NMR T1 relaxation measurements were conducted to elucidate the local environment and dynamics of the 23Na counterions located inside the aqueous channels. 2H NMR line shape analyses were used to characterize the local structure and dynamics near the hydrophilic headgroup. 29 Si NMR studies were performed on silica nanocomposites formed with these LLC structures. Finally, the macroscopic alignment behavior of these novel LLCs using shear and magnetic fields was examined.

Coupling between the Dynamics of Water and Surfactants in Lyotropic Liquid Crystals.

PubMed

McDaniel, Jesse G; Yethiraj, Arun

2017-05-18

Bilayers composed of lipid or surfactant molecules are central to biological membranes and lamellar lyotropic liquid crystalline (LLC) phases. Common to these systems are phases that exhibit either ordered or disordered packing of the hydrophobic tails. In this work, we study the impact of surfactant ordering, i.e., disordered L α and ordered L β LLC phases, on the dynamics of water and sodium ions in the lamellar phases of dicarboxylate gemini surfactants. We study the different phases at identical hydration levels by changing the length of the hydrophobic tails; surfactants with shorter tails form L α phases and those with longer tails form L β phases. We find that the L α phases exhibit lower density and greater compressibility than the L β phases, with a hydration-dependent headgroup surface area. These structural differences significantly affect the relative dynamic properties of the phases, primarily the mobility of the surfactant molecules tangential to the bilayer surface, as well as the rates of water and ion diffusion. We find ∼20-50% faster water diffusion in the L α phases compared to the L β phases, with the differences most pronounced at low hydration. This coupling between water dynamics and surfactant mobility is verified using additional simulations in which the surfactant tails are frozen. Our study indicates that gemini surfactant LLCs provide an important prototypical system for characterizing properties shared with more complex biological lipid membranes.

Aqueous cholesteric liquid crystals using uncharged rodlike polypeptides. Polypeptide vesicles by conformation-specific assembly. Ordered chiral macroporous hybrid silica-polypeptide composites

NASA Astrophysics Data System (ADS)

Bellomo, Enrico Giuseppe

2005-07-01

Aqueous cholesteric liquid crystals using uncharged rodlike polypeptides . The aqueous, lyotropic liquid-crystalline phase behavior of an alpha helical polypeptide, has been studied using optical microscopy and X-ray scattering. Solutions of optically pure polypeptide were found to form cholesteric liquid crystals at volume fractions that decreased with increasing average chain length. At very high volume fractions, the formation of a hexagonal mesophase was observed. The pitch of the cholesteric phase could be varied by a mixture of enantiomeric samples, where the pitch increased as the mixture approached equimolar. The cholesteric phases could be untwisted, using either magnetic field or shear flow, into nematic phases, which relaxed into cholesterics upon removal of field or shear. We have found that the phase diagram of this polypeptide in aqueous solution parallels that of poly(gamma-benzyl glutamate) in organic solvents, thus providing a useful system for liquid-crystal applications requiring water as solvent. Polypeptide vesicles by conformation-specific assembly. We have found that block copolymers composed of polypeptide segments provide significant advantages in controlling both the function and supramolecular structure of bioinspired self-assemblies. Incorporation of the stable chain conformations found in proteins into block copolymers was found to provide an additional element of control, beyond amphiphilicity and composition that defines self-assembled architecture. The abundance of functionality present in amino acids, and the ease by which they can be incorporated into these materials, also provides a powerful mechanism to impart block copolypeptides with function. This combination of structure and function work synergistically to enable significant advantages in the preparation of therapeutic agents as well as provide insight into design of self-assemblies beginning to approach the complexity of natural structures such as virus capsids. Ordered chiral macroporous hybrid silica-polypeptide composites. The mineralization of organic templates has been investigated as an effective way to control the size and structure of inorganic frameworks. Hybrid structures incorporating polypeptide with silica have been prepared and characterized using X-ray scattering, TGA, SEM and TEM. The results support the interaction between silica and polymer to form ordered chiral macroporous structures that can be easily controlled by polymer molecular weight and volume fraction.

Water freezing and ice melting

DOE PAGES

Malolepsza, Edyta; Keyes, Tom

2015-10-12

The generalized replica exchange method (gREM) is designed to sample states with coexisting phases and thereby to describe strong first order phase transitions. The isobaric MD version of the gREM is presented and applied to freezing of liquid water, and melting of hexagonal and cubic ice. It is confirmed that coexisting states are well sampled. The statistical temperature as a function of enthalpy, T S(H), is obtained. Hysteresis between freezing and melting is observed and discussed. The entropic analysis of phase transitions is applied and equilibrium transition temperatures, latent heats, and surface tensions are obtained for hexagonal ice↔liquid and cubicmore » ice↔liquid, with excellent agreement with published values. A new method is given to assign water molecules among various symmetry types. As a result, pathways for water freezing, ultimately leading to hexagonal ice, are found to contain intermediate layered structures built from hexagonal and cubic ice.« less

Switchable polarization-sensitive surface plasmon resonance of highly stable gold nanorods liquid crystals composites

NASA Astrophysics Data System (ADS)

Liu, Qingkun; Qian, Jun; Cai, Fuhong; Smalyukh, Ivan I.; He, Sailing

2011-12-01

In this work, we demonstrate the bulk self-alignment of gold nanorods (GNRs) dispersed in lyotropic nematic liquid crystals (LCs) with high optical absorption coefficient at the surface plasmon resonant wavelength. The polymer-coated GNRs which show spontaneous long-range orientational ordering along the director of LC host exhibit long-term stability as well as high concentration. External magnetic field and shearing allow for alignment and realignment of the orientation of gold nanorods by changing the director of the liquid crystal matrix. This results in a switchable polarization-sensitive surface plasmon resonance exhibiting stark differences from that of the same nanorods in isotropic fluids. The devise-scale bulk nanoparticle alignment may enable optical metamaterial mass production and control of surface plasmon resonance of nanoparticles.

Anisotropic surface melting in lyotropic cubic crystals: part 2: facet-by-facet melting at Ia3d/vapor interfaces.

PubMed

Leroy, S; Grenier, J; Rohe, D; Even, C; Pieranski, P

2006-05-01

From experiments with metal crystals, in the vicinity of their crystal/liquid/vapor triple points, it is known that melting of crystals starts on their surfaces and is anisotropic. Recently, we have shown that anisotropic surface melting occurs also in lyotropic systems. In our previous paper (Eur. Phys. J. E 19, 223 (2006)), we have focused on the case of poor faceting at the Pn3m/L1 interface in C12EO2/water binary mixtures. There anisotropic melting occurs in the vicinity of a Pn3m/L3/L1 triple point. In the present paper, we focus on the opposite case of a rich devil's-staircase-type faceting at Ia3d/vapor interfaces in monoolein/water and phytantriol/water mixtures. We show that anisotropic surface melting takes place in these systems in a narrow humidity range close to the Ia3d-L2 transition. As whole (hkl) sets of facets disappear one after another when the transition is approached, surface melting occurs in a facet-by-facet type.

Lyotropic chromonic liquid crystals: From viscoelastic properties to living liquid crystals

NASA Astrophysics Data System (ADS)

Zhou, Shuang

Lyotropic chromonic liquid crystal (LCLC) represents a broad range of molecules, from organic dyes and drugs to DNA, that self-assemble into linear aggregates in water through face-to-face stacking. These linear aggregates of high aspect ratio are capable of orientational order, forming, for example nematic phase. Since the microscopic properties (such as length) of the chromonic aggregates are results of subtle balance between energy and entropy, the macroscopic viscoelastic properties of the nematic media are sensitive to change of external factors. In the first part of this thesis, by using dynamic light scattering and magnetic Frederiks transition techniques, we study the Frank elastic moduli and viscosity coefficients of LCLC disodium cromoglycate (DSCG) and sunset yellow (SSY) as functions of concentration c , temperature T and ionic contents. The elastic moduli of splay (K1) and bend (K3) are in the order of 10pN, about 10 times larger than the twist modulus (K2). The splay modulus K1 and the ratio K1/K3 both increase substantially as T decreases or c increases, which we attribute to the elongation of linear aggregates at lower T or higher c . The bend viscosity is comparable to that of thermotropic liquid crystals, while the splay and twist viscosities are several orders of magnitude larger, changing exponentially with T . Additional ionic additives into the system influence the viscoelastic properties of these systems in a dramatic and versatile way. For example, monovalent salt NaCl decreases bend modulus K3 and increases twist viscosity, while an elevated pH decreases all the parameters. We attribute these features to the ion-induced changes in length and flexibility of building units of LCLC, the chromonic aggregates, a property not found in conventional thermotropic and lyotropic liquid crystals form by covalently bound units of fixed length. The second part of the thesis studies a new active bio-mechanical hybrid system called living liquid crystal (LLC), constructed by mixing LCLC with self-propelled microorganism, bacteria strain called Bacillus subtilis . The coupling between bacterial flow and the nematic long-rang order of the LCLC matrix results in a wealth of intriguing dynamic phenomena, among which are 1) programmable trajectories of bacterial motion guided by patterned director field, 2) cargo particle transportation along such trajectories, 3) local melting of the liquid crystal caused by the bacteria-produced shear flow, 4) birefringence-enabled visualization of microflow generated by nanometer-thick bacterial flagella and 5) activity triggered transition from non-flow uniform state into a flowing one-dimensional pattern and its evolution into a turbulent array of topological defects. In addition, due to the long-rang elastic interaction mediated by the nematic matrix, LLC shows collective dynamics at very low fraction of bacteria, on the order of 0.2%, about 1/10 of bacteria fraction needed in isotropic media for collective motion. Our work suggests an unorthodox design concept to control and manipulate the dynamic behavior of soft active matter and opens the door for potential biosensing and biomedical applications.

Accelerated stability assay (ASA) for colloidal systems.

PubMed

Chong, Josephine Y T; Mulet, Xavier; Boyd, Ben J; Drummond, Calum J

2014-05-12

Assessment of the stability of colloidal systems, in particular lyotropic liquid crystalline dispersions, such as cubosomes and hexosomes, is typically performed qualitatively or with limited throughput on specialized instruments. Here, an accelerated stability assay for colloidal particles has been developed in 384-well plates with standard laboratory equipment. These protocols enable quantitative assessments of colloidal stability. To demonstrate the applicability of the assay, several steric stabilizers for cubic phase nanostructured particles (cubosomes) have been compared to the current "gold standard" Pluronic F127.

Multilayer hexagonal silicon forming in slit nanopore

PubMed Central

He, Yezeng; Li, Hui; Sui, Yanwei; Qi, Jiqiu; Wang, Yanqing; Chen, Zheng; Dong, Jichen; Li, Xiongying

2015-01-01

The solidification of two-dimensional liquid silicon confined to a slit nanopore has been studied using molecular dynamics simulations. The results clearly show that the system undergoes an obvious transition from liquid to multilayer hexagonal film with the decrease of temperature, accompanied by dramatic change in potential energy, atomic volume, coordination number and lateral radial distribution function. During the cooling process, some hexagonal islands randomly appear in the liquid first, then grow up to grain nuclei, and finally connect together to form a complete polycrystalline film. Moreover, it is found that the quenching rate and slit size are of vital importance to the freezing structure of silicon film. The results also indicate that the slit nanopore induces the layering of liquid silicon, which further induces the slit size dependent solidification behavior of silicon film with different electrical properties. PMID:26435518

Lyotropic Liquid Crystal Phases from Anisotropic Nanomaterials

PubMed Central

Dierking, Ingo

2017-01-01

Liquid crystals are an integral part of a mature display technology, also establishing themselves in other applications, such as spatial light modulators, telecommunication technology, photonics, or sensors, just to name a few of the non-display applications. In recent years, there has been an increasing trend to add various nanomaterials to liquid crystals, which is motivated by several aspects of materials development. (i) addition of nanomaterials can change and thus tune the properties of the liquid crystal; (ii) novel functionalities can be added to the liquid crystal; and (iii) the self-organization of the liquid crystalline state can be exploited to template ordered structures or to transfer order onto dispersed nanomaterials. Much of the research effort has been concentrated on thermotropic systems, which change order as a function of temperature. Here we review the other side of the medal, the formation and properties of ordered, anisotropic fluid phases, liquid crystals, by addition of shape-anisotropic nanomaterials to isotropic liquids. Several classes of materials will be discussed, inorganic and mineral liquid crystals, viruses, nanotubes and nanorods, as well as graphene oxide. PMID:28974025

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 is incredible freedom in designing the block copolymer architecture in order to optimize the mechanical and other properties of the membrane without sacrificing conductivity. The derived scaling relationships are shown to be general for many block copolymer and ionic liquid chemistries. In certain cases, the mechanism of ion conduction in the ionic liquid is affected by block copolymer nanoconfinement. The introduction of excess neutral imidazole to [Im][TFSI] leads to enhanced proton conductivity as well as a high H+ transference number due to facilitated proton hopping between imidazole molecules. We show that there is increased proton hopping when the nonstoichiometric ionic liquid is confined to lamellar block copolymer nanodomains, which we hypothesize is due to changes in the hydrogen bond structure of the ionic liquid under confinement. This, in combination with unique ion aggregation behavior, leads to a lower activation energy for macroscopic ion transport compared to that in a corresponding homopolymer/ionic liquid mixture. Through this work, we further the understanding of the relationship between membrane composition, structure, and ion transport. The findings presented herein portend the rational design of nanostructured membranes having improved mechanical properties and conductivity.

Individual behavior and pairwise interactions between microswimmers in anisotropic liquid

NASA Astrophysics Data System (ADS)

Sokolov, Andrey; Zhou, Shuang; Lavrentovich, Oleg D.; Aranson, Igor S.

2015-01-01

A motile bacterium swims by generating flow in its surrounding liquid. Anisotropy of the suspending liquid significantly modifies the swimming dynamics and corresponding flow signatures of an individual bacterium and impacts collective behavior. We study the interactions between swimming bacteria in an anisotropic environment exemplified by lyotropic chromonic liquid crystal. Our analysis reveals a significant localization of the bacteria-induced flow along a line coaxial with the bacterial body, which is due to strong viscosity anisotropy of the liquid crystal. Despite the fact that the average viscosity of the liquid crystal is two to three orders of magnitude higher than the viscosity of pure water, the speed of bacteria in the liquid crystal is of the same order of magnitude as in water. We show that bacteria can transport a cargo (a fluorescent particle) along a predetermined trajectory defined by the direction of molecular orientation of the liquid crystal. We demonstrate that while the hydrodynamic interaction between flagella of two close-by bacteria is negligible, the observed convergence of the swimming speeds as well as flagella waves' phase velocities may occur due to viscoelastic interaction between the bacterial bodies.

Coupling between the Dynamics of Water and Surfactants in Lyotropic Liquid Crystals

DOE PAGES

McDaniel, Jesse G.; Yethiraj, Arun

2017-04-26

Bilayers composed of lipid or surfactant molecules are central to biological membranes and lamellar lyotropic liquid crystalline (LLC) phases. Common to these systems are phases that exhibit either ordered or disordered packing of the hydrophobic tails. In this work, we study the impact of surfactant ordering, i.e., disordered L α and ordered L β LLC phases, on the dynamics of water and sodium ions in the lamellar phases of dicarboxylate gemini surfactants. We study the different phases at identical hydration levels by changing the length of the hydrophobic tails; surfactants with shorter tails form L α phases and those withmore » longer tails form L β phases. We find that the L α phases exhibit lower density and greater compressibility than the L β phases, with a hydration-dependent headgroup surface area. These structural differences significantly affect the relative dynamic properties of the phases, primarily the mobility of the surfactant molecules tangential to the bilayer surface, as well as the rates of water and ion diffusion. We find ~20–50% faster water diffusion in the L α phases compared to the L β phases, with the differences most pronounced at low hydration. This coupling between water dynamics and surfactant mobility is verified using additional simulations in which the surfactant tails are frozen. Our study indicates that gemini surfactant LLCs provide an important prototypical system for characterizing properties shared with more complex biological lipid membranes.« less

Computational model for living nematic

NASA Astrophysics Data System (ADS)

Genkin, Mikhail; Sokolov, Andrey; Lavrentovich, Oleg; Aranson, Igor

A realization of an active system has been conceived by combining swimming bacteria and a lyotropic nematic liquid crystal. Here, by coupling the well-established and validated model of nematic liquid crystals with the bacterial dynamics we developed a computational model describing intricate properties of such a living nematic. In faithful agreement with the experiment, the model reproduces the onset of periodic undulation of the nematic director and consequent proliferation of topological defects with the increase in bacterial concentration. It yields testable prediction on the accumulation and transport of bacteria in the cores of +1/2 topological defects and depletion of bacteria in the cores of -1/2 defects. Our new experiment on motile bacteria suspended in a free-standing liquid crystalline film fully confirmed this prediction. This effect can be used to capture and manipulation of small amounts of bacteria.

Nanoparticles in ionic liquids: interactions and organization.

PubMed

He, Zhiqi; Alexandridis, Paschalis

2015-07-28

Ionic liquids (ILs), defined as low-melting organic salts, are a novel class of compounds with unique properties and a combinatorially great chemical diversity. Ionic liquids are utilized as synthesis and dispersion media for nanoparticles as well as for surface functionalization. Ionic liquid and nanoparticle hybrid systems are governed by a combined effect of several intermolecular interactions between their constituents. For each interaction, including van der Waals, electrostatic, structural, solvophobic, steric, and hydrogen bonding, the characterization and quantitative calculation methods together with factors affecting these interactions are reviewed here. Various self-organized structures based on nanoparticles in ionic liquids are generated as a result of a balance of these intermolecular interactions. These structures, including colloidal glasses and gels, lyotropic liquid crystals, nanoparticle-stabilized ionic liquid-containing emulsions, ionic liquid surface-functionalized nanoparticles, and nanoscale ionic materials, possess properties of both ionic liquids and nanoparticles, which render them useful as novel materials especially in electrochemical and catalysis applications. This review of the interactions within nanoparticle dispersions in ionic liquids and of the structure of nanoparticle and ionic liquid hybrids provides guidance on the rational design of novel ionic liquid-based materials, enabling applications in broad areas.

Phosphine oxide surfactants revisited.

PubMed

Stubenrauch, Cosima; Preisig, Natalie; Laughlin, Robert G

2016-04-01

This review summarizes everything we currently know about the nonionic surfactants alkyl dimethyl (C(n)DMPO) and alkyl diethyl (C(n)DEPO) phosphine oxide (PO surfactants). The review starts with the synthesis and the general properties (Section 2) of these compounds and continues with their interfacial properties (Section 3) such as surface tension, surface rheology, interfacial tension and adsorption at solid surfaces. We discuss studies on thin liquid films and foams stabilized by PO surfactants (Section 4) as well as studies on their self-assembly into lyotropic liquid crystals and microemulsions, respectively (Section 5). We aim at encouraging colleagues from both academia and industry to take on board PO surfactants whenever possible and feasible because of their broad variety of excellent properties. Copyright © 2016 Elsevier B.V. All rights reserved.

Aligned Layers of Silver Nano-Fibers.

PubMed

Golovin, Andrii B; Stromer, Jeremy; Kreminska, Liubov

2012-02-01

We describe a new dichroic polarizers made by ordering silver nano-fibers to aligned layers. The aligned layers consist of nano-fibers and self-assembled molecular aggregates of lyotropic liquid crystals. Unidirectional alignment of the layers is achieved by means of mechanical shearing. Aligned layers of silver nano-fibers are partially transparent to a linearly polarized electromagnetic radiation. The unidirectional alignment and density of the silver nano-fibers determine degree of polarization of transmitted light. The aligned layers of silver nano-fibers might be used in optics, microwave applications, and organic electronics.

Enzymatic biofuel cell based on electrodes modified with lipid liquid-crystalline cubic phases

NASA Astrophysics Data System (ADS)

Nazaruk, Ewa; Smoliński, Sławomir; Swatko-Ossor, Marta; Ginalska, Grażyna; Fiedurek, Jan; Rogalski, Jerzy; Bilewicz, Renata

Two glassy carbon electrodes modified with enzymes embedded in lyotropic liquid-crystalline cubic phase were used for the biofuel cell construction. The monoolein liquid-crystalline film allowed to avoid separators in the biofuel cell. Glucose and oxygen as fuels, and glucose oxidase and laccase as anode and cathode biocatalysts, respectively were used. The biofuel cell parameters were examined in McIlvaine buffer, pH 7 solution containing 15 mM of glucose and saturated with dioxygen. A series of mediators were tested taking into account their formal potentials, stability in the cubic phase and efficiency of mediation. Most stable was the biofuel cell based on tetrathiafulvalene (TTF) and 2,2‧-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) as anode and cathode mediators, respectively. The open-circuit voltage was equal to 450 ± 40 mV. The power densities and current densities were measured for all the systems studied.

Influence of the particle parameters on the stability of magnetic dopants in a ferrolyotropic suspension

NASA Astrophysics Data System (ADS)

Appel, Ingo; Behrens, Silke

2017-06-01

The doping of liquid crystals with magnetic nanoparticles increases the magnetic susceptibility and the sensitivity to small magnetic fields. This offers interesting possibilities for controlling optical properties via external magnetic fields. The stabilization of magnetic nanoparticles in the liquid crystalline host, however, is challenging, since magnetic dipolar interactions and LC-mediated forces may result in their aggregation and even phase separation. So far, only few groups have investigated the long-term stability of these systems. In the present study, a set of magnetic iron oxide nanoparticles with different particle size, shape and surface properties was synthesized by thermal decomposition or co-precipitation. The magnetic nanoparticles were further integrated in a model liquid crystalline host (i.e., the lyotropic system potassium laurate/1-decanol/water) to investigate the effect of the different particle parameters on the stability of the resulting ferrolyotrope.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Salamone, J.C.; Clough, S.B.; Jamison, D.E.

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 ismore » 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.« less

Chiral nematic porous germania and germanium/carbon films

NASA Astrophysics Data System (ADS)

Xu, Jing; Nguyen, Thanh-Dinh; Xie, Kai; Hamad, Wadood Y.; MacLachlan, Mark J.

2015-07-01

We report our extensive attempts and, ultimately, success to produce crack-free, chiral nematic GeO2/cellulose nanocrystal (CNC) composite films with tunable photonic properties from the controlled assembly of germanium(iv) alkoxides with the lyotropic liquid-crystalline CNCs in a mixed solvent of water/DMF. With different pyrolysis conditions, the photonic GeO2/CNC composites can be converted into freestanding chiral nematic films of amorphous GeO2, and semiconducting mesoporous GeO2/C and Ge/C replicas. These new materials are promising for chiral separation, enantioselective adsorption, catalysis, sensing, optoelectronics, and lithium ion batteries. Furthermore, the new, reproducible synthesis strategies developed may be applicable for constructing other composites and porous materials with chiral nematic ordering.We report our extensive attempts and, ultimately, success to produce crack-free, chiral nematic GeO2/cellulose nanocrystal (CNC) composite films with tunable photonic properties from the controlled assembly of germanium(iv) alkoxides with the lyotropic liquid-crystalline CNCs in a mixed solvent of water/DMF. With different pyrolysis conditions, the photonic GeO2/CNC composites can be converted into freestanding chiral nematic films of amorphous GeO2, and semiconducting mesoporous GeO2/C and Ge/C replicas. These new materials are promising for chiral separation, enantioselective adsorption, catalysis, sensing, optoelectronics, and lithium ion batteries. Furthermore, the new, reproducible synthesis strategies developed may be applicable for constructing other composites and porous materials with chiral nematic ordering. Electronic supplementary information (ESI) available: TGA, IR, Raman, TEM, SEM, BET. See DOI: 10.1039/c5nr02520f

Hexagonal comb cells of honeybees are not produced via a liquid equilibrium process

NASA Astrophysics Data System (ADS)

Bauer, Daniel; Bienefeld, Kaspar

2013-01-01

The nests of European honeybees ( Apis mellifera) are organised into wax combs that contain many cells with a hexagonal structure. Many previous studies on comb-building behaviour have been made in order to understand how bees produce this geometrical structure; however, it still remains a mystery. Direct construction of hexagons by bees was suggested previously, while a recent hypothesis postulated the self-organised construction of hexagonal comb cell arrays; however, infrared and thermographic video observations of comb building in the present study failed to support the self-organisation hypothesis because bees were shown to be engaged in direct construction. Bees used their antennae, mandibles and legs in a regular sequence to manipulate the wax, while some bees supported their work by actively warming the wax. During the construction of hexagonal cells, the wax temperature was between 33.6 and 37.6 °C. This is well below 40 °C, i.e. the temperature at which wax is assumed to exist in the liquid equilibrium that is essential for self-organised building.

In vitro permeation of diclofenac salts from lyotropic liquid crystalline systems.

PubMed

Yariv, Doron; Efrat, Rivka; Libster, Dima; Aserin, Abraham; Garti, Nissim

2010-07-01

In this paper we examined feasible correlations between the structure of different lyotropic mesophases and transdermal administration of three diclofenac derivatives with varying degrees of kosmotropic or chaotropic properties, solubilized within the mesophases. It was found that the most chaotropic derivative of diclofenac diethyl amine (DEA-DFC) interacted with the polar heads of glycerol monooleate (GMO), thus expanding the water-lipid interface of the lamellar and cubic mesophases. This effect was detected by an increase in the lattice parameter of both mesophases, enhanced elastic properties, and increased solid-like response of the systems in the presence of DEA. Potassium diclofenac (K-DFC), a less chaotropic salt, had less pronounced effect on the structural features of the mesophases. Kosmotropic Na+ salt (Na-DFC) had only minor influence on both lamellar and cubic structures. The locus of solubilization of the molecules with the host mesophases was correlated with their delivery. It was suggested that transdermal delivery of kosmotropic Na-DFC was accelerated by the aqueous phase and less constrained by the interaction with monoglyceride. On the other hand, the chaotropic cations (K+ and DEA+), presumably entrapped in the water-lipid interface, interacted with monoglyceride headgroups, which is likely to be the key cause for their sustained administration. 2010 Elsevier B.V. All rights reserved.

Identification of Clathrate Hydrates, Hexagonal Ice, Cubic Ice, and Liquid Water in Simulations: the CHILL+ Algorithm.

PubMed

Nguyen, Andrew H; Molinero, Valeria

2015-07-23

Clathrate hydrates and ice I are the most abundant crystals of water. The study of their nucleation, growth, and decomposition using molecular simulations requires an accurate and efficient algorithm that distinguishes water molecules that belong to each of these crystals and the liquid phase. Existing algorithms identify ice or clathrates, but not both. This poses a challenge for cases in which ice and hydrate coexist, such as in the synthesis of clathrates from ice and the formation of ice from clathrates during self-preservation of methane hydrates. Here we present an efficient algorithm for the identification of clathrate hydrates, hexagonal ice, cubic ice, and liquid water in molecular simulations. CHILL+ uses the number of staggered and eclipsed water-water bonds to identify water molecules in cubic ice, hexagonal ice, and clathrate hydrate. CHILL+ is an extension of CHILL (Moore et al. Phys. Chem. Chem. Phys. 2010, 12, 4124-4134), which identifies hexagonal and cubic ice but not clathrates. In addition to the identification of hydrates, CHILL+ significantly improves the detection of hexagonal ice up to its melting point. We validate the use of CHILL+ for the identification of stacking faults in ice and the nucleation and growth of clathrate hydrates. To our knowledge, this is the first algorithm that allows for the simultaneous identification of ice and clathrate hydrates, and it does so in a way that is competitive with respect to existing methods used to identify any of these crystals.

Pressure-temperature phase behavior of mixtures of natural sphingomyelin and ceramide extracts.

PubMed

Barriga, Hanna M G; Parsons, Edward S; McCarthy, Nicola L C; Ces, Oscar; Seddon, John M; Law, Robert V; Brooks, Nicholas J

2015-03-31

Ceramides are a group of sphingolipids that act as highly important signaling molecules in a variety of cellular processes including differentiation and apoptosis. The predominant in vivo synthetic pathway for ceramide formation is via sphingomyelinase catalyzed hydrolysis of sphingomyelin. The biochemistry of this essential pathway has been studied in detail; however, there is currently a lack of information on the structural behavior of sphingomyelin- and ceramide-rich model membrane systems, which is essential for developing a bottom-up understanding of ceramide signaling and platform formation. We have studied the lyotropic phase behavior of sphingomyelin-ceramide mixtures in excess water as a function of temperature (30-70 °C) and pressure (1-200 MPa) by small- and wide-angle X-ray scattering. At low ceramide concentrations the mixtures form the ripple gel phase (P(β)') below the gel transition temperature for sphingomyelin, and this observation has been confirmed by atomic force microscopy. Formation of the ripple gel phase can also be induced at higher temperatures via the application of hydrostatic pressure. At high ceramide concentration an inverse hexagonal phase (HII) is formed coexisting with a cubic phase.

Novel agrochemical conjugates with self-assembling behaviour.

PubMed

Liu, Qingtao; Graham, Bim; Hawley, Adrian; Dong, Yao-Da; Boyd, Ben J

2018-02-15

That conjugation of agrichemicals to pro-assembly hydrophobic moieties will enable enhanced compatibility and loading with host lyotropic liquid crystalline carrier matrix, and potentially self-assemble in their own right in aqueous environments. A series of lipid-like agrochemical-conjugates were synthesized using specific amphiphilic entities conjugated onto the agrochemicals, picloram and 2,4-dichlorophenoxyacetic acid (2,4-D). The self-assembly behaviour and compatibility of the novel entities when incorporated into phytantriol and monoolein-based liquid crystalline systems were examined using small angle X-ray scattering, cryo-TEM and polarized optical microscopy. Compared to agrochemical-conjugates with simple alkyl ester groups, the esterification of the agrochemicals with amphiphilic groups such as phytantriol and monoolein led to greater structural compatibility and consequently a greater loading of the agrochemicals in the liquid crystalline systems without destabilizing phase structure. Picloram-monoolein and picloram-monoelaidin can self-assemble to form lamellar structures in water. However, certain agrochemical-conjugates such as picloram-monoelaidin and picloram-PEGn-oleate showed poor compatibility with liquid crystalline systems, resulting in phase separation. Copyright © 2017 Elsevier Inc. All rights reserved.

Preparation and optical properties of fullerene/ferrocene hybrid hexagonal nanosheets and large-scale production of fullerene hexagonal nanosheets.

PubMed

Wakahara, Takatsugu; Sathish, Marappan; Miyazawa, Kun'ichi; Hu, Chunping; Tateyama, Yoshitaka; Nemoto, Yoshihiro; Sasaki, Toshio; Ito, Osamu

2009-07-29

The supramolecular nanoarchitectures, C(60)/ferrocene nanosheets, were prepared by a simple liquid-liquid interfacial precipitation method and fully characterized by means of SEM, STEM, HRTEM, XRD, Raman and UV-vis-NIR spectra. The highly crystallized C(60)/ferrocene hexagonal nanosheets had a size of ca. 9 microm and the formulation C(60)(ferrocene)(2). A strong charge-transfer (CT) band between ferrocene and C(60) was observed at 782 nm, indicating the presence of donor-acceptor interaction in the nanosheets. Upon heating the nanosheets to 150 degrees C, the CT band disappeared due to the sublimation of ferrocene from the C(60)/ferrocene hybrid, and C(60) nanosheets with an fcc crystal structure and the same shape and size as the C(60)/ferrocene nanosheets were obtained.

Hexagonal convection patterns and their evolutionary scenarios in electroconvection induced by a strong unipolar injection

NASA Astrophysics Data System (ADS)

Luo, Kang; Wu, Jian; Yi, Hong-Liang; Liu, Lin-Hua; Tan, He-Ping

2018-05-01

A regular hexagonal pattern of three-dimensional electroconvective flow induced by unipolar injection in dielectric liquids is numerically observed by solving the fully coupled governing equations using the lattice Boltzmann method. A small-amplitude perturbation in the form of a spatially periodic pattern of hexagonal cells is introduced initially. The transient development of convective cells that undergo a sequence of transitions agrees with the idea of flow seeking an optimal scale. Stable hexagonal convective cells and their subcritical bifurcation together with a hysteresis loop are clearly observed. In addition, the stability of the hexagonal flow pattern is analyzed in a wide range of relevant parameters, including the electric Rayleigh number T , nondimensional mobility M , and wave number k . It is found that centrally downflowing hexagonal cells, which are characterized by the central region being empty of charge, are preferred in the system.

Spatially orthogonal chemical functionalization of a hierarchical pore network for catalytic cascade reactions

NASA Astrophysics Data System (ADS)

Parlett, Christopher M. A.; Isaacs, Mark A.; Beaumont, Simon K.; Bingham, Laura M.; Hondow, Nicole S.; Wilson, Karen; Lee, Adam F.

2016-02-01

The chemical functionality within porous architectures dictates their performance as heterogeneous catalysts; however, synthetic routes to control the spatial distribution of individual functions within porous solids are limited. Here we report the fabrication of spatially orthogonal bifunctional porous catalysts, through the stepwise template removal and chemical functionalization of an interconnected silica framework. Selective removal of polystyrene nanosphere templates from a lyotropic liquid crystal-templated silica sol-gel matrix, followed by extraction of the liquid crystal template, affords a hierarchical macroporous-mesoporous architecture. Decoupling of the individual template extractions allows independent functionalization of macropore and mesopore networks on the basis of chemical and/or size specificity. Spatial compartmentalization of, and directed molecular transport between, chemical functionalities affords control over the reaction sequence in catalytic cascades; herein illustrated by the Pd/Pt-catalysed oxidation of cinnamyl alcohol to cinnamic acid. We anticipate that our methodology will prompt further design of multifunctional materials comprising spatially compartmentalized functions.

Swimming in an anisotropic fluid: How speed depends on alignment angle

NASA Astrophysics Data System (ADS)

Shi, Juan; Powers, Thomas R.

2017-12-01

Orientational order in a fluid affects the swimming behavior of flagellated microorganisms. For example, bacteria tend to swim along the director in lyotropic nematic liquid crystals. To better understand how anisotropy affects propulsion, we study the problem of a sheet supporting small-amplitude traveling waves, also known as the Taylor swimmer, in a nematic liquid crystal. For the case of weak anchoring of the nematic director at the swimmer surface and in the limit of a minimally anisotropic model, we calculate the swimming speed as a function of the angle between the swimmer and the nematic director. The effect of the anisotropy can be to increase or decrease the swimming speed, depending on the angle of alignment. We also show that elastic torque dominates the viscous torque for small-amplitude waves and that the torque tends to align the swimmer along the local director.

Anomalous rheological behavior of long glass fiber reinforced polypropylene

NASA Astrophysics Data System (ADS)

Kim, Dong Hak; Lee, Young Sil; Son, Younggon

2012-12-01

Dynamic rheological properties of PP-based long glass fiber-reinforced thermoplastics (LFT) were investigated. Weight fractions of the glass fibers investigated in the present study ranged from 0.15 to 0.5, which are higher than those of previous studies. We observed very abnormal rheological behavior. Complex viscosity (η*) of the LFT increased with the glass fiber content up to 40 wt. %. However, the η* with a weight fraction of 0.5 is observed to be lower than that of LFT with a weight fraction of 0.4 in spite of higher glass fiber content. From various experiments, we found that this abnormal behavior is analogous to the rheological behavior of a lyotropic liquid crystalline polymer solution and concluded that the abnormal rheological behavior for the LFT is attributed to the formation of a liquid crystal- like structure at high concentrations of long glass fibers.

Liquid crystalline pattern formation in drying droplets of biopolymers

NASA Astrophysics Data System (ADS)

Smalyukh, Ivan; Zribi, Olena; Butler, John; Lavrentovich, Oleg; Wong, Gerard

2006-03-01

When a droplet of DNA in water dries out, a ring-like deposit is observed along the perimeter, similar to the stains in spilled drops of coffee. However, the dried ring of DNA is a self-similar birefringent pattern composed of extended molecules. We examine dynamics of the pattern formation at the droplet's rim. This gives us an insight into the underlining physics. During the major part of drying process the contact line is pinned so that DNA molecules are brought to the perimeter and extended by the radial capillary flow. Lyotropic nematic phase is formed in which highly concentrated DNA aligns along the triple line to minimize elastic energy. When the contact angle becomes small, the contact line starts to retract and the radial dilative stress causes buckling distortions at the rim which then propagate deep into the elastic liquid- crystalline medium and give rise to the pattern.

Fluctuating hydrodynamics and microrheology of a dilute suspension of swimming bacteria.

PubMed

Lau, A W C; Lubensky, T C

2009-07-01

A bacterial bath is a model active system consisting of a population of rodlike motile or self-propelled bacteria suspended in a fluid environment. This system can be viewed as an active, nonequilibrium version of a lyotropic liquid crystal or as a generalization of a driven diffusive system. We derive a set of phenomenological equations, which include the effects of internal force generators in the bacteria, describing the hydrodynamic flow, orientational dynamics of the bacteria, and fluctuations induced by both thermal and nonthermal noises. These equations violate the fluctuation dissipation theorem and the Onsager reciprocity relations. We use them to provide a quantitative account of results from recent microrheological experiments on bacterial baths.

Synthesis of three-dimensionally ordered macro-/mesoporous Pt with high electrocatalytic activity by a dual-templating approach

NASA Astrophysics Data System (ADS)

Zhang, Chengwei; Yang, Hui; Sun, Tingting; Shan, Nannan; Chen, Jianfeng; Xu, Lianbin; Yan, Yushan

2014-01-01

Three dimensionally ordered macro-/mesoporous (3DOM/m) Pt catalysts are fabricated by chemical reduction employing a dual-templating synthesis approach combining both colloidal crystal (opal) templating (hard-templating) and lyotropic liquid crystal templating (soft-templating) techniques. The macropore walls of the prepared 3DOM/m Pt exhibit a uniform mesoporous structure composed of polycrystalline Pt nanoparticles. Both the size of the mesopores and Pt nanocrystallites are in the range of 3-5 nm. The 3DOM/m Pt catalyst shows a larger electrochemically active surface area (ECSA), and higher catalytic activity as well as better poisoning tolerance for methanol oxidation reaction (MOR) than the commercial Pt black catalyst.

Liquid phase deposition synthesis of hexagonal molybdenum trioxide thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deki, Shigehito; Beleke, Alexis Bienvenu; Kotani, Yuki

2009-09-15

Hexagonal molybdenum trioxide thin films with good crystallinity and high purity have been fabricated by the liquid phase deposition (LPD) technique using molybdic acid (H{sub 2}MoO{sub 4}) dissolved in 2.82% hydrofluoric acid (HF) and H{sub 3}BO{sub 3} as precursors. The crystal was found to belong to a hexagonal hydrate system MoO{sub 3}.nH{sub 2}O (napprox0.56). The unit cell lattice parameters are a=10.651 A, c=3.725 A and V=365.997 A{sup 3}. Scanning electron microscope (SEM) images of the as-deposited samples showed well-shaped hexagonal rods nuclei that grew and where the amount increased with increase in reaction time. X-ray photon electron spectroscopy (XPS) spectramore » showed a Gaussian shape of the doublet of Mo 3d core level, indicating the presence of Mo{sup 6+} oxidation state in the deposited films. The deposited films exhibited an electrochromic behavior by lithium intercalation and deintercalation, which resulted in coloration and bleaching of the film. Upon dehydration at about 450 deg. C, the hexagonal MoO{sub 3}.nH{sub 2}O was transformed into the thermodynamically stable orthorhombic phase. - Abstract: SEM photograph of typical h-MoO{sub 3}.nH{sub 2}O thin film nuclei obtained after 36 h at 40 deg. C by the LPD method. Display Omitted« less

Crystallization, melting, and structure of water nanoparticles at atmospherically relevant temperatures.

PubMed

Johnston, Jessica C; Molinero, Valeria

2012-04-18

Water nanoparticles play an important role in atmospheric processes, yet their equilibrium and nonequilibrium liquid-ice phase transitions and the structures they form on freezing are not yet fully elucidated. Here we use molecular dynamics simulations with the mW water model to investigate the nonequilibrium freezing and equilibrium melting of water nanoparticles with radii R between 1 and 4.7 nm and the structure of the ice formed by crystallization at temperatures between 150 and 200 K. The ice crystallized in the particles is a hybrid form of ice I with stacked layers of the cubic and hexagonal ice polymorphs in a ratio approximately 2:1. The ratio of cubic ice to hexagonal ice is insensitive to the radius of the water particle and is comparable to that found in simulations of bulk water around the same temperature. Heating frozen particles that contain multiple crystallites leads to Ostwald ripening and annealing of the ice structures, accompanied by an increase in the amount of ice at the expense of the liquid water, before the particles finally melt from the hybrid ice I to liquid, without a transition to hexagonal ice. The melting temperatures T(m) of the nanoparticles are not affected by the ratio of cubic to hexagonal layers in the crystal. T(m) of the ice particles decreases from 255 to 170 K with the particle size and is well described by the Gibbs-Thomson equation, T(m)(R) = T(m)(bulk) - K(GT)/(R - d), with constant K(GT) = 82 ± 5 K·nm and a premelted liquid of width d = 0.26 ± 0.05 nm, about one monolayer. The freezing temperatures also decrease with the particles' radii. These results are important for understanding the composition, freezing, and melting properties of ice and liquid water particles under atmospheric conditions. © 2012 American Chemical Society

In-situ functionalization of mesoporous hexagonal ZnO synthesized in task specific ionic liquid as a photocatalyst for elimination of SO2, NOx, and CO

NASA Astrophysics Data System (ADS)

Kowsari, Elaheh; Abdpour, Soheil

2017-12-01

A novel mesoporous structure of zinc oxide was synthesized in hydrothermal autocalve in the presence of a functional ionic liquid (FIL) {[CH2CH2] O2 (mm)2}. This FIL with ether groups was used simultaneously as a designer templating agent and a source of the hydroxyl radical. The presence of this ionic liquid led to producing ethylene glycol in the reaction media, which adsorb on the surface of mesoporous hexagonal ZnO plates. These mesoporous structures can adsorb pollutant gases and increase photocatalytic oxidation of pollutant gases in compare with commercial ZnO nanoparticles and agglomerated nanoparticles synthesized in this work. XPS data confirmed ethylene glycol production by the ionic liquid, which could prove a role for ionic liquids as designers. The estimated BET surface area values of ZnO hexagonal mesoporous plates and agglomerated particles were 84 m2/g and 12 m2/g respectively. Optical properties of the mesoporous structures were analyzed by photoluminescence spectroscopy and diffuse reflectance UV-visible spectroscopy. The performance of these structures as efficient photocatalysts was further demonstrated by their removal of NOx, SO2, and CO under UV irradiation. The removal of NOx, SO2, and CO under UV irradiation was 56%, 81%, and 35% respectively, after 40 min of irradiation time. Reusability of the photocatalyst was determined; the results show no significant decrease of activity of photocatalyst. after five cycles.

A molecular design principle of lyotropic liquid-crystalline conjugated polymers with directed alignment capability for plastic electronics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Bong-Gi; Jeong, Eun Jeong; Chung, Jong Won

Conjugated polymers with a one-dimensional p-orbital overlap exhibit optoelectronic anisotropy. Their unique anisotropic properties can be fully realized in device applications only when the conjugated chains are aligned. Here, we report a molecular design principle of conjugated polymers to achieve concentration-regulated chain planarization, self-assembly, liquid-crystal-like good mobility and non-interdigitated side chains. As a consequence of these intra- and intermolecular attributes, chain alignment along an applied flow field occurs. This liquid-crystalline conjugated polymer was realized by incorporating intramolecular sulphur–fluorine interactions and bulky side chains linked to a tetrahedral carbon having a large form factor. By optimizing the polymer concentration and themore » flow field, we could achieve a high dichroic ratio of 16.67 in emission from conducting conjugated polymer films. Two-dimensional grazing-incidence X-ray diffraction was performed to analyse a well-defined conjugated polymer alignment. Thin-film transistors built on highly aligned conjugated polymer films showed more than three orders of magnitude faster carrier mobility along the conjugated polymer alignment direction than the perpendicular direction.« less

Germanium layers grown by zone thermal crystallization from a discrete liquid source

NASA Astrophysics Data System (ADS)

Yatsenko, A. N.; Chebotarev, S. N.; Lozovskii, V. N.; Mohamed, A. A. A.; Erimeev, G. A.; Goncharova, L. M.; Varnavskaya, A. A.

2017-11-01

It is proposed and investigated a method for growing thin uniform germanium layers onto large silicon substrates. The technique uses the hexagonally arranged local sources filled with liquid germanium. Germanium evaporates on very close substrate and in these conditions the residual gases vapor pressure highly reduces. It is shown that to achieve uniformity of the deposited layer better than 97% the critical thickness of the vacuum zone must be equal to l cr = 1.2 mm for a hexagonal arranged system of round local sources with the radius of r = 0.75 mm and the distance between the sources of h = 0.5 mm.

Influence of vitamin E acetate and other lipids on the phase behavior of mesophases based on unsaturated monoglycerides.

PubMed

Sagalowicz, L; Guillot, S; Acquistapace, S; Schmitt, B; Maurer, M; Yaghmur, A; de Campo, L; Rouvet, M; Leser, M; Glatter, O

2013-07-02

The phase behavior of the ternary unsaturated monoglycerides (UMG)-DL-α-tocopheryl acetate-water system has been studied. The effects of lipid composition in both bulk and dispersed lyotropic liquid crystalline phases and microemulsions were investigated. In excess water, progressive addition of DL-α-tocopheryl acetate to a binary UMG mixture results in the following phase sequence: reversed bicontinuous cubic phase, reversed hexagonal (H(II)) phase, and a reversed microemulsion. The action of DL-α-tocopheryl acetate is then compared to that of other lipids such as triolein, limonene, tetradecane, and DL-α-tocopherol. The impact of solubilizing these hydrophobic molecules on the UMG-water phase behavior shows some common features. However, the solubilization of certain molecules, like DL-α-tocopherol, leads to the presence of the reversed micellar cubic phase (space group number 227 and symmetry Fd3m) while the solubilization of others does not. These differences in phase behavior are discussed in terms of physical-chemical characteristics of the added lipid molecule and its interaction with UMG and water. From an applications point of view, phase behavior as a function of the solubilized content of guest molecules (lipid additive in our case) is crucial since macroscopic properties such as molecular release depend strongly on the phase present. The effect of two hydrophilic emulsifiers, used to stabilize the aqueous dispersions of UMG, was studied and compared. Those were Pluronic F127, which is the most commonly used stabilizer for these kinds of inverted type structures, and the partially hydrolyzed emulsifier lecithin (Emultop EP), which is a well accepted food-grade emulsifier. The phase behavior of particles stabilized by the partially hydrolyzed lecithin is similar to that of bulk sample at full hydration, but this emulsifier interacts significantly with the internal structure and affects it much more than F127.

Bulk and dispersed aqueous behaviour of an endogenous lipid, selachyl alcohol: Effect of Tween 80 and Pluronic F127 on nanostructure.

PubMed

Younus, Mohammad; Hawley, Adrian; Boyd, Ben J; Rizwan, Shakila B

2018-05-07

Tween 80 has been reported to provide a means of targeting drug nanocarriers to the blood- brain barrier. This study investigated the influence of addition of Tween 80 on the formation of different bulk and dispersed lyotropic liquid crystalline phases in selachyl alcohol-based systems. The effect of increasing concentrations of Tween 80 and Pluronic F127 (as a control) (0-25% w/w relative to SA) on the bulk phase behaviour and dispersions of selachyl alcohol (SA) were investigated using small angle X-ray scattering, dynamic light scattering, and cryogenic transmission electron microscopy. The addition of Tween 80 to SA bulk phase samples triggered concentration-dependent phase changes with the structure sequentially evolving from a reverse hexagonal phase (H 2 ) to a mixed H 2 and inverse bicontinuous cubic (V 2 ) then a V 2 phase alone. In contrast, the addition of Pluronic F127 resulted in a phase change from H 2 phase to a mixed lamellar and H 2 phase system. The mean particle size of internally structured particles was 125-190 nm with low polydispersity indices (0.1-0.2). Nanoparticles retained the bulk phase internal structure in the presence of Tween 80, whereas in the presence of Pluronic F127, the additional lamellar phase that formed in bulk phase systems was not observed. Cryo-TEM revealed the formation of cubosomes and hexosomes by SA in excess water in the presence of Tween 80 and Pluronic F127 respectively. In summary, it was shown that stabilisation of SA dispersions using Tween 80 resulted in a decrease in negative curvature leading to a change in internal structure from H 2 to V 2 phase. The studies provide the core understanding of particle structure to progress these structured lipid nanocarriers into delivery studies with Tween 80 as a mechanism to target the blood-brain barrier. Crown Copyright © 2018. Published by Elsevier B.V. All rights reserved.

Epidermal growth factor receptor-targeted lipid nanoparticles retain self-assembled nanostructures and provide high specificity

NASA Astrophysics Data System (ADS)

Zhai, Jiali; Scoble, Judith A.; Li, Nan; Lovrecz, George; Waddington, Lynne J.; Tran, Nhiem; Muir, Benjamin W.; Coia, Gregory; Kirby, Nigel; Drummond, Calum J.; Mulet, Xavier

2015-02-01

Next generation drug delivery utilising nanoparticles incorporates active targeting to specific sites. In this work, we combined targeting with the inherent advantages of self-assembled lipid nanoparticles containing internal nano-structures. Epidermal growth factor receptor (EGFR)-targeting, PEGylated lipid nanoparticles using phytantriol and 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-PEG-maleimide amphiphiles were created. The self-assembled lipid nanoparticles presented here have internal lyotropic liquid crystalline nano-structures, verified by synchrotron small angle X-ray scattering and cryo-transmission electron microscopy, that offer the potential of high drug loading and enhanced cell penetration. Anti-EGFR Fab' fragments were conjugated to the surface of nanoparticles via a maleimide-thiol reaction at a high conjugation efficiency and retained specificity following conjugation to the nanoparticles. The conjugated nanoparticles were demonstrated to have high affinity for an EGFR target in a ligand binding assay.Next generation drug delivery utilising nanoparticles incorporates active targeting to specific sites. In this work, we combined targeting with the inherent advantages of self-assembled lipid nanoparticles containing internal nano-structures. Epidermal growth factor receptor (EGFR)-targeting, PEGylated lipid nanoparticles using phytantriol and 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-PEG-maleimide amphiphiles were created. The self-assembled lipid nanoparticles presented here have internal lyotropic liquid crystalline nano-structures, verified by synchrotron small angle X-ray scattering and cryo-transmission electron microscopy, that offer the potential of high drug loading and enhanced cell penetration. Anti-EGFR Fab' fragments were conjugated to the surface of nanoparticles via a maleimide-thiol reaction at a high conjugation efficiency and retained specificity following conjugation to the nanoparticles. The conjugated nanoparticles were demonstrated to have high affinity for an EGFR target in a ligand binding assay. Electronic supplementary information (ESI) available: Fig. S1-S4. See DOI: 10.1039/c4nr05200e

Structure and reactions in some amphiphilic association systems

NASA Astrophysics Data System (ADS)

Guo, Rong

1999-06-01

The partial determinations of phase diagrams for some typical surfactants, such as SDS, CTAB and Triton X-100, give the basic aggregated states of the surfactant systems. In the micellar solutions, the diffusion coefficients of some surfactant association systems are determined by the cyclic voltammetry without any probe and used to describe the phase structure. (1) The first CMC, which represents the formation of spherical micelles, and the second CMC, which represents the transformation from spherical to rod-like micelles, are measured. The first and the second CMC are 8.0 x 10-3 mol. L -1 and 5.6 x 10-3 mol. L-1 for SDS, 8.9 x 10-4 mol. L-1 and 2.1 x 10-2 mol. L-1 for CTAB, and 3.2 x 10 -4 mol. L-1 and 1.3 x 10-3 mol. L-1 for Triton X-100, respectively. (2) The addition of polar additives, such as ethanol and benzyl alcohol (BA) in SDS micelles, or hexanol in Triton X-100 micelles, increases the diffusion coefficients and diffusion activation energy, decreases the micropolarity of the micelles with different shape, and causes the transformation from rod-like micelles to spherical ones or from spherical micelles to bicontinuous structure. (3) The isotropic region, which connects to the water comer in the phase diagram, is probably not an area of a single O/W structure, but an area with three different structures---the rod structure, spherical structure and the bicontinuous one. In the lyotropic liquid crystalline phase, the measurements of the small angle X-ray diffraction indicate that the structure parameters, such as interlayer spacing and water penetration, are related to the compositions of the surfactant association systems. The lamellar liquid crystal has a high water penetration but the hexagonal liquid crystal only has a water penetration about 0.05. Some surfactant association systems have been applied in the hydrotrope action of vitamin C (VC) and preparation of nanoparticles, respectively. Vitamin C (VC) can be used as hydrotrope agent in the cationic surfactant CTAB system with various co-surfactants: n-pentanol, n-octanol, n-valeric acid, and n-caproic acid, but not in SDS or Triton X-100 systems. Presence of VC stabilizes both W/O and O/W microemulsions but destabilizes the lamellar liquid crystalline phase. Hence, the "phase transition" from the lamellar liquid crystalline phase to the isotropic phase of O/W, W/O and bicontinuous structure phase occurs with the addition of VC. The hydrotropic action of VC has been used in sunscreens to increase the solubility of sunscreen E 557. The UV absorption spectra of E557 in various media surprisingly had a dependence on the colloid structure. A new method, the preparation of water-soluble nanoparticles, has been found by employing the effect of the penetration of solvent from water layer to amphiphilic layer in lamellar liquid crystals on the solubility of inorganic salts. Water-insoluble nanoparticles have been synthesized by the reaction of two water-soluble inorganic salts in the lamellar liquid crystal. The particle size is less than 10nm and can be controlled by the thickness of the solvent layer in the lamellar liquid crystal. The lamellar liquid crystalline phase of the Triton X-100/decanol/water system has been chosen as a medium because of its large lamellar liquid crystal region and its stability when inorganic salts are added.

Ribbon phase in a phase-separated lyotropic lamellar-sponge mixture under shear flow

NASA Astrophysics Data System (ADS)

Cristobal, G.; Rouch, J.; Panizza, P.; Narayanan, T.

2001-07-01

We report the effect of shear flow on a phase-separated system composed of lyotropic lamellar (Lα) and sponge (L3) phases in a mixture of brine, surfactant, and cosurfactant. Optical microscopy, small-angle light, and x-ray scattering measurements are consistent with the existence of a steady state made of multilamellar ribbonlike structures aligned in the flow direction. At high shear rates, these ribbonlike structures become unstable and break up into monodisperse droplets resulting in a shear-thickening transition.

Epitaxial Garnets and Hexagonal Ferrites.

DTIC Science & Technology

1982-04-20

goenv.o -,y la)ers were YIG (yttrium iron garnet ) films grown by liquid phase epitaxy w:* ( LPE ) on gadolinium gallium garnet (GGG) substrates. Magnetic...containing three epitaxial layers. In addition to the MSW work oil garnets , LPE of lithium ferrite and hexagonal fertites was studied. A substituted lead...of a stripline. The other layers are epitaxial films , generally YIG (yttrium iron garnet ) with magnetic properties adjusted by suitable modifications

Bacterial Motility Reveals Unknown Molecular Organization

PubMed Central

Duchesne, Ismaël; Rainville, Simon; Galstian, Tigran

2015-01-01

The water solubility of lyotropic liquid crystals (LCs) makes them very attractive to study the behavior of biological microorganisms in an environment where local symmetry is broken (as often encountered in nature). Several recent studies have shown a dramatic change in the behavior of flagellated bacteria when swimming in solutions of the lyotropic LC disodium cromoglycate (DSCG). In this study, the movements of Escherichia coli bacteria in DSCG-water solutions of different concentrations are observed to improve our understanding of this phenomenon. In addition, the viscosity of DSCG aqueous solutions is measured as a function of concentration at room temperature. We also experimentally identify a previously undescribed isotropic pretransition zone where bacteria start sticking to each other and to surfaces. Simple estimations show that the unbalanced osmotic pressure induced depletion force might be responsible for this sticking phenomenon. An estimate of the bacteria propulsive force and the DSCG aggregates length (versus concentration) are calculated from the measured viscosity of the medium. All these quantities are found to undergo a strong increase in the pretransition zone, starting at a threshold concentration of 6 ± 1 wt % DSCG that is well below the known isotropic-LC transition (∼10 wt %). This study also shines light on the motility of flagellated bacteria in realistic environments, and it opens new avenues for interesting applications such as the use of motile microorganisms to probe the physical properties of their host or smart bandages that could guide bacteria out of wounds. PMID:26588572

The search for new amphiphiles: synthesis of a modular, high-throughput library

PubMed Central

Feast, George C; Lepitre, Thomas; Mulet, Xavier; Conn, Charlotte E; Hutt, Oliver E

2014-01-01

Summary Amphiphilic compounds are used in a variety of applications due to their lyotropic liquid-crystalline phase formation, however only a limited number of compounds, in a potentially limitless field, are currently in use. A library of organic amphiphilic compounds was synthesised consisting of glucose, galactose, lactose, xylose and mannose head groups and double and triple-chain hydrophobic tails. A modular, high-throughput approach was developed, whereby head and tail components were conjugated using the copper-catalysed azide–alkyne cycloaddition (CuAAC) reaction. The tails were synthesised from two core alkyne-tethered intermediates, which were subsequently functionalised with hydrocarbon chains varying in length and degree of unsaturation and branching, while the five sugar head groups were selected with ranging substitution patterns and anomeric linkages. A library of 80 amphiphiles was subsequently produced, using a 24-vial array, with the majority formed in very good to excellent yields. A preliminary assessment of the liquid-crystalline phase behaviour is also presented. PMID:25161714

The search for new amphiphiles: synthesis of a modular, high-throughput library.

PubMed

Feast, George C; Lepitre, Thomas; Mulet, Xavier; Conn, Charlotte E; Hutt, Oliver E; Savage, G Paul; Drummond, Calum J

2014-01-01

Amphiphilic compounds are used in a variety of applications due to their lyotropic liquid-crystalline phase formation, however only a limited number of compounds, in a potentially limitless field, are currently in use. A library of organic amphiphilic compounds was synthesised consisting of glucose, galactose, lactose, xylose and mannose head groups and double and triple-chain hydrophobic tails. A modular, high-throughput approach was developed, whereby head and tail components were conjugated using the copper-catalysed azide-alkyne cycloaddition (CuAAC) reaction. The tails were synthesised from two core alkyne-tethered intermediates, which were subsequently functionalised with hydrocarbon chains varying in length and degree of unsaturation and branching, while the five sugar head groups were selected with ranging substitution patterns and anomeric linkages. A library of 80 amphiphiles was subsequently produced, using a 24-vial array, with the majority formed in very good to excellent yields. A preliminary assessment of the liquid-crystalline phase behaviour is also presented.

Mesomorphic glass nanocomposites made of metal alkanoates and nanoparticles as emerging nonlinear-optical materials

NASA Astrophysics Data System (ADS)

Garbovskiy, Y.; Klimusheva, G.; Mirnaya, T.

2016-09-01

Mesomorphic metal alkanoates is very promising yet overlooked class of nonlinear-optical materials. Metal alkanoates can exhibit a broad variety of condensed states of matter including solid crystals, plastic crystals, lyotropic and thermotropic ionic liquid crystals, liquids, mesomorphic glasses, and Langmuir-Blodgett films. Glass-forming properties of metal alkanoates combined with their use as nano-reactors and anisotropic host open up simple and efficient way to design various photonic nanomaterials. Despite very interesting physics, the experimental data on optical and nonlinearoptical properties of such materials are scarce. The goal of the present paper is to fill the gap by discussing recent advances in the field of photonic materials made of metal alkanoates, organic dyes, and nanoparticles. Optical and nonlinear-optical properties of the following materials are reviewed: (i) mesomorphic glass doped with organic dyes; (ii) smectic glass composed of cobalt alkanoates; (iii) semiconductor nanoparticles embedded in a glassy host; (iv) metal nanoparticles - glass (the cobalt octanoate) nanocomposites.

Hexagonal bubble formation and nucleation in sodium chloride solution

NASA Astrophysics Data System (ADS)

Wang, Lifen; Liu, Lei; Mohsin, Ali; Wen, Jianguo; Gu, Gong; Miller, Dean

The bubble is formed frequently at a solid-liquid interface when the surface of the solid or liquid has a tendency of accumulating molecular species due to unbalanced surface hydrophobicity attraction. Morphology and shape of the bubble are thought to be associated with the Laplace pressure that spherical-cap-shaped object are commonly observed. Dynamic surface nanobubble formation and nucleation in the controlled system have been not fully investigated due to the direct visualization challenge in liquid systems. Here, utilizing in situ TEM, dynamic formation and collapse of spherical-shaped nanobubbles were observed at the water-graphene interface, while hexagonal nanobubbles grew and merged with each other at water-crystalline sodium chloride interface. Our finding demonstrates that different hydrophobic-hydrophilic interaction systems give rise to the varied morphology of surface nanobubble, leading to the fundamental understanding of the interface-interaction-governed law on the formation of surface nanobubble.

Topological Defects in a Living Nematic Ensnare Swimming Bacteria

NASA Astrophysics Data System (ADS)

Genkin, Mikhail M.; Sokolov, Andrey; Lavrentovich, Oleg D.; Aranson, Igor S.

2017-01-01

Active matter exemplified by suspensions of motile bacteria or synthetic self-propelled particles exhibits a remarkable propensity to self-organization and collective motion. The local input of energy and simple particle interactions often lead to complex emergent behavior manifested by the formation of macroscopic vortices and coherent structures with long-range order. A realization of an active system has been conceived by combining swimming bacteria and a lyotropic liquid crystal. Here, by coupling the well-established and validated model of nematic liquid crystals with the bacterial dynamics, we develop a computational model describing intricate properties of such a living nematic. In faithful agreement with the experiment, the model reproduces the onset of periodic undulation of the director and consequent proliferation of topological defects with the increase in bacterial concentration. It yields a testable prediction on the accumulation of bacteria in the cores of +1 /2 topological defects and depletion of bacteria in the cores of -1 /2 defects. Our dedicated experiment on motile bacteria suspended in a freestanding liquid crystalline film fully confirms this prediction. Our findings suggest novel approaches for trapping and transport of bacteria and synthetic swimmers in anisotropic liquids and extend a scope of tools to control and manipulate microscopic objects in active matter.

Epitaxial Garnets and Hexagonal Ferrites.

DTIC Science & Technology

1983-12-01

operating at frequencies between 1 GHz and 25 GHz. 2. Investigate LPE growth of lithium ferrite with the objective of preparing low-loss, large area films ...and hexagonal ferrites when the series of contracts began in 1975. At that time the liquid phase epitaxy method for growth of magnetic garnet films ...principal interest in epitaxial garnets was for magnetic bubble memories. For this Uapplication the films had to be about 3pm thick with low defect density

Epitaxial Garnets and Hexagonal Ferrites.

DTIC Science & Technology

1980-02-28

shaped LPE garnet samples with 31.5um film thickness. We were informed that initial evalu- ation showed acceptably low insertion loss and that the material...frequencies above 25 GHz. c. Furnish up to eight (8) liquid phase epitaxy yttrium iron garnet films to RADC/EEA for testing and evaluation. These tasks...a "Method for Controlling Resonance Frequency of Yttrium Iron Garnet Films ." A patent, "Epitaxial Growth of M-type Hexagonal Ferrite Films on Spinel

Topological defects in a living nematic ensnare swimming bacteria [Linking bacterial motility and liquid crystallinity in a model of living nematic

DOE Office of Scientific and Technical Information (OSTI.GOV)

Genkin, Mikhail Mikhailovich; Sokolov, Andrey; Lavrentovich, Oleg D.

Active matter exemplified by suspensions of motile bacteria or synthetic self-propelled particles exhibits a remarkable propensity to self-organization and collective motion. The local input of energy and simple particle interactions often lead to complex emergent behavior manifested by the formation of macroscopic vortices and coherent structures with long-range order. A realization of an active system has been conceived by combining swimming bacteria and a lyotropic liquid crystal. Here, by coupling the well-established and validated model of nematic liquid crystals with the bacterial dynamics, we develop a computational model describing intricate properties of such a living nematic. In faithful agreement withmore » the experiment, the model reproduces the onset of periodic undulation of the director and consequent proliferation of topological defects with the increase in bacterial concentration. It yields a testable prediction on the accumulation of bacteria in the cores of +1/2 topological defects and depletion of bacteria in the cores of -1/2 defects. Our dedicated experiment on motile bacteria suspended in a freestanding liquid crystalline film fully confirms this prediction. Lastly, our findings suggest novel approaches for trapping and transport of bacteria and synthetic swimmers in anisotropic liquids and extend a scope of tools to control and manipulate microscopic objects in active matter.« less

Topological defects in a living nematic ensnare swimming bacteria [Linking bacterial motility and liquid crystallinity in a model of living nematic

DOE PAGES

Genkin, Mikhail Mikhailovich; Sokolov, Andrey; Lavrentovich, Oleg D.; ...

2017-03-08

Active matter exemplified by suspensions of motile bacteria or synthetic self-propelled particles exhibits a remarkable propensity to self-organization and collective motion. The local input of energy and simple particle interactions often lead to complex emergent behavior manifested by the formation of macroscopic vortices and coherent structures with long-range order. A realization of an active system has been conceived by combining swimming bacteria and a lyotropic liquid crystal. Here, by coupling the well-established and validated model of nematic liquid crystals with the bacterial dynamics, we develop a computational model describing intricate properties of such a living nematic. In faithful agreement withmore » the experiment, the model reproduces the onset of periodic undulation of the director and consequent proliferation of topological defects with the increase in bacterial concentration. It yields a testable prediction on the accumulation of bacteria in the cores of +1/2 topological defects and depletion of bacteria in the cores of -1/2 defects. Our dedicated experiment on motile bacteria suspended in a freestanding liquid crystalline film fully confirms this prediction. Lastly, our findings suggest novel approaches for trapping and transport of bacteria and synthetic swimmers in anisotropic liquids and extend a scope of tools to control and manipulate microscopic objects in active matter.« less

Orientational order in smectic liquid-crystalline phases of amphiphilic diols

NASA Astrophysics Data System (ADS)

Giesselmann, Frank; Germer, Roland; Saipa, Alexander

2005-07-01

The thermotropic smectic phases of amphiphilic 2-(trans-4-n-alkylcyclohexyl)-propane-1,3-diols were investigated by means of small- and wide-angle x-ray scattering and values of the smectic (bi-)layer spacing, the orientational order parameters ⟨P2⟩ and ⟨P4⟩, the orientational distribution function as well as the intralayer correlation length were extracted from the scattering profiles. The results for the octyl homolog indicate that these smectic phases combine a very high degree of smectic one-dimensional-translational order with remarkably low orientational order, the order parameter of which (⟨P2⟩≈0.56) is far below those values typically found in nonamphiphilic smectics. This combination, quite exceptional in thermotropic smectics, most likely originates from the intermolecular hydrogen bonding between the terminal diol groups which seems to be the specific driving force in the formation of the thermotropic smectic structure in these amphiphiles and leads to a type of microphase segregation. Even in the absence of a solvent, the liquid-crystalline ordering of the amphiphilic mesogens comes close to the structure of the so-called neat soaps, found in lyotropic liquid crystals.

Dynamics of water confined in lyotropic liquid crystals: Molecular dynamics simulations of the dynamic structure factor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mantha, Sriteja; Yethiraj, Arun

2016-02-24

The properties of water under confinement are of practical and fundamental interest. Here in this work we study the properties of water in the self-assembled lyotropic phases of gemini surfactants with a focus on testing the standard analysis of quasi-elastic neutron scattering (QENS) experiments. In QENS experiments the dynamic structure factor is measured and fit to models to extract the translational diffusion constant, D T , and rotational relaxation time, τ R. We test this procedure by using simulation results for the dynamic structure factor, extracting the dynamic parameters from the fit as is typically done in experiments, and comparingmore » the values to those directly measured in the simulations. We find that the decoupling approximation, where the intermediate scattering function is assumed to be a product of translational and rotational contributions, is quite accurate. The jump-diffusion and isotropic rotation models, however, are not accurate when the degree of confinement is high. In particular, the exponential approximations for the intermediate scattering function fail for highly confined water and the values of D T and τ R can differ from the measured value by as much as a factor of two. Other models have more fit parameters, however, and with the range of energies and wave-vectors accessible to QENS, the typical analysis appears to be the best choice. In the most confined lamellar phase, the dynamics are sufficiently slow that QENS does not access a large enough time scale and neutron spin echo measurements would be a valuable technique in addition to QENS.« less

2D-crystallization of Rhodococcus 20S proteasome at the liquid-liquid interface

NASA Astrophysics Data System (ADS)

Aoyama, Kazuhiro

1996-10-01

The 2D-crystallization method using the liquid-liquid interface between a aqueous phase (protein solution) and a thin organic liquid (dehydroabietylamine) layer has been applied to the Rhodococcus 20S proteasome. The 20S proteasome is known to be the core complex of the 26S proteasome, which is the central protease of the ubiquitin-dependent pathway. Two types of ordered arrays were obtained, both large enough for high resolution analysis by electron crystallography. The first one had a four-fold symmetry, whereas the second one was found out to be a hexagonally close-packed array. By image analysis based on a real space correlation averaging (CAV) technique, the close-packed array was found to be hexagonally packed, but the molecules had presumably rotational freedom. The four-fold array was found to be a true crystal with p4 symmetry. Lattice constants were a = b = 20.0 nm and α = 90°. The unit cell of this crystal contained two molecules. The diffraction pattern computed from the original picture showed spots up to (4, 5) that corresponds to 3.1 nm resolution. After applying an unbending procedure, the diffraction pattern showed spots extending to 1.8 nm resolution.

Structural Rheology of the Smectic Phase

PubMed Central

Fujii, Shuji; Komura, Shigeyuki; Lu, Chun-Yi David

2014-01-01

In this review article, we discuss the rheological properties of the thermotropic smectic liquid crystal 8CB with focal conic domains (FCDs) from the viewpoint of structural rheology. It is known that the unbinding of the dislocation loops in the smectic phase drives the smectic-nematic transition. Here we discuss how the unbinding of the dislocation loops affects the evolution of the FCD size, linear and nonlinear rheological behaviors of the smectic phase. By studying the FCD formation from the perpendicularly oriented smectic layers, we also argue that dislocations play a key role in the structural development in layered systems. Furthermore, similarities in the rheological behavior between the FCDs in the smectic phase and the onion structures in the lyotropic lamellar phase suggest that these systems share a common physical origin for the elasticity. PMID:28788123

A 2D/3D hybrid integral imaging display by using fast switchable hexagonal liquid crystal lens array

NASA Astrophysics Data System (ADS)

Lee, Hsin-Hsueh; Huang, Ping-Ju; Wu, Jui-Yi; Hsieh, Po-Yuan; Huang, Yi-Pai

2017-05-01

The paper proposes a new display which could switch 2D and 3D images on a monitor, and we call it as Hybrid Display. In 3D display technologies, the reduction of image resolution is still an important issue. The more angle information offer to the observer, the less spatial resolution would offer to image resolution because of the fixed panel resolution. Take it for example, in the integral photography system, the part of image without depth, like background, will reduce its resolution by transform from 2D to 3D image. Therefore, we proposed a method by using liquid crystal component to quickly switch the 2D image and 3D image. Meanwhile, the 2D image is set as a background to compensate the resolution.. In the experiment, hexagonal liquid crystal lens array would be used to take the place of fixed lens array. Moreover, in order to increase lens power of the hexagonal LC lens array, we applied high resistance (Hi-R) layer structure on the electrode. Hi-R layer would make the gradient electric field and affect the lens profile. Also, we use panel with 801 PPI to display the integral image in our system. Hence, the consequence of full resolution 2D background with the 3D depth object forms the Hybrid Display.

Polymorphism of phosphoric oxide

USGS Publications Warehouse

Hill, W.L.; Faust, G.T.; Hendricks, S.B.

1943-01-01

The melting points and monotropic relationship of three crystalline forms of phosphoric oxide were determined by the method of quenching. Previous vapor pressure data are discussed and interpreted to establish a pressure-temperature diagram (70 to 600??) for the one-component system. The system involves three triple points, at which solid, liquid and vapor (P4O10) coexist in equilibrium, namely: 420?? and 360 cm., 562?? and 43.7 cm. and 580?? and 55.5 cm., corresponding to the hexagonal, orthorhombic and stable polymorphs, respectively, and at least two distinct liquids, one a stable polymer of the other, which are identified with the melting of the stable form and the hexagonal modification, respectively. Indices of refraction of the polymorphs and glasses were determined. The density and the thermal, hygroscopic and structural properties of the several phases are discussed.

Uniform hexagonal graphene flakes and films grown on liquid copper surface.

PubMed

Geng, Dechao; Wu, Bin; Guo, Yunlong; Huang, Liping; Xue, Yunzhou; Chen, Jianyi; Yu, Gui; Jiang, Lang; Hu, Wenping; Liu, Yunqi

2012-05-22

Unresolved problems associated with the production of graphene materials include the need for greater control over layer number, crystallinity, size, edge structure and spatial orientation, and a better understanding of the underlying mechanisms. Here we report a chemical vapor deposition approach that allows the direct synthesis of uniform single-layered, large-size (up to 10,000 μm(2)), spatially self-aligned, and single-crystalline hexagonal graphene flakes (HGFs) and their continuous films on liquid Cu surfaces. Employing a liquid Cu surface completely eliminates the grain boundaries in solid polycrystalline Cu, resulting in a uniform nucleation distribution and low graphene nucleation density, but also enables self-assembly of HGFs into compact and ordered structures. These HGFs show an average two-dimensional resistivity of 609 ± 200 Ω and saturation current density of 0.96 ± 0.15 mA/μm, demonstrating their good conductivity and capability for carrying high current density.

Uniform hexagonal graphene flakes and films grown on liquid copper surface

PubMed Central

Geng, Dechao; Wu, Bin; Guo, Yunlong; Huang, Liping; Xue, Yunzhou; Chen, Jianyi; Yu, Gui; Jiang, Lang; Hu, Wenping; Liu, Yunqi

2012-01-01

Unresolved problems associated with the production of graphene materials include the need for greater control over layer number, crystallinity, size, edge structure and spatial orientation, and a better understanding of the underlying mechanisms. Here we report a chemical vapor deposition approach that allows the direct synthesis of uniform single-layered, large-size (up to 10,000 μm2), spatially self-aligned, and single-crystalline hexagonal graphene flakes (HGFs) and their continuous films on liquid Cu surfaces. Employing a liquid Cu surface completely eliminates the grain boundaries in solid polycrystalline Cu, resulting in a uniform nucleation distribution and low graphene nucleation density, but also enables self-assembly of HGFs into compact and ordered structures. These HGFs show an average two-dimensional resistivity of 609 ± 200 Ω and saturation current density of 0.96 ± 0.15 mA/μm, demonstrating their good conductivity and capability for carrying high current density. PMID:22509001

Liquid core photonic crystal fiber with low-refractive-index liquids for optofluidic applications.

PubMed

Park, Jiyoung; Kang, Doo-Eui; Paulson, Bjorn; Nazari, Tavakol; Oh, Kyunghwan

2014-07-14

A defectless hexagonal air-silica photonic crystal fiber (PCF) structure with its central hole selectively filled by a low-refractive-index liquid is numerically analyzed. Despite the fact that the refractive index of the liquid is significantly lower than that of silica, we found an optimal range of waveguide parameters to ensure light guidance through the liquid core in the fundamental mode, maximizing the light-liquid interaction over a desired wavelength range. Using the vectorial finite element method (FEM), we report detailed parametric studies in terms of the effective index, chromatic dispersion, optical loss, and modal intensity distribution of the liquid core PCFs.

Role of Molecular Structure on X-ray Diffraction in Thermotropic Uniaxial and Biaxial Nematic Liquid Crystal Phases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Acharya, Bharat R.; Kang, Shin-Woong; Prasad, Veena

2009-08-27

X-ray diffraction is one of the most definitive methods to determine the structure of condensed matter phases, and it has been applied to unequivocally infer the structures of conventional calamitic and lyotropic liquid crystals. With the advent of bent-core and tetrapodic mesogens and the discovery of the biaxial nematic phase in them, the experimental results require more careful interpretation and analysis. Here, we present ab-initio calculations of X-ray diffraction patterns in the isotropic, uniaxial nematic, and biaxial nematic phases of bent-core mesogens. A simple Meier-Saupe-like molecular distribution function is employed to describe both aligned and unaligned mesophases. The distribution functionmore » is decomposed into two, polar and azimuthal, distribution functions to calculate the effect of the evolution of uniaxial and biaxial nematic orientational order. The calculations provide satisfactory semiquantitative interpretations of experimental results. The calculations presented here should provide a pathway to more refined and quantitative analysis of X-ray diffraction data from the biaxial nematic phase.« less

Role of Molecular Structure on X-ray Diffraction in Uniaxial and Biaxial Phases of Thermotropic Liquid Crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Acharya, Bharat R.; Kang, Shin-Woong; Prasad, Veena

2009-04-29

X-ray diffraction is one of the most definitive methods to determine the structure of condensed matter phases, and it has been applied to unequivocally infer the structures of conventional calamitic and lyotropic liquid crystals. With the advent of bent-core and tetrapodic mesogens and the discovery of the biaxial nematic phase in them, the experimental results require more careful interpretation and analysis. Here, we present ab-initio calculations of X-ray diffraction patterns in the isotropic, uniaxial nematic, and biaxial nematic phases of bent-core mesogens. A simple Meier-Saupe-like molecular distribution function is employed to describe both aligned and unaligned mesophases. The distribution functionmore » is decomposed into two, polar and azimuthal, distribution functions to calculate the effect of the evolution of uniaxial and biaxial nematic orientational order. The calculations provide satisfactory semiquantitative interpretations of experimental results. The calculations presented here should provide a pathway to more refined and quantitative analysis of X-ray diffraction data from the biaxial nematic phase.« less

Positron annihilation lifetime spectroscopy (PALS) as a characterization technique for nanostructured self-assembled amphiphile systems.

PubMed

Dong, Aurelia W; Pascual-Izarra, Carlos; Pas, Steven J; Hill, Anita J; Boyd, Ben J; Drummond, Calum J

2009-01-08

Positron annihilation lifetime spectroscopy (PALS) has potential as a novel rapid characterization method for self-assembly amphiphile systems; however, a lack of systematic correlation of PALS parameters with structural attributes has limited its more widespread application. In this study, using the well-characterized phytantriol/water and the phytantriol/vitamin E acetate/water self-assembly amphiphile systems, the impact of systematic structural changes controlled by changes in composition and temperature on PALS parameters has been studied. The PALS parameters (orthopositronium (oPs) lifetime and intensity signatures) were shown to be sensitive to the molecular packing and mobility of the self-assembled lipid molecules in various lyotropic liquid crystalline phases, enabling differentiation between liquid crystalline structures. The oPs lifetime, related to the molecular packing and mobility, is correlated with rheological properties of the individual mesophases. The oPs lifetime links the lipid chain packing and mobility in the various mesophases to resultant macroscopic properties, such as permeability, which is critical for the use of these mesophase structures as diffusion-controlled release matrices for active liposoluble compounds.

What Determines the Ice Polymorph in Clouds?

PubMed

Hudait, Arpa; Molinero, Valeria

2016-07-20

Ice crystals in the atmosphere nucleate from supercooled liquid water and grow by vapor uptake. The structure of the ice polymorph grown has strong impact on the morphology and light scattering of the ice crystals, modulates the amount of water vapor in ice clouds, and can impact the molecular uptake and reactivity of atmospheric aerosols. Experiments and molecular simulations indicate that ice nucleated and grown from deeply supercooled liquid water is metastable stacking disordered ice. The ice polymorph grown from vapor has not yet been determined. Here we use large-scale molecular simulations to determine the structure of ice that grows as a result of uptake of water vapor in the temperature range relevant to cirrus and mixed-phase clouds, elucidate the molecular mechanism of the formation of ice at the vapor interface, and compute the free energy difference between cubic and hexagonal ice interfaces with vapor. We find that vapor deposition results in growth of stacking disordered ice only under conditions of extreme supersaturation, for which a nonequilibrium liquid layer completely wets the surface of ice. Such extreme conditions have been used to produce stacking disordered frost ice in experiments and may be plausible in the summer polar mesosphere. Growth of ice from vapor at moderate supersaturations in the temperature range relevant to cirrus and mixed-phase clouds, from 200 to 260 K, produces exclusively the stable hexagonal ice polymorph. Cubic ice is disfavored with respect to hexagonal ice not only by a small penalty in the bulk free energy (3.6 ± 1.5 J mol(-1) at 260 K) but also by a large free energy penalty at the ice-vapor interface (89.7 ± 12.8 J mol(-1) at 260 K). The latter originates in higher vibrational entropy of the hexagonal-terminated ice-vapor interface. We predict that the free energy penalty against the cubic ice interface should decrease strongly with temperature, resulting in some degree of stacking disorder in ice grown from vapor in the tropical tropopause layer, and in polar stratospheric and noctilucent clouds. Our findings support and explain the evolution of the morphology of ice crystals from hexagonal to trigonal symmetry with decreasing temperature, as reported by experiments and in situ measurements in clouds. We conclude that selective growth of the elusive cubic ice polymorph by manipulation of the interfacial properties can likely be achieved at the ice-liquid interface but not at the ice-vapor interface.

Charge Structure and Counterion Distribution in Hexagonal DNA Liquid Crystal

PubMed Central

Dai, Liang; Mu, Yuguang; Nordenskiöld, Lars; Lapp, Alain; van der Maarel, Johan R. C.

2007-01-01

A hexagonal liquid crystal of DNA fragments (double-stranded, 150 basepairs) with tetramethylammonium (TMA) counterions was investigated with small angle neutron scattering (SANS). We obtained the structure factors pertaining to the DNA and counterion density correlations with contrast matching in the water. Molecular dynamics (MD) computer simulation of a hexagonal assembly of nine DNA molecules showed that the inter-DNA distance fluctuates with a correlation time around 2 ns and a standard deviation of 8.5% of the interaxial spacing. The MD simulation also showed a minimal effect of the fluctuations in inter-DNA distance on the radial counterion density profile and significant penetration of the grooves by TMA. The radial density profile of the counterions was also obtained from a Monte Carlo (MC) computer simulation of a hexagonal array of charged rods with fixed interaxial spacing. Strong ordering of the counterions between the DNA molecules and the absence of charge fluctuations at longer wavelengths was shown by the SANS number and charge structure factors. The DNA-counterion and counterion structure factors are interpreted with the correlation functions derived from the Poisson-Boltzmann equation, MD, and MC simulation. Best agreement is observed between the experimental structure factors and the prediction based on the Poisson-Boltzmann equation and/or MC simulation. The SANS results show that TMA is too large to penetrate the grooves to a significant extent, in contrast to what is shown by MD simulation. PMID:17098791

Freezing, melting and structure of ice in a hydrophilic nanopore.

PubMed

Moore, Emily B; de la Llave, Ezequiel; Welke, Kai; Scherlis, Damian A; Molinero, Valeria

2010-04-28

The nucleation, growth, structure and melting of ice in 3 nm diameter hydrophilic nanopores are studied through molecular dynamics simulations with the mW water model. The melting temperature of water in the pore was T(m)(pore) = 223 K, 51 K lower than the melting point of bulk water in the model and in excellent agreement with experimental determinations for 3 nm silica pores. Liquid and ice coexist in equilibrium at the melting point and down to temperatures as low as 180 K. Liquid water is located at the interface of the pore wall, increasing from one monolayer at the freezing temperature, T(f)(pore) = 195 K, to two monolayers a few degrees below T(m)(pore). Crystallization of ice in the pore occurs through homogeneous nucleation. At the freezing temperature, the critical nucleus contains approximately 75 to 100 molecules, with a radius of gyration similar to the radius of the pore. The critical nuclei contain features of both cubic and hexagonal ice, although stacking of hexagonal and cubic layers is not defined until the nuclei reach approximately 150 molecules. The structure of the confined ice is rich in stacking faults, in agreement with the interpretation of X-ray and neutron diffraction experiments. Though the presence of cubic layers is twice as prevalent as hexagonal ones, the crystals should not be considered defective Ic as sequences with more than three adjacent cubic (or hexagonal) layers are extremely rare in the confined ice.

Time- and Space-Resolved SAXS Experiments Inform on Phase Transition Kinetics in Hydrated, Liquid-Crystalline Films of Polyion-Surfactant Ion "Complex Salts".

PubMed

Li, Joaquim; Gustavsson, Charlotte; Piculell, Lennart

2016-05-24

Detailed time- and space-resolved SAXS experiments show the variation with hydration of liquid crystalline structures in ethanol-cast 5-80 μm thick films of polyion-surfactant ion "complex salts" (CS). The CS were dodecyl- (C12) or hexadecyl- (C16) trimethylammonium surfactants with polyacrylate (DP 25 or 6000) counter-polyions. The experiments were carried out on vertical films in humid air above a movable water bath, so that gradients of hydration were generated, which could rapidly be altered. Scans over different positions along a film, kept fixed relative to the bath, showed that the surfactant aggregates of the various liquid-crystalline CS structures grow in cross-sectional area with decreasing hydration. This behavior is attributed to the low water content. Studies of films undergoing rapid dehydration, made possible by the original experimental setup, gave strong evidence that some of the investigated systems remain kinetically trapped for minutes in a nonequilibrium Pm3n micellar cubic phase before switching to the equilibrium P6mm 2D hexagonal phase. Both the length of the polyion and the length of the surfactant hydrocarbon "tail" affect the kinetics of the phase transition. The slowness of the cubic-to-hexagonal structural transition is attributed to the fact that it requires major rearrangements of the polyions and surfactant ions relative to each other. By contrast, other structure changes, such as between the hexagonal and rectangular phases, were observed to occur much more rapidly.

Disorder from the Bulk Ionic Liquid in Electric Double Layer Transistors

DOE PAGES

Petach, Trevor A.; Reich, Konstantin V.; Zhang, Xiao; ...

2017-07-28

Ionic liquid gating has a number of advantages over solid-state gating, especially for flexible or transparent devices and for applications requiring high carrier densities. But, the large number of charged ions near the channel inevitably results in Coulomb scattering, which limits the carrier mobility in otherwise clean systems. We develop a model for this Coulomb scattering. We then validate our model experimentally using ionic liquid gating of graphene across varying thicknesses of hexagonal boron nitride, demonstrating that disorder in the bulk ionic liquid often dominates the scattering.

Dislocations and other topological oddities

NASA Astrophysics Data System (ADS)

Pieranski, Pawel

2016-03-01

We will show that the book Dislocations by Jacques Friedel, published half a century ago, can still be recommended, in agreement with the author's intention, as a textbook ;for research students at University and for students at engineering schools as well as for research engineers;. Indeed, today dislocations are known to occur not only in solid crystals but also in many other systems discovered more recently such as colloidal crystals or liquid crystals having periodic structures. Moreover, the concept of dislocations is an excellent starting point for lectures on topological defects occurring in systems equipped with order parameters resulting from broken symmetries: disclinations in nematic or hexatic liquid crystals, dispirations in chiral smectics or disorientations in lyotropic liquid crystals. The discussion of dislocations in Blue Phases will give us an opportunity to call on mind Sir Charles Frank, friend of Jacques Friedel since his Bristol years, who called these ephemeral mesophases ;topological oddities;. Being made of networks of disclinations, Blue Phases are similar to Twist Grain Boundary (TGB) smectic phases, which are made of networks of screw dislocations and whose existence was predicted by de Gennes in 1972 on the basis of the analogy between smectics and superconductors. We will stress that the book by Jacques Friedel contains seeds of this analogy.

Assembly, Elasticity, and Structure of Lyotropic Chromonic Liquid Crystals and Disordered Colloids

NASA Astrophysics Data System (ADS)

Davidson, Zoey S.

This dissertation describes experiments which explore the structure and dynamics in two classes of soft materials: lyotropic chromonic liquid crystals and colloidal glasses and super-cooled liquids. The first experiments found that the achiral LCLCs, sunset yellow FCF (SSY) and disodium cromoglycate (DSCG) both exhibit spontaneous mirror symmetry breaking in the nematic phase driven by a giant elastic anisotropy of their twist modulus compared to their splay and bend moduli. Resulting structures of the confined LCLCs display interesting director configurations due to interplay of topologically required defects and twisted director fields. At higher concentrations, the LCLC compounds form columnar phases. We studied the columnar phase confined within spherical drops and discovered and understood configurations of the LC that sometimes led to non-spherical droplet shapes. The second experiments with SSY LCLCs confined in hollow cylinders uncovered director configurations which were driven in large measure by an exotic elastic modulus known as saddle-splay. We measured this saddle-splay modulus in a LCLC for the first time and found it to be more than 50 times greater than the twist elastic modulus. This large relative value of the saddle-splay modulus violates a theoretical result/assumption known as the Ericksen inequality. A third group of experiments on LCLCs explored the drying process of sessile drops containing SSY solutions, including evaporation dynamics, morphology, and deposition patterns. These drops differ from typical, well-studied evaporating colloidal drops primarily due to the LCLC's concentration-dependent isotropic, nematic, and columnar phases. Phase separation occurs during evaporation, creating surface tension gradients and significant density and viscosity variation within the droplet. Thus, the drying multiphase drops exhibit new convective currents, drop morphologies, deposition patterns, as well as a novel ordered crystalline phase. Finally, experiments in colloidal glasses and super-cooled liquids were initiated to probe the relationship between structure and dynamics in their constituent particles. The displacements of individual particles in the colloids can be decomposed into small cage fluctuations and large rearrangements into new cages. We found a correlation between the rate of rearrangement and the local cage structure associated with each particle. Particle trajectories of a two-dimensional binary mixture of soft colloids are captured by video microscopy. We use a machine learning method to calculate particle "softness'', which indicates the likelihood of rearrangement based on many radial structural features for each particle. We measured the residence time between consecutive rearrangements and related probability distribution functions (PDFs). The softness-dependent conditional PDF is well fit by an exponential with decay time decreasing monotonically with increasing softness. Using these data and a simple thermal activation model, we determined activation energies for rearrangements.

Elasticity and hydrodynamic properties of ``doped solvent dilute'' lamellar phases

NASA Astrophysics Data System (ADS)

Nallet, Frédéric; Roux, Didier; Quilliet, Catherine; Fabre, Pascale; Milner, Scott T.

1994-09-01

The equilibrium fluctuations and weakly out-of-equilibrium relaxation properties of “doped solvent" dilute lamellar phases are investigated, both theoretically and experimentally, in the low-frequency, long-wavelength limit. The physical system of interest is a three-component smectic A lyotropic liquid crystal where surfactant bilayers infinite in extent are periodically stacked along one direction in space and separated by a colloidal solution. Two experimentally relevant modes are found in the lowest frequency part of the fluctuation spectrum of such multicomponent systems. Both are associated to the relaxation of coupled layer displacement and colloid concentration waves. In the limit of small coupling, one mode is close to the well-known undulation/baroclinic mode of two-component lamellar phases, while the other corresponds to the Brownian diffusive motion of the colloid in an anisotropic medium. Elastic constants of the smectic liquid crystal and diffusion parameters of the colloidal solution may be deduced from a measurement of the anisotropic dispersion relation of these two modes, as illustrated by dynamic light scattering experiments on the ferrosmectic system. Les fluctuations à l'équilibre ainsi que la relaxation des états légèrement en dehors de l'équilibre des phases lamellaires à “solvant dopé” sont étudiées, aussi bien d'un point de vue théorique qu'expérimental, dans la limite de basses fréquences et de grandes longueurs d'onde. Les systèmes décrits sont des cristaux-liquides smectiques A lyotropes formés de trois constituants : un tensioactif en solution dans une suspension colloïdale forme des bicouches de grande extension latérale qui s'empilent de façon périodique le long d'une direction dans l'espace. Avec de tels systèmes anisotropes et à plusieurs constituants deux modes présents dans la partie à basse fréquence du spectre des fluctuations (associés à la relaxation d'ondes, couplées, de concentration colloïdale et de déplacement des couches smectiques) ont une certaine importance expérimentale. Dans la limite d'un couplage faible, l'un des deux modes est similaire au mode barocline des phases lamellaires à deux constituants ; le second s'identifie au mouvement brownien de diffusion d'un colloïde dans un substrat anisotrope. Les constantes élastiques du cristal liquide smectique de même que le coefficient de diffusion du colloïde peuvent en principe être déduits de la mesure des relations anisotropes de dispersion de ces deux modes ; cela est illustré par des expériences de diffusion quasi-élastique de la lumière sur des ferrosmectiques.

Materials with engineered mesoporosity for programmed mass transport

NASA Astrophysics Data System (ADS)

Gough, Dara V.

Transport in nanostructured materials is of great interest for scientists in various fields, including molecular sequestration, catalysis, artificial photosynthesis and energy storage. This thesis will present work on the transport of molecular and ionic species in mesoporous materials (materials with pore sizes between 2 and 50 nm). Initially, discussion will focus on the synthesis of mesoporous ZnS nanorattles and the size selected mass transport of small molecules through the mesopores. Discussion will then shift of exploration of cation exchange and electroless plating of metals to alter the mesoporous hollow sphere (MHS) materials and properties. The focus of discussion will then shift to the transport of ions into and out of a hierarchically structured gold electrode. Finally, a model gamma-bactiophage was developed to study the electromigration of charged molecules into and out of a confined geometry. A catalytically active biomolecular species was encapsulated within the central cavity of ZnS MHS. Both the activity of the encapsulated enzyme and the size-selective transport through the wall of the MHS were verified through the use of a common fluorogen, hydrogen peroxide, and sodium azide. Additionally, the protection of the enzyme was shown through size-selected blocking of a protease. The mesoporous hollow sphere system introduces size-selectivity to catalyzed chemical reactions; future work may include variations in pore sizes, and pore wall chemical functionalization. The pore size in ZnS mesoporous hollow spheres is controlled between 2.5 and 4.1 nm through swelling of the lyotropic liquid crystal template. The incorporation of a swelling agent is shown to linearly vary the hexagonal lyotropic liquid crystalline phase, which templates the mesopores, while allowing the high fidelity synthesis of mesoporous hollow spheres. Fluorescnently labeled ssDNA was utilized as a probe to explore the change in mesopore permeability afforded by the swollen template relative to the unswollen template. Electroless plating and cation exchange were explored as methods to vary the shell material of MHS. Mesoporous Ni MHS were obtained by the reduction of Ni2+ with dimethylamine borane onto a CML latex core. However, the resultant MHS were damaged due to core swelling during etch. To successfully obtain undeformed MHS, a silica core must be utilized; one possible route to explore, in order to reach this goal, is the surface chemistry/ligand effects on Ni2+. Cation exchange was performed in order to obtain CuS MHS; however, it proved an unsuccessful route to PbS, S and HgS. CdS-ZnS, Bi2S3 and Ag2S MHS were obtained only with significant defects. A novel hierarchically structured material, porous opal, was prepared using a colloidal crystal template and the dealloying of silver from gold and possed porosity on length scales range from 10s of nanometers (due to the colloidal crystal template) down to ca. 10 nm (due to dealloying). The transport properties of the material were studied using cyclic voltammetry and electrochemical impedance spectroscopy. The porous opal was found to posses enhanced charge transport properties relative to a unimodal porous gold film and a higher surface area than a gold opal. An equivalent circuit model was presented to explain the enhanced charge transport properties. A biomimetic system for studying the translocation of polymers through a channel and into a spherical cavity was developed based on inspiration from the gamma-bacteriophage. The nanocavity system was synthesized using two template length scales: 250 nm and 1.2 mum. Fabrication challenges that arose when using 1.2 mum colloidal templates were addressed, and the system was optimized for confinement studies of plasmid dsDNA.

Naturally engineered glycolipid biosurfactants leading to distinctive self-assembled structures.

PubMed

Imura, Tomohiro; Ohta, Noboru; Inoue, Katsuaki; Yagi, Naoto; Negishi, Hideyuki; Yanagishita, Hiroshi; Kitamoto, Dai

2006-03-08

Self-assembling properties of "natural" glycolipid biosurfactants, mannosyl-erythritol lipids A and B (MEL-A, MEL-B), which are abundantly produced from yeast strains, were investigated by using the fluorescence-probe method, dynamic light-scattering (DLS) analysis, freeze-fracture transmission electron microscopy (FF-TEM), and synchrotron small/wide-angle X-ray scattering (SAXS/WAXS) analysis, among other methods. Both MEL-A and MEL-B exhibit excellent self-assembly properties at extremely low concentrations; they self-assemble into large unilamellar vesicles (LUV) just above their critical-aggregation concentration (CAC). The CAC(I) value was found to be 4.0x10(-6) M for MEL-A and 6.0x10(-6) M for MEL-B. Moreover, the self-assembled structure of MEL-A above a CAC(II) value of 2.0x10(-5) M was found to drastically change into sponge structures (L3) composed of a network of randomly connected bilayers that are usually obtained from a complicated multicomponent "synthetic" surfactant system. Interestingly, the average water-channel diameter of the sponge structure was 100 nm. This is relatively large compared with those obtained from "synthetic" surfactant systems. In addition, MEL-B, which has a hydroxyl group at the C-4' position on mannose instead of an acetyl group, gives only one CAC; the self-assembled structure of MEL-B seems to gradually move from LUV to multilamellar vesicles (MLV) with lattice constants of 4.4 nm, depending on the concentration. Furthermore, the lyotropic-liquid-crystal-phase observation at high concentrations demonstrates the formation of an inverted hexagonal phase (H2) for MEL-A, together with a lamella phase (L(alpha)) for MEL-B, indicating a difference between MEL-A and MEL-B molecules in the spontaneous curvature of the assemblies. These results clearly show that the difference in spontaneous curvature caused by the single acetyl group on the head group probably decides the direction of self-assembly of glycolipid biosurfactants. The unique and complex molecular structures with several chiral centers that are molecularly engineered by microorganisms must have led to the sophisticated self-assembling properties of the glycolipid biosurfactants.

Microstructure and phase behavior in colloids and liquid crystals

NASA Astrophysics Data System (ADS)

Lohr, Matthew Alan

This thesis describes our investigation of microstructure and phase behavior in colloids and liquid crystals. The first set of experiments explores the phase behavior of helical packings of thermoresponsive microspheres inside glass capillaries as a function of volume fraction. Stable helical packings are observed with long-range orientational order. Some of these packings evolve abruptly to disordered states as the volume fraction is reduced. We quantify these transitions using correlation functions and susceptibilities of an orientational order parameter. The emergence of coexisting metastable packings, as well as coexisting ordered and disordered states, is also observed. These findings support the notion of phase-transition-like behavior in quasi-one-dimensional systems. The second set of experiments investigates cross-over behavior from glasses with attractive interactions to sparse gel-like states. In particular, the vibrational modes of quasi-two-dimensional disordered colloidal packings of hard colloidal spheres with short-range attractions are measured as a function of packing fraction. A crossover from glassy to sparse gel-like states is indicated by an excess of low-frequency phonon modes. This change in vibrational mode distribution appears to arise from highly localized vibrations that tend to involve individual and/or small clusters of particles with few local bonds. These mode behaviors and corresponding structural insights may serve as a useful signature for glass-gel transitions in wider classes of attractive packings. A third set of experiments explores the director structures of aqueous lyotropic chromonic liquid crystal (LCLC) films created on square lattice cylindrical-micropost substrates. The structures are manipulated by modulating of the concentration-dependent elastic properties of LCLC s via drying. Nematic LCLC films exhibit preferred bistable alignment along the diagonals of the micropost lattice. Columnar LCLC films form two distinct director and defect configurations: a diagonally aligned director pattern with local squares of defects, and an off-diagonal configuration with zig-zag defects. The formation of these patterns appears to be tied to the relative free energy costs of splay and bend deformations in the precursor nematic films. The observed nematic and columnar configurations are understood numerically using a Landau-de Gennes free energy model. This work provides first examples of quasi-2D micropatterning of LC films in the columnar phase and the first micropatterning of lyotropic LC films in general, as well as demonstrating alignment and configuration switching of typically difficult-to-align LCLC films via bulk elastic properties.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petach, Trevor A.; Reich, Konstantin V.; Zhang, Xiao

Ionic liquid gating has a number of advantages over solid-state gating, especially for flexible or transparent devices and for applications requiring high carrier densities. But, the large number of charged ions near the channel inevitably results in Coulomb scattering, which limits the carrier mobility in otherwise clean systems. We develop a model for this Coulomb scattering. We then validate our model experimentally using ionic liquid gating of graphene across varying thicknesses of hexagonal boron nitride, demonstrating that disorder in the bulk ionic liquid often dominates the scattering.

Calorimetric and counterion binding studies of the interactions between micelles and ions. The observation of lyotropic series

DOE Office of Scientific and Technical Information (OSTI.GOV)

Larsen, J.W.; Magid, L.J.

1974-09-04

Heats of transfer of a variety of salts from water to solutions of hexadecyltrimethylammonium bromide (CTAB), dodecyltrimethylammonium bromide (DTAB), and sodium dodecyl sulfate (NaLS) were measured. Lyotropic series for both cations and anions were observed for all soaps, the series for the 2 cationic soaps being almost identical. The dependence of the observed heats of transfer for anions from H/sub 2/O to CTAB and DTAB solutions and for cations from H2O to NaLS solutions on the hydrated radii of the ions involved supports the contention that favorable binding of counterions depends on how closely they can approach the charged micellarmore » surfaces. It is clear that a lyotropic series similar to that existing for proteins exists for ion binding to micelles. The controlling factor in this binding seems to be the distance of closest approach of the ion to the micelle, although polarizable organic ions may be the exceptions. Chain length has little effect on binding. It is felt that the work discussed has established the usefulness of a calorimetric investigation and the use of ion-specific electrodes for characterizing surfactant systems containing more than one species of counterions. (37 refs.)« less

Design, characterization, and biological evaluation of curcumin-loaded surfactant-based systems for topical drug delivery.

PubMed

Fonseca-Santos, Bruno; Dos Santos, Aline Martins; Rodero, Camila Fernanda; Gremião, Maria Palmira Daflon; Chorilli, Marlus

From previous studies, it has been found that curcumin exhibits an anti-inflammatory activity and is being used for the treatment of skin disorders; however, it is hydrophobic and has weak penetrating ability, resulting in poor drug transport through the stratum corneum. The aim of this study was to develop liquid crystalline systems for topical administration of curcumin for the treatment of inflammation. These liquid crystalline systems were developed from oleic acid, polyoxypropylene (5) polyoxyethylene (20) cetyl alcohol, and water as the surfactant, oil phase, and aqueous phase, respectively. These systems were characterized, and polarized light microscopy showed anisotropy with lamellar mesophases (Formulation 1) and hexagonal mesophases (Formulations 2 and 3), which were confirmed by the peak ratio measured using small-angle X-ray scattering. In addition, rheological tests revealed that the formulations exhibited gel-like behavior (G'>G″), as evidenced by the increased G' values that indicate structured systems. Texture profile analysis showed that hexagonal mesophases have high values of hardness, adhesiveness, and compressibility, which indicate structured systems. In vitro studies on bioadhesion revealed that the hexagonal mesophases increased the bioadhesiveness of the systems to the skin of the pig ear. An in vivo inflammation experiment showed that the curcumin-loaded hexagonal mesophase exhibited an anti-inflammatory activity as compared to the positive control (dexamethasone). The results suggest that this system has a potential to be used as a bioadhesive vehicle for the topical administration of curcumin. Therefore, it is possible to conclude that these systems can be used for the optimization of drug delivery systems to the skin.

Living liquid crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, S.; Sokolov, A.; Lavrentovich, O. D.

2014-01-13

Collective motion of self-propelled organisms or synthetic par­ticles, often termed •active fluid,• has attracted enormous atten­tion in the broad scientific community because of its fundamentally nonequilibrium nature. Energy input and interactions among the moving units and the medium lead to complex dynamics. Here,we introduce a class of active matter-living liquid crystals (UCs}­ that combines living swimming bacteria with a lyotropic liquid crystal. The physical properties of LLCs can be controlled by the amount of oxygen available to bacteria, by concentration of ingre­dients, or by temperature. Our studies reveal a wealth of intriguing dynamic phenomena. caused by the coupling between themore » activity-triggered flow and long-range orientational order of the medium. Among these are (i) nonlinear trajectories of bacterial motion guided by nonuniform director, (ii) local melting of the liquid crystal caused by the bacteria-produced shear flows, (iii) activity-triggered transition from a nonflowing uniform state into a flowing one-dimensional periodic pattern and its evolution into a turbulent array of topological defects, and (iv) birefringence­ enabled visualization of microflow generated by the nanometers­ thick bacterial flagella. Unlike their isotropic counterpart, the LLCs show collective dynamic effects at very low volume fraction of bacteria, on the order of 0.2%. Our work suggests an unorthodox design concept to control and manipulate the dynamic behavior of soft active matter and opens the door for potential biosensing and biomedical applications.« less

Importance of hydrophobic traps for proton diffusion in lyotropic liquid crystals

DOE PAGES

McDaniel, Jesse G.; Yethiraj, Arun

2016-03-04

The diffusion of protons in self-assembled systems is potentially important for the design of efficient proton exchange membranes. In this work, we study proton dynamics in a low-water content, lamellar phase of an sodium-carboxylate gemini surfactant/water system using computer simulations. The hopping of protons via the Grotthuss mechanism is explicity allowed through the multi-state empirical valence bond (MS-EVB) method. We find that the hydronium ion is trapped on the hydrophobic side of the surfactant-water interface, and proton diffusion then proceeds by hopping between surface sites. The importance of hydrophobic traps is surprising, because one would expect the hydronium ions tomore » be trapped at the charged head-groups. Finally, the physics illustrated in this system should be relevant to the proton dynamics in other amphiphilic membrane systems, whenever there exists exposed hydrophobic surface regions.« less

Characterization and In Vitro Permeation Study of Cubic Liquid Crystal Containing Sinomenine Hydrochloride.

PubMed

Chu, Xiaoqin; Li, Qian; Gui, Shuangying; Li, Zhengguang; Cao, Jiaojiao; Jiang, Jianqin

2018-05-08

This study developed a new transdermal delivery system for the improved delivery of sinomenine hydrochloride (SH). The delivery system utilized the advantages of lyotropic liquid crystals (LLC) creating an adaptable system that offers a variety of options for the field of transdermal delivery. The formulation was prepared, characterized, and evaluated for its skin penetration in vitro. In the study, the appearance of samples was characterized by visual observation, and these LLC gels were colorless and transparent. Polarizing light microscopy (PLM) and small-angle X-ray diffraction (SAXS) were used to analyze the internal structures of gels, and the gels displayed a cubic double-diamond (P n 3 m ) internal structure with a dark field of vision. The Franze diffusion cell was used to evaluate its skin penetration. There were several factors which might influence the skin penetration of drugs, such as drug loading, water content, and the layer spacing of the LLC. In our case, drug concentration gradient played a more powerful role. The result of in vitro permeation studies demonstrated that the drug concentration was higher; the cumulative osmotic quantity of SH (Q) was greater. Therefore, the system was a promising formulation for successful percutaneous delivery of SH through the skin.

Lyotropic liquid crystal behaviour of azelate and succinate monoester surfactants based on fragrance alcohols.

PubMed

Marchal, Frédéric; Nardello-Rataj, Véronique; Chailloux, Nelly; Aubry, Jean-Marie; Tiddy, Gordon J T

2008-05-01

Azelaic acid was used as a starting material for the preparation of new monoester surfactants based on fragrance alcohols. Sodium monocitronellyl azelate (citroC(9)Na) and sodium monomenthyl azelate (menC(9)Na) were synthesized and their aqueous phase behaviour was studied. For comparison, monoesters derived from succinic anhydride, i.e. sodium monocitronellyl succinate (citroC(4)Na) and sodium monomenthyl succinate (menC(4)Na), were also prepared as well as sodium monodecyl succinate (C(10)C(4)Na) and sodium monodecyl azelate (C(10)C(9)Na) in order to study the effect of the position of the ester function inside the hydrophobic tail and of branching and unsaturation respectively. Liquid crystal structures were examined by optical polarising microscopy and schematic partial binary phase diagrams (surfactant+water, 0-100 wt%, 10-90 degrees C) of the surfactants were established. Succinate surfactants behave as longer alkyl chain surfactants than their azelate counterparts, meaning that these last ones probably adopt a more folded conformation, with the ester function more frequently present at the micelle surface. This conformation would result in a rougher micelle surface, making it slightly less easy for micelles to pack in liquid crystalline phases. It was also shown that the tendency to adopt a more folded conformation and to form smaller micelles is ranked in this order: monomenthyl>monocitronellyl>monodecyl.

Liquid Quasicrystals

NASA Astrophysics Data System (ADS)

Ungar, Goran

Following the discovery of quasicrystals by Shechtman and Cahn in 1984, for the following 20 years the new field of QCs was confined to metal alloys and atomic-scale structures. Then, with the discovery of a liquid crystal phase possessing dodecagonal QC symmetry], research interest has extended from metal alloys to those where the motifs were no longer single atoms but assemblies of many molecules. In dendron-based liquid quasicrystals (LQC) between 10-50 molecules form a supramolecular sphere with 103 - 104 atoms. In 2007 a 2-d quasiperiodic phase was found in three-arm star ABC polymers. In 2012 the first linear diblock copolymer was reported to form a sphere-based bulk QC phase, similar to that in dendrimer LQC but on a still larger scale. In the same year bulk QC domains were reported in ``hard'' nanoporous silica, produced however, again from a ``soft'' lyotropic template. The symmetry of all confirmed soft QCs so far is 12-fold. Another important development in soft QCs is the observation of complex QC approximants in a number of side-branched polyphilic LC honeycombs, described by multicolour tilings. In fact, recently we found a genuine dodecagonal QC in such systems, the first example of a 2D LQC. Furthermore, we succeeded in direct AFM imaging of the xy plane of a dendrimer LQC. The images confirm the ``half-step'' inflation rule, proposed earlier but not confirmed until now. Funding is acknowledged from Leverhulme Trust.

Conductivity of an inverse lyotropic lamellar phase under shear flow

NASA Astrophysics Data System (ADS)

Panizza, P.; Soubiran, L.; Coulon, C.; Roux, D.

2001-08-01

We report conductivity measurements on solutions of closed compact monodisperse multilamellar vesicles (the so-called ``onion texture'') formed by shearing an inverse lyotropic lamellar Lα phase. The conductivity measured in different directions as a function of the applied shear rate reveals a small anisotropy of the onion structure due to the existence of free oriented membranes. The results are analyzed in terms of a simple model that allows one to deduce the conductivity tensor of the Lα phase itself and the proportion of free oriented membranes. The variation of these two parameters is measured along a dilution line and discussed. The high value of the conductivity perpendicular to the layers with respect to that of solvent suggests the existence of a mechanism of ionic transport through the insulating solvent.

Liquid Crystalline Assembly of Coil-Rod-Coil Molecules with Lateral Methyl Groups into 3-D Hexagonal and Tetragonal Assemblies

PubMed Central

Wang, Zhuoshi; Lan, Yu; Zhong, Keli; Liang, Yongri; Chen, Tie; Jin, Long Yi

2014-01-01

In this paper, we report the synthesis and self-assembly behavior of coil-rod-coil molecules, consisting of three biphenyls linked through a vinylene unit as a conjugated rod segment and poly(ethylene oxide) (PEO) with a degree of polymerization (DP) of 7, 12 and 17, incorporating lateral methyl groups between the rod and coil segments as the coil segment. Self-organized investigation of these molecules by means of differential scanning calorimetry (DSC), thermal polarized optical microscopy (POM) and X-ray diffraction (XRD) reveals that the lateral methyl groups attached to the surface of rod and coil segments, dramatically influence the self-assembling behavior in the liquid-crystalline mesophase. Molecule 1 with a relatively short PEO coil length (DP = 7) self-assembles into rectangular and oblique 2-dimensional columnar assemblies, whereas molecules 2 and 3 with DP of 12 and 17 respectively, spontaneously self-organize into unusual 3-dimensional hexagonal close-packed or body-centered tetragonal assemblies. PMID:24699045

Liquid-like ionic conduction in solid lithium and sodium monocarba- closo-decaborates near or at room temperature

DOE PAGES

Tang, Wan Si; Matsuo, Motoaki; Wu, Hui; ...

2016-02-05

Both LiCB 9H 10 and NaCB 9H 10 exhibit liquid-like cationic conductivities (≥0.03 S cm –1) in their disordered hexagonal phases near or at room temperature. Furthermore, these unprecedented conductivities and favorable stabilities enabled by the large pseudoaromatic polyhedral anions render these materials in their pristine or further modified forms as promising solid electrolytes in next-generation, power devices.

Nanolayered Features of Collagen-like Peptides

NASA Technical Reports Server (NTRS)

Valluzzi, Regina; Bini, Elisabetta; Haas, Terry; Cebe, Peggy; Kaplan, David L.

2003-01-01

We have been investigating collagen-like model oligopeptides as molecular bases for complex ordered biomimetic materials. The collagen-like molecules incorporate aspects of native collagen sequence and secondary structure. Designed modifications to native primary and secondary structure have been incorporated to control the nanostructure and microstructure of the collagen-like materials produced. We find that the collagen-like molecules form a number of lyotropic rod liquid crystalline phases, which because of their strong temperature dependence in the liquid state can also be viewed as solvent intercalated thermotropic liquid crystals. The liquid crystalline phases formed by the molecules can be captured in the solid state by drying off solvent, resulting in solid nanopatterned (chemically and physically) thermally stable (to greater than 100 C) materials. Designed sequences which stabilize smectic phases have allowed a variety of nanoscale multilayered biopolymeric materials to be developed. Preliminary investigations suggest that chemical patterns running perpendicular to the smectic layer plane can be functionalized and used to localize a variety of organic, inorganic, and organometallic moieties in very simple multilayered nanocomposites. The phase behavior of collagen-like oligopeptide materials is described, emphasizing the correlation between mesophase, molecular orientation, and chemical patterning at the microscale and nanoscale. In many cases, the textures observed for smectic and hexatic phase collagens are remarkably similar to the complex (and not fully understood) helicoids observed in biological collagen-based tissues. Comparisons between biological morphologies and collagen model liquid crystalline (and solidified materials) textures may help us understand the molecular features which impart order and function to the extracellular matrix and to collagen-based mineralized tissues. Initial studies have utilized synthetic collagen-like peptides while future work will also focus on similar sequences generated via genetic engineering methods.

Long-wavelength Instability in Surface-tension-driven Bénard Convection

NASA Astrophysics Data System (ADS)

van Hook, Stephen J.

1997-03-01

Laboratory experiments and numerical simulations reveal that a liquid layer heated from below and possessing a free upper surface can undergo a long-wavelength deformational instability that causes rupture of the interface.(S. J. VanHook, M. F. Schatz, W. D. McCormick, J. B. Swift, and H. L. Swinney, Phys. Rev. Lett.) 75, 4397 (1995). Depending on the depth and thermal conductivity of the liquid and the overlying gas layer, the interface can rupture downwards and form a dry spot or rupture upwards and form a high spot. This long-wavelength instability competes with the formation of Bénard hexagons for thin or viscous liquid layers, or for liquid layers in microgravity.

Structural modeling of carbonaceous mesophase amphotropic mixtures under uniaxial extensional flow.

PubMed

Golmohammadi, Mojdeh; Rey, Alejandro D

2010-07-21

The extended Maier-Saupe model for binary mixtures of model carbonaceous mesophases (uniaxial discotic nematogens) under externally imposed flow, formulated in previous studies [M. Golmohammadi and A. D. Rey, Liquid Crystals 36, 75 (2009); M. Golmohammadi and A. D. Rey, Entropy 10, 183 (2008)], is used to characterize the effect of uniaxial extensional flow and concentration on phase behavior and structure of these mesogenic blends. The generic thermorheological phase diagram of the single-phase binary mixture, given in terms of temperature (T) and Deborah (De) number, shows the existence of four T-De transition lines that define regions that correspond to the following quadrupolar tensor order parameter structures: (i) oblate (perpendicular, parallel), (ii) prolate (perpendicular, parallel), (iii) scalene O(perpendicular, parallel), and (iv) scalene P(perpendicular, parallel), where the symbols (perpendicular, parallel) indicate alignment of the tensor order ellipsoid with respect to the extension axis. It is found that with increasing T the dominant component of the mixture exhibits weak deviations from the well-known pure species response to uniaxial extensional flow (uniaxial perpendicular nematic-->biaxial nematic-->uniaxial parallel paranematic). In contrast, the slaved component shows a strong deviation from the pure species response. This deviation is dictated by the asymmetric viscoelastic coupling effects emanating from the dominant component. Changes in conformation (oblate <==> prolate) and orientation (perpendicular <==> parallel) are effected through changes in pairs of eigenvalues of the quadrupolar tensor order parameter. The complexity of the structural sensitivity to temperature and extensional flow is a reflection of the dual lyotropic/thermotropic nature (amphotropic nature) of the mixture and their cooperation/competition. The analysis demonstrates that the simple structures (biaxial nematic and uniaxial paranematic) observed in pure discotic mesogens under uniaxial extensional flow are significantly enriched by the interaction of the lyotropic/thermotropic competition with the binary molecular architectures and with the quadrupolar nature of the flow.

Effect of the concentration of magnetic grains on the linear-optical-absorption coefficient of ferrofluid-doped lyotropic mesophases: deviation from the Beer-Lambert law.

PubMed

Cuppo, F L S; Gómez, S L; Figueiredo Neto, A M

2004-04-01

In this paper is reported a systematic experimental study of the linear-optical-absorption coefficient of ferrofluid-doped isotropic lyotropic mixtures as a function of the magnetic-grains concentration. The linear optical absorption of ferrolyomesophases increases in a nonlinear manner with the concentration of magnetic grains, deviating from the usual Beer-Lambert law. This behavior is associated to the presence of correlated micelles in the mixture which favors the formation of small-scale aggregates of magnetic grains (dimers), which have a higher absorption coefficient with respect to that of isolated grains. We propose that the indirect heating of the micelles via the ferrofluid grains (hyperthermia) could account for this nonlinear increase of the linear-optical-absorption coefficient as a function of the grains concentration.

Release of salicylic acid, diclofenac acid and diclofenac acid salts from isotropic and anisotropic nonionic surfactant systems across rat skin.

PubMed

Gabboun, N H; Najib, N M; Ibrahim, H G; Assaf, S

2001-01-05

Release of salicylic acid, diclofenac acid, diclofenac diethylamine and diclofenac sodium, from lyotropic structured systems, namely; neat and middle liquid crystalline phases, across mid-dorsal hairless rat skin into aqueous buffer were studied. Release results were compared with those from the isotropic systems. The donor systems composed of the surfactant polyoxyethylene (20) isohexadecyl ether, HCl buffer of pH 1 or distilled water and the specific drug. High performance liquid chromatography (HPLC) methods were used to monitor the transfer of the drugs across the skin barrier. Results indicated that the rate-determining step in the transport process was the release of the drug from the specified donor system. Further, apparent zero order release was demonstrated with all systems. Except for diclofenac sodium, drug fluxes decreased as the donor medium changed from isotropic to anisotropic. The decrease in fluxes was probably due to the added constrains on the movement of drug molecules. By changing the anisotropic donor medium from neat to middle phase, drug flux decreased in case of salicylic acid and diclofenac sodium. In the mean time, flux increased in case of the diethylamine salt and appeared nearly similar in case of diclofenac acid. Rates of drug transfer across the skin from the anisotropic donors seemed to be largely controlled by the entropy contribution to the transport process. The type and extent of drug-liquid crystal interactions probably influenced the latter.

Dilute and Semidilute Solutions of a Nonionic, Rigid, Water-soluble Polymer

NASA Astrophysics Data System (ADS)

Russo, Paul; Huberty, Wayne; Zhang, Donghui; Water-Soluble Rodlike Polymer Team Collaboration

2014-03-01

The solution physics of random polymer chains was established largely on the behavior of commercial polymers such as polystyrene for organic solvents or nonionic poly(ethyleneoxide) for aqueous solvents. Not only are these materials widely available for industrial use, they can be synthesized to be essentially monodisperse. When it comes to stiff polymers, good choices are few and less prone to be used in industrial applications. Much was learned from polypeptides such as poly(benzylglutamate) or poly(stearylglutamate) in polar organic solvents and nonpolar organic solvents, respectively, but aqueous systems generally require charge. Poly(Nɛ-2-[2-(2-Methoxyethoxy) ethoxy]acetyl-L-Lysine) a.k.a. PEGL was pioneered by Deming and coworkers. In principle, PEGL provides a convenient platform from which to study stiff polymer behavior--phase relations, dynamics, liquid crystal formation and gelation--all with good molecular weight control and uniformity and without electrical charge. Still, a large gap in knowledge exists between PEGL and traditional rodlike polymer systems. To narrow this gap, dynamic and static scattering, circular dichroism, and viscosity measurements have been made in dilute and semidilute solutions as necessary preliminaries for lyotropic liquid crystalline and gel phases. Supported by NSF DMR 1306262. Department of Chemistry and Macromolecular Studies Group. Current address: Georgia Institute of Technology, School of Materials Science and Engineering.

Lyotropic Liquid Crystalline Nanoparticles of Amphotericin B: Implication of Phytantriol and Glyceryl Monooleate on Bioavailability Enhancement.

PubMed

Jain, Sanyog; Yadav, Pooja; Swami, Rajan; Swarnakar, Nitin Kumar; Kushwah, Varun; Katiyar, Sameer S

2018-05-01

Implication of different dietary specific lipids such as phytantriol (PT) and glyceryl monooleate (GMO) on enhancing the oral bioavailability of amphotericin B (AmB) was examined. Liquid crystalline nanoparticles (LCNPs) were prepared using hydrotrope method, followed by in vitro characterization, Caco-2 cell monolayer uptake, and in vivo pharmacokinetic and toxicity evaluation. Optimized AmB-LCNPs displayed small particle size (< 210 nm) with a narrow distribution (~ 0.2), sustained drug release and high gastrointestinal stability, and reduced hemolytic toxicity. PLCNPs presented slower release, i.e., ~ 80% as compared to ~ 90% release in case of GLCNPs after 120 h. Significantly higher uptake in Caco-2 monolayer substantiated the role of LCNPs in increasing the intestinal permeability followed by increased drug titer in plasma. Pharmacokinetic studies demonstrated potential of PT in enhancing the bioavailability (approximately sixfold) w.r.t. of its native counterpart with reduced nephrotoxicity as presented by reduced nephrotoxicity biomarkers and histology studies. These studies established usefulness of PLCNPs over GLCNPs and plain drug. It can be concluded that acid-resistant lipid, PT, can be utilized efficiently as an alternate lipid for the preparation of LCNPs to enhance bioavailability and to reduce nephrotoxicity of the drug as compared to other frequently used lipid, i.e., GMO.

Vapor-Deposited Glasses with Long-Range Columnar Liquid Crystalline Order

DOE PAGES

Gujral, Ankit; Gomez, Jaritza; Ruan, Shigang; ...

2017-10-04

Anisotropic molecular packing, particularly in highly ordered liquid crystalline arrangements, has the potential for optimizing performance in organic electronic and optoelectronic applications. Here we show that physical vapor deposition can be used to prepare highly organized glassy solids of discotic liquid crystalline systems. Using grazing incidence X-ray scattering, atomic force microscopy, and UV–vis spectroscopy, we compare three systems: a rectangular columnar liquid crystal, a hexagonal columnar liquid crystal, and a nonmesogen. The packing motifs accessible by vapor deposition are highly organized for the liquid crystalline systems with columns propagating either in-plane or out-of-plane depending upon the substrate temperature during deposition.more » As a result, the structures formed at a given substrate temperature can be understood as resulting from partial equilibration toward the structure of the equilibrium liquid crystal surface during the deposition process.« less

Vapor-Deposited Glasses with Long-Range Columnar Liquid Crystalline Order

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gujral, Ankit; Gomez, Jaritza; Ruan, Shigang

Anisotropic molecular packing, particularly in highly ordered liquid crystalline arrangements, has the potential for optimizing performance in organic electronic and optoelectronic applications. Here we show that physical vapor deposition can be used to prepare highly organized glassy solids of discotic liquid crystalline systems. Using grazing incidence X-ray scattering, atomic force microscopy, and UV–vis spectroscopy, we compare three systems: a rectangular columnar liquid crystal, a hexagonal columnar liquid crystal, and a nonmesogen. The packing motifs accessible by vapor deposition are highly organized for the liquid crystalline systems with columns propagating either in-plane or out-of-plane depending upon the substrate temperature during deposition.more » As a result, the structures formed at a given substrate temperature can be understood as resulting from partial equilibration toward the structure of the equilibrium liquid crystal surface during the deposition process.« less

Chiral symmetry breaking by spatial confinement in tactoidal droplets of lyotropic chromonic liquid crystals

PubMed Central

Tortora, Luana; Lavrentovich, Oleg D.

2011-01-01

In many colloidal systems, an orientationally ordered nematic (N) phase emerges from the isotropic (I) melt in the form of spindle-like birefringent tactoids. In cases studied so far, the tactoids always reveal a mirror-symmetric nonchiral structure, sometimes even when the building units are chiral. We report on chiral symmetry breaking in the nematic tactoids formed in molecularly nonchiral polymer-crowded aqueous solutions of low-molecular weight disodium cromoglycate. The parity is broken by twisted packing of self-assembled molecular aggregates within the tactoids as manifested by the observed optical activity. Fluorescent confocal microscopy reveals that the chiral N tactoids are located at the boundaries of cells. We explain the chirality induction as a replacement of energetically costly splay packing of the aggregates within the curved bipolar tactoidal shape with twisted packing. The effect represents a simple pathway of macroscopic chirality induction in an organic system with no molecular chirality, as the only requirements are orientational order and curved shape of confinement. PMID:21402929

Quantifying the transport properties of lipid mesophases by theoretical modelling of diffusion experiments

NASA Astrophysics Data System (ADS)

Antognini, Luca M.; Assenza, Salvatore; Speziale, Chiara; Mezzenga, Raffaele

2016-08-01

Lyotropic Liquid Crystals (LLCs) are a class of lipid-based membranes with a strong potential for drug-delivery employment. The characterization and control of their transport properties is a central issue in this regard, and has recently prompted a notable volume of research on the topic. A promising experimental approach is provided by the so-called diffusion setup, where the drug molecules diffuse from a feeding chamber filled with water to a receiving one passing through a LLC. In the present work we provide a theoretical framework for the proper description of this setup, and validate it by means of targeted experiments. Due to the inhomogeneity of the system, a rich palette of different diffusion dynamics emerges from the interplay of the different time- and lengthscales thereby present. Our work paves the way to the employment of diffusion experiments to quantitatively characterize the transport properties of LLCs, and provides the basic tools for device diffusion setups with controlled kinetic properties.

Roles of Chemical Functionality and Pore Curvature in the Design of Nanoporous Proton Conductors

DOE PAGES

Jackson, Grayson L.; Perroni, Dominic V.; Mahanthappa, Mahesh K.

2017-10-03

Nanoporous proton-transporting media are critical components in fuel cells and other electrochemical devices, yet general molecular design criteria for new materials with enhanced performance remain obscure. Aqueous lyotropic liquid crystals (LLCs) comprise a platform for detailed studies of the molecular-level features governing proton transport in monodisperse, water-filled nanopores lined with well-defined chemical functionalities. Here, we report new alkylsulfonic acid LLCs that exhibit H+ conductivities as high as σ = 380 mS/cm at 80°C, which rival those of more acidic, perfluorinated polymers, thus demonstrating that the acidity of the pore functionality is not the sole determinant of proton transport. Direct experimentalmore » comparisons of LLCs with convex and concave nanopores of similar dimensions indicate that H+ conductivities therein sensitively depend on the hydration state of the acid functionalities and the pore curvature. These experiments suggest that judicious manipulation of pore curvature provides a new means for optimizing the activities of proton-exchange membranes and nanoporous solid acid catalysts.« less

Rheological behavior, zeta potential, and accelerated stability tests of Buriti oil (Mauritia flexuosa) emulsions containing lyotropic liquid crystals.

PubMed

Zanatta, Cinthia Fernanda; de Faria Sato, Anne Miwa Callejón; de Camargo, Flavio Bueno; Campos, Patrícia Maria Berardo Gonçalves Maia; Rocha-Filho, Pedro Alves

2010-01-01

It is well known that the Amazon region presents a huge biodiversity; therefore, countless natural resources are being employed in the production of phytocosmetics and phytomedicines. The purpose of this work was to obtain emulsions produced with Buriti oil and non-ionic surfactants. Two surfactant systems were employed (Steareth-2 associated to Ceteareth-5 and to Ceteareth-20) to produce the emulsions using phase diagram method. Emulsions were obtained by echo-planar imaging method at 75°C. Rheological behavior and zeta potential were evaluated, and accelerated stability tests were performed. All emulsions analyzed presented pseudoplastic behavior. Zeta potential values were obtained between -14.2 and -53.3 mV. The formulations did not show changes in either physical stability, pH, or rheological behavior after accelerated stability tests. Significant differences were observed only after temperature cycling test. Based on these results, the emulsions obtained could be considered as promising delivery systems.

Improving the Durability of Methanol Oxidation Reaction Electro-Catalysts Through the Modification of Carbon Architectures

DTIC Science & Technology

2014-01-01

zeolite template was used in conjunction with liquid cyanamide to form a carbon nitride structure with a better 2D mesoporous hexagonal framework, resulting...the core. Both hybrid inorganic–organic polymer networks and 139 zeolitic inorganic–organic polymer electrolyte materials were used to impregnate an

Friction of water on graphene and hexagonal boron nitride from ab initio methods: very different slippage despite very similar interface structures.

PubMed

Tocci, Gabriele; Joly, Laurent; Michaelides, Angelos

2014-12-10

Friction is one of the main sources of dissipation at liquid water/solid interfaces. Despite recent progress, a detailed understanding of water/solid friction in connection with the structure and energetics of the solid surface is lacking. Here, we show for the first time that ab initio molecular dynamics can be used to unravel the connection between the structure of nanoscale water and friction for liquid water in contact with graphene and with hexagonal boron nitride. We find that although the interface presents a very similar structure between the two sheets, the friction coefficient on boron nitride is ≈ 3 times larger than that on graphene. This comes about because of the greater corrugation of the energy landscape on boron nitride arising from specific electronic structure effects. We discuss how a subtle dependence of the friction on the atomistic details of a surface, which is not related to its wetting properties, may have a significant impact on the transport of water at the nanoscale, with implications for the development of membranes for desalination and for osmotic power harvesting.

A curcumin-loaded liquid crystal precursor mucoadhesive system for the treatment of vaginal candidiasis.

PubMed

Salmazi, Rafael; Calixto, Giovana; Bernegossi, Jéssica; Ramos, Matheus Aparecido dos Santos; Bauab, Taís Maria; Chorilli, Marlus

2015-01-01

Women often develop vaginal infections that are caused primarily by organisms of the genus Candida. The current treatments of vaginal candidiasis usually involve azole-based antifungals, though fungal resistance to these compounds has become prevalent. Therefore, much attention has been given to molecules with antifungal properties from natural sources, such as curcumin (CUR). However, CUR has poor solubility in aqueous solvents and poor oral bioavailability. This study attempted to overcome this problem by developing, characterizing, and evaluating the in vitro antifungal action of a CUR-loaded liquid crystal precursor mucoadhesive system (LCPM) for vaginal administration. A low-viscosity LCPM (F) consisting of 40% wt/wt polyoxpropylene-(5)-polyoxyethylene-(20)-cetyl alcohol, 50% wt/wt oleic acid, and 10% wt/wt chitosan dispersion at 0.5% with the addition of 16% poloxamer 407 was developed to take advantage of the lyotropic phase behavior of this formulation. Notably, F could transform into liquid crystal systems when diluted with artificial vaginal mucus at ratios of 1:3 and 1:1 (wt/wt), resulting in the formation of F30 and F100, respectively. Polarized light microscopy and rheological studies revealed that F behaved like an isotropic formulation, whereas F30 and F100 behaved like an anisotropic liquid crystalline system (LCS). Moreover, F30 and F100 presented higher mucoadhesion to porcine vaginal mucosa than F. The analysis of the in vitro activity against Candida albicans revealed that CUR-loaded F was more potent against standard and clinical strains compared with a CUR solution. Therefore, the vaginal administration of CUR-loaded LCPMs represents a promising platform for the treatment of vaginal candidiasis.

A curcumin-loaded liquid crystal precursor mucoadhesive system for the treatment of vaginal candidiasis

PubMed Central

Salmazi, Rafael; Calixto, Giovana; Bernegossi, Jéssica; Ramos, Matheus Aparecido dos Santos; Bauab, Taís Maria; Chorilli, Marlus

2015-01-01

Women often develop vaginal infections that are caused primarily by organisms of the genus Candida. The current treatments of vaginal candidiasis usually involve azole-based antifungals, though fungal resistance to these compounds has become prevalent. Therefore, much attention has been given to molecules with antifungal properties from natural sources, such as curcumin (CUR). However, CUR has poor solubility in aqueous solvents and poor oral bioavailability. This study attempted to overcome this problem by developing, characterizing, and evaluating the in vitro antifungal action of a CUR-loaded liquid crystal precursor mucoadhesive system (LCPM) for vaginal administration. A low-viscosity LCPM (F) consisting of 40% wt/wt polyoxpropylene-(5)-polyoxyethylene-(20)-cetyl alcohol, 50% wt/wt oleic acid, and 10% wt/wt chitosan dispersion at 0.5% with the addition of 16% poloxamer 407 was developed to take advantage of the lyotropic phase behavior of this formulation. Notably, F could transform into liquid crystal systems when diluted with artificial vaginal mucus at ratios of 1:3 and 1:1 (wt/wt), resulting in the formation of F30 and F100, respectively. Polarized light microscopy and rheological studies revealed that F behaved like an isotropic formulation, whereas F30 and F100 behaved like an anisotropic liquid crystalline system (LCS). Moreover, F30 and F100 presented higher mucoadhesion to porcine vaginal mucosa than F. The analysis of the in vitro activity against Candida albicans revealed that CUR-loaded F was more potent against standard and clinical strains compared with a CUR solution. Therefore, the vaginal administration of CUR-loaded LCPMs represents a promising platform for the treatment of vaginal candidiasis. PMID:26257519

CuS nanoplates from ionic liquid precursors—Application in organic photovoltaic cells

NASA Astrophysics Data System (ADS)

Kim, Yohan; Heyne, Benjamin; Abouserie, Ahed; Pries, Christopher; Ippen, Christian; Günter, Christina; Taubert, Andreas; Wedel, Armin

2018-05-01

Hexagonal p-type semiconductor CuS nanoplates were synthesized via a hot injection method from bis(trimethylsilyl)sulfide and the ionic liquid precursor bis(N-dodecylpyridinium) tetrachloridocuprate(ii). The particles have a broad size distribution with diameters between 30 and 680 nm and well-developed crystal habits. The nanoplates were successfully incorporated into organic photovoltaic (OPV) cells as hole conduction materials. The power conversion efficiency of OPV cells fabricated with the nanoplates is 16% higher than that of a control device fabricated without the nanoplates.

Self-assembly and continuous growth of hexagonal graphene flakes on liquid Cu

NASA Astrophysics Data System (ADS)

Cho, Seong-Yong; Kim, Min-Sik; Kim, Minsu; Kim, Ki-Ju; Kim, Hyun-Mi; Lee, Do-Joong; Lee, Sang-Hoon; Kim, Ki-Bum

2015-07-01

Graphene growth on liquid Cu has received great interest, owing to the self-assembly behavior of hexagonal graphene flakes with aligned orientation and to the possibility of forming a single grain of graphene through a commensurate growth of these graphene flakes. Here, we propose and demonstrate a two-step growth process which allows the formation of self-assembled, completely continuous graphene on liquid Cu. After the formation of full coverage on the liquid Cu, grain boundaries were revealed via selective hydrogen etching and the original grain boundaries were clearly resolved. This result indicates that, while the flakes self-assembled with the same orientation, there still remain structural defects, gaps and voids that were not resolved by optical microscopy or scanning electron microscopy. To overcome this limitation, the two-step growth process was employed, consisting of a sequential process of a normal single-layer graphene growth and self-assembly process with a low carbon flux, followed by the final stage of graphene growth at a high degree of supersaturation with a high carbon flux. Continuity of the flakes was verified via hydrogen etching and a NaCl-assisted oxidation process, as well as by measuring the electrical properties of the graphene grown by the two-step process. Two-step growth can provide a continuous graphene layer, but commensurate stitching should be further studied.Graphene growth on liquid Cu has received great interest, owing to the self-assembly behavior of hexagonal graphene flakes with aligned orientation and to the possibility of forming a single grain of graphene through a commensurate growth of these graphene flakes. Here, we propose and demonstrate a two-step growth process which allows the formation of self-assembled, completely continuous graphene on liquid Cu. After the formation of full coverage on the liquid Cu, grain boundaries were revealed via selective hydrogen etching and the original grain boundaries were clearly resolved. This result indicates that, while the flakes self-assembled with the same orientation, there still remain structural defects, gaps and voids that were not resolved by optical microscopy or scanning electron microscopy. To overcome this limitation, the two-step growth process was employed, consisting of a sequential process of a normal single-layer graphene growth and self-assembly process with a low carbon flux, followed by the final stage of graphene growth at a high degree of supersaturation with a high carbon flux. Continuity of the flakes was verified via hydrogen etching and a NaCl-assisted oxidation process, as well as by measuring the electrical properties of the graphene grown by the two-step process. Two-step growth can provide a continuous graphene layer, but commensurate stitching should be further studied. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr03352g

Cerium-doped -Ni(OH)2 hexagon nanosheets: an effective photocatalyst for degradation of the emerging water pollutant naproxen.

PubMed

Regmi, Chhabilal; Maya-Flores, Etel; Lee, Soo Wohn; Rodríguez-González, Vicente

2018-06-21

Nickel hydroxide β-Ni(OH)2 hexagonal nanosheets were synthetized via a hydrothermal exfoliation process. The practical microwave assisted hydrothermal method facilitated obtain layered nickel 3D nanoplates with cerium functionalization in 5h. The as-produced nanostructures were characterized by XRD, XPS, FESEM, FT-IR, PL, UV-vis, and BET techniques. The hydroxilated structures are nano-thick hexagonal plates having sides with 28 nm in length and 5 nm of average thickness. UV and PL irradiation was used to study the photoactive properties in the degradation of a pharmaceutical emerging pollutant, naproxen. UV-vis spectroscopy and high-performance liquid chromatography (HPLC) monitoring indicated that the Ni(OH)2-Ce nanostructures are an effective photocatalyst for naproxen degradation including 40 % of mineralization of this highly recalcitrant drug. The photocatalyst showed stability for two consecutive cycles, preserving its photoactive and structural characteristics. Ce3+ doped nanoplates and surface functionalized Ce4+ act as charge separators and scavenging agents for the enhanced photodegradation of naproxen. © 2018 IOP Publishing Ltd.

Light scattering and random lasing in aqueous suspensions of hexagonal boron nitride nanoflakes

NASA Astrophysics Data System (ADS)

O'Brien, S. A.; Harvey, A.; Griffin, A.; Donnelly, T.; Mulcahy, D.; Coleman, J. N.; Donegan, J. F.; McCloskey, D.

2017-11-01

Liquid phase exfoliation allows large scale production of 2D materials in solution. The particles are highly anisotropic and strongly scatter light. While spherical particles can be accurately and precisely described by a single parameter—the radius, 2D nanoflakes, however, cannot be so easily described. We investigate light scattering in aqueous solutions of 2D hexagonal boron nitride nanoflakes in the single and multiple scattering regimes. In the single scattering regime, the anisotropic 2D materials show a much stronger depolarization of light when compared to spherical particles of similar size. In the multiple scattering regime, the scattering as a function of optical path for hexagonal boron nitride nanoflakes of a given lateral length was found to be qualitatively equivalent to scattering from spheres with the same diameter. We also report the presence of random lasing in high concentration suspensions of aqueous h-BN mixed with Rhodamine B dye. The h-BN works as a scattering agent and Rhodamine B as a gain medium for the process. We observed random lasing at 587 nm with a threshold energy of 0.8 mJ.

Light scattering and random lasing in aqueous suspensions of hexagonal boron nitride nanoflakes.

PubMed

O'Brien, S A; Harvey, A; Griffin, A; Donnelly, T; Mulcahy, D; Coleman, J N; Donegan, J F; McCloskey, D

2017-11-24

Liquid phase exfoliation allows large scale production of 2D materials in solution. The particles are highly anisotropic and strongly scatter light. While spherical particles can be accurately and precisely described by a single parameter-the radius, 2D nanoflakes, however, cannot be so easily described. We investigate light scattering in aqueous solutions of 2D hexagonal boron nitride nanoflakes in the single and multiple scattering regimes. In the single scattering regime, the anisotropic 2D materials show a much stronger depolarization of light when compared to spherical particles of similar size. In the multiple scattering regime, the scattering as a function of optical path for hexagonal boron nitride nanoflakes of a given lateral length was found to be qualitatively equivalent to scattering from spheres with the same diameter. We also report the presence of random lasing in high concentration suspensions of aqueous h-BN mixed with Rhodamine B dye. The h-BN works as a scattering agent and Rhodamine B as a gain medium for the process. We observed random lasing at 587 nm with a threshold energy of 0.8 mJ.

Synthesis and liquid crystalline properties of mono-, di- and tri-O-alkyl pentaerythritol derivatives bearing tri-, di- or monogalactosyl heads: the effects of curvature of molecular packing on mesophase formation.

PubMed

Dumoulin, Fabienne; Lafont, Dominique; Huynh, Thai-Lê; Boullanger, Paul; Mackenzie, Grahame; West, Jon J; Goodby, John W

2007-01-01

Self-organisation and self-assembly are critical to the stability of synthetic and biological membranes. Of particular importance is consideration of the packing arrangements of the various molecular species. Both phospho- and glycolipids can pack in ways in which curvature can be introduced into self-organised or self-assembled systems. For instance, it is known that the degree of curvature can affect the structures of any condensed phases that are formed. In this article we report on a systematic study in which we have varied the shapes of glycolipids and examined the condensed phases that they form. In doing so, we have also unified the shape dependency of lyotropic liquid crystals with those of thermotropic liquid crystals. In order to undertake this systematic study a range of different pentaerythritol derivatives was synthesized, which covers combinations of one to three alkyl chains of different lengths (6,7,9,10,11,12,14,16 carbon atoms) and three to one galactosyl heads. Mono- and di-O-galactosyl derivatives were prepared directly by glycosylation of the corresponding alcohols using 2,3,4,6-tetra-O-benzoyl or acetyl-alpha-D-galactopyranosyl trichloroacetimidate or bromide as the donors; the tri-O-galactosyl derivatives were synthesized from O-alkyl-O-benzyl di-O-galactosyl pentaerythritol intermediates, followed by de-O-benzylation and glycosylation steps. All of the fully deprotected products were obtained by standard methods, and their self-organising and self-assembling properties examined.

Preparing highly ordered glasses of discotic liquid crystalline systems by vapor deposition

NASA Astrophysics Data System (ADS)

Gujral, Ankit; Gomez, Jaritza; Bishop, Camille E.; Toney, Michael F.; Ediger, M. D.

Anisotropic molecular packing, particularly in highly ordered liquid-crystalline arrangements, has the potential for optimizing performance in organic electronic and optoelectronic applications. Here we show that physical vapor deposition can be used to prepare highly organized out-of-equilibrium (glassy) solids of discotic liquid-crystalline (LC) systems. Using grazing incidence x-ray scattering, we compare 3 systems: a rectangular columnar LC, a hexagonal columnar LC and a non-liquid crystal former. The packing motifs accessible by vapor deposition are highly organized and vary from face-on to edge-on columnar arrangements depending upon substrate temperature. A subset of these structures cannot be accessed under equilibrium conditions. The structures formed at a given substrate temperature can be understood as the result of the system partially equilibrating toward the structure of the free surface of the equilibrium liquid crystal. Consistent with this view, the structures formed are independent of the substrate material.

Capillary Pressure of a Liquid Between Uniform Spheres Arranged in a Square-Packed Layer

NASA Technical Reports Server (NTRS)

Alexader, J. Iwan D.; Slobozhanin, Lev A.; Collicott, Steven H.

2004-01-01

The capillary pressure in the pores defined by equidimensional close-packed spheres is analyzed numerically. In the absence of gravity the menisci shapes are constructed using Surface Evolver code. This permits calculation the free surface mean curvature and hence the capillary pressure. The dependences of capillary pressure on the liquid volume constructed here for a set of contact angles allow one to determine the evolution of basic capillary characteristics under quasi-static infiltration and drainage. The maximum pressure difference between liquid and gas required for a meniscus passing through a pore is calculated and compared with that for hexagonal packing and with approximate solution given by Mason and Morrow [l]. The lower and upper critical liquid volumes that determine the stability limits for the equilibrium capillary liquid in contact with square packed array of spheres are tabulated for a set of contact angles.

Domain configurations in dislocations embedded hexagonal manganite systems: From the view of graph theory

NASA Astrophysics Data System (ADS)

Cheng, Shaobo; Zhang, Dong; Deng, Shiqing; Li, Xing; Li, Jun; Tan, Guotai; Zhu, Yimei; Zhu, Jing

2018-04-01

Topological defects and their interactions often arouse multiple types of emerging phenomena from edge states in Skyrmions to disclination pairs in liquid crystals. In hexagonal manganites, partial edge dislocations, a prototype topological defect, are ubiquitous and they significantly alter the topologically protected domains and their behaviors. Herein, combining electron microscopy experiment and graph theory analysis, we report a systematic study of the connections and configurations of domains in this dislocation embedded system. Rules for domain arrangement are established. The dividing line between domains, which can be attributed by the strain field of dislocations, is accurately described by a genus model from a higher dimension in the graph theory. Our results open a door for the understanding of domain patterns in topologically protected multiferroic systems.

Two-dimensional liquid crystalline growth within a phase-field-crystal model.

PubMed

Tang, Sai; Praetorius, Simon; Backofen, Rainer; Voigt, Axel; Yu, Yan-Mei; Wang, Jincheng

2015-07-01

By using a two-dimensional phase-field-crystal (PFC) model, the liquid crystalline growth of the plastic triangular phase is simulated with emphasis on crystal shape and topological defect formation. The equilibrium shape of a plastic triangular crystal (PTC) grown from an isotropic phase is compared with that grown from a columnar or smectic-A (CSA) phase. While the shape of a PTC nucleus in the isotropic phase is almost identical to that of the classical PFC model, the shape of a PTC nucleus in CSA is affected by the orientation of stripes in the CSA phase, and irregular hexagonal, elliptical, octagonal, and rectangular shapes are obtained. Concerning the dynamics of the growth process, we analyze the topological structure of the nematic order, which starts from nucleation of +1/2 and -1/2 disclination pairs at the PTC growth front and evolves into hexagonal cells consisting of +1 vortices surrounded by six satellite -1/2 disclinations. It is found that the orientational and the positional order do not evolve simultaneously; the orientational order evolves behind the positional order, leading to a large transition zone, which can span over several lattice spacings.

Phase Behavior and Conductivity of Phosphonated Block Copolymers Containing Ionic Liquids

NASA Astrophysics Data System (ADS)

Jung, Ha Young; Kim, Sung Yeon; Park, Moon Jeong

2015-03-01

As the focus on proton exchange fuel cells continues to escalate in the era of alternative energy systems, the rational design of sulfonated polymers has emerged as a key technique for enhancing device efficiency. While the sulfonic acid group guarantees high proton conductivity of membranes under humidified conditions, the growing need for high temperature operation has discouraged their practical uses in fuel cells. In this respect, phosphonated polymers have drawn intensive attention in recent years owing to their self-dissociation ability. In this study, we have synthesized a set of phosphonated block copolymers, poly(styrenephosphonate-methylbutylene) (PSP- b - PMB), by varying phosphonation level (PL). A wide variety of self-assembled morphologies, i.e., disordered, lamellar, hexagonally perforated lamellae and hexagonally packed cylindrical phases, were observed with PL. Remarkably, upon comparing the morphology of PSP- b-PMB and that of sulfonated analog, we found distinctly dissimilar domain sizes at the same molecular weight and composition. A range of ionic liquids (ILs) were incorporated into the PSP- b-PMB block copolymers and their ion transport properties were examined. It has been revealed that the degree of confinement of ionic phases (domain size) impacts the ion mobility and proton dissociation efficiency of IL-containing polymers.

The structure of an integral membrane peptide: a deuterium NMR study of gramicidin.

PubMed Central

Prosser, R S; Daleman, S I; Davis, J H

1994-01-01

Solid state deuterium NMR was employed on oriented multilamellar dispersions consisting of 1,2-dilauryl-sn-glycero-3-phosphatidylcholine and deuterium (2H) exchange-labeled gramicidin D, at a lipid to protein molar ratio (L/P) of 15:1, in order to study the dynamic structure of the channel conformation of gramicidin in a liquid crystalline phase. The corresponding spectra were used to discriminate between several structural models for the channel structure of gramicidin (based on the left- and right-handed beta 6.3 LD helix) and other models based on a structure obtained from high resolution NMR. The oriented spectrum is complicated by the fact that many of the doublets, corresponding to the 20 exchangeable sites, partially overlap. Furthermore, the asymmetry parameter, eta, of the electric field gradient tensor of the amide deuterons is large (approximately 0.2) and many of the amide groups are involved in hydrogen bonding, which is known to affect the quadrupole coupling constant. In order to account for these complications in simulating the spectra in the fast motional regime, an ab initio program called Gaussian 90 was employed, which permitted us to calculate, by quantum mechanical means, the complete electric field gradient tensor for each residue in gramicidin (using two structural models). Our results indicated that the left-handed helical models were inconsistent with our observed spectra, whereas a model based on the high-resolution structure derived by Arseniev and coworkers, but relaxed by a simple energy minimization procedure, was consistent with our observed spectra. The molecular order parameter was then estimated from the motional narrowing assuming the relaxed (right-handed) Arseniev structure. Our resultant order parameter of SZZ = 0.91 translates into an rms angle of 14 degrees, formed by the helix axis and the local bilayer normal. The strong resemblance between our spectra (and also those reported for gramicidin in 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC) multilayers) and the spectra of the same peptide incorporated in a lyotropic nematic phase, suggests that the lyotropic nematic phase simulates the local environment of the lipid bilayer. PMID:7520293

Tunable liquid optics: electrowetting-controlled liquid mirrors based on self-assembled Janus tiles.

PubMed

Bucaro, Michael A; Kolodner, Paul R; Taylor, J Ashley; Sidorenko, Alex; Aizenberg, Joanna; Krupenkin, Tom N

2009-04-09

In this paper, we describe a tunable, high-reflectivity optofluidic device based on self-assembly of anisotropically functionalized hexagonal micromirrors (Janus tiles) on the surface of an oil droplet to create a concave liquid mirror. The liquid mirror is deposited on a patterned transparent electrode that allows the focal length and axial position to be electrically controlled. The mirror is mechanically robust and retains its integrity even at high levels of vibrational excitation of the interface. The use of reflection instead of refraction overcomes the limited available refractive-index contrast between pairs of density-matched liquids, allowing stronger focusing than is possible for a liquid lens of the same geometry. This approach is compatible with optical instruments that could provide novel functionality-for example, a dynamic 3D projector, i.e., a light source which can scan an image onto a moving, nonplanar focal surface. Janus tiles with complex optical properties can be manufactured using our approach, thus potentially enabling a wide range of novel optical elements.

Tunable liquid optics: electrowetting-controlled liquid mirrors based on self-assembled Janus tiles

NASA Astrophysics Data System (ADS)

Krupenkin, Tom; Bucaro, Mike; Kolodner, Paul; Taylor, Ashley; Sidorenko, Alex; Aizenberg, Joanna

2009-03-01

In this work we describe a tunable, high-reflectivity optofluidic device based on self-assembly of anisotropically-functionalized hexagonal micromirrors (Janus tiles) on the surface of an oil droplet to create a concave liquid mirror. The liquid mirror is deposited on a patterned transparent electrode that allows the focal length and axial position to be electrically controlled. The mirror is mechanically robust and retains its integrity even at high levels of vibrational excitation of the interface. The use of reflection instead of refraction overcomes the limited available refractive-index contrast between pairs of density-matched liquids, allowing stronger focusing than is possible for a liquid lens of the same geometry. This approach is compatible with optical instruments that could provide novel functionality - for example, a dynamic 3D projector; i.e., a light source which can scan an image onto a moving, non-planar focal surface. Janus tiles with complex optical properties can be manufactured using our approach, thus potentially enabling a wide range of novel optical elements.

Soft Soil Improvement for Sub-grade Layer Using Hexagonal Micropiles Layout

NASA Astrophysics Data System (ADS)

Ambak, K.; Abdullah, N. A. H.; Yusoff, M. F.; Abidin, M. H. Z.

2018-04-01

Soft soil problems are often associated with sediment and stability where it represents a major challenge in Geotechnical Engineering. Research on a soft soil was carried out to determine the level of sediment resulting from the applied load and thus compare the most ideal form of arrangement by the results obtained from bearing capacity. The study was conducted at Research Centre for Soft Soil (RECESS), UTHM by using kaolin. There are several tests conducted on kaolin before the arrangement of pile which is liquid limit test. Through these tests, the level of water content can be maintained which is 1.2 liquid limit where it is in the homogeneous condition. Density test also carried to know weight of kaolin and water that needed in the model. Meanwhile, large strain consolidation test carried on the soil by placing a load of 8 kPa. Then, the pile was arranged in the soil in the shape of a hexagon and square. Load was increased to 12 kPa and imposed on the surface of the pile with a different forms. After 24 hours, the reading of sediment was measured everyday and the process collecting data conducted for 3 week. Based on data obtained, time against sediment can be plotted. To determine the bearing capacity, direct shear test was conducted to get the value coefficient of cohesion, c as a parameter in the calculation of the soil bearing capacity. The results showed that the rate of settlement occurs is different where hexagonal form less the rate of settlement compared to square form which is 64.2% while the results of bearing capacity have the same value.

Formulation of Poloxamers for Drug Delivery

PubMed Central

Bodratti, Andrew M.; Alexandridis, Paschalis

2018-01-01

Poloxamers, also known as Pluronics®, are block copolymers of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO), which have an amphiphilic character and useful association and adsorption properties emanating from this. Poloxamers find use in many applications that require solubilization or stabilization of compounds and also have notable physiological properties, including low toxicity. Accordingly, poloxamers serve well as excipients for pharmaceuticals. Current challenges facing nanomedicine revolve around the transport of typically water-insoluble drugs throughout the body, followed by targeted delivery. Judicious design of drug delivery systems leads to improved bioavailability, patient compliance and therapeutic outcomes. The rich phase behavior (micelles, hydrogels, lyotropic liquid crystals, etc.) of poloxamers makes them amenable to multiple types of processing and various product forms. In this review, we first present the general solution behavior of poloxamers, focusing on their self-assembly properties. This is followed by a discussion of how the self-assembly properties of poloxamers can be leveraged to encapsulate drugs using an array of processing techniques including direct solubilization, solvent displacement methods, emulsification and preparation of kinetically-frozen nanoparticles. Finally, we conclude with a summary and perspective. PMID:29346330

Hydration of dimethyldodecylamine-N-oxide: enthalpy and entropy driven processes.

PubMed

Kocherbitov, Vitaly; Söderman, Olle

2006-07-13

Dimethyldodecylamine-N-oxide (DDAO) has only one polar atom that is able to interact with water. Still, this surfactant shows very hydrophilic properties: in mixtures with water, it forms normal liquid crystalline phases and micelles. Moreover, there is data in the literature indicating that the hydration of this surfactant is driven by enthalpy while other studies show that hydration of surfactants and lipids typically is driven by entropy. Sorption calorimetry allows resolving enthalpic and entropic contributions to the free energy of hydration at constant temperature and thus directly determines the driving forces of hydration. The results of the present sorption calorimetric study show that the hydration of liquid crystalline phases of DDAO is driven by entropy, except for the hydration of the liquid crystalline lamellar phase which is co-driven by enthalpy. The exothermic heat effect of the hydration of the lamellar phase arises from formation of strong hydrogen bonds between DDAO and water. Another issue is the driving forces of the phase transitions caused by the hydration. The sorption calorimetric results show that the transitions from the lamellar to cubic and from the cubic to the hexagonal phase are driven by enthalpy. Transitions from solid phases to the liquid crystalline lamellar phase are entropically driven, while the formation of the monohydrate from the dry surfactant is driven by enthalpy. The driving forces of the transition from the hexagonal phase to the isotropic solution are close to zero. These sorption calorimetric results are in good agreement with the analysis of the binary phase diagram based on the van der Waals differential equation. The phase diagram of the DDAO-water system determined using DSC and sorption calorimetry is presented.

Transferable model of water with variable molecular size

NASA Astrophysics Data System (ADS)

Kiss, Péter T.; Baranyai, András

2011-06-01

By decreasing the steepness of the repulsive wing in the intermolecular potential, one can extend the applicability of a water model to the high pressure region. Exploiting this trivial possibility, we published a polarizable model of water which provided good estimations not only of gas clusters, ambient liquid, hexagonal ice, but ice VII at very high pressures as well [A. Baranyai and P. Kiss, J. Chem. Phys. 133, 144109 (2010), 10.1063/1.3490660]. This straightforward method works well provided the closest O-O distance is reasonably shorter in the high pressure phase than in hexagonal ice. If these O-O distances are close to each other and we fit the interactions to obtain an accurate picture of hexagonal ice, we underestimate the density of the high-pressure phases. This can be overcome if models use contracted molecules under high external pressure.In this paper we present a method, which is capable to describe the contraction of water molecules under high pressure by using two simple repulsion-attraction functions. These functions represent the dispersion interaction under low pressure and high pressure. The switch function varies between 0 and 1 and portions the two repulsions among the individual particles. The argument of the switch function is a virial-type expression, which can be interpreted as a net force compressing the molecule. We calculated the properties of gas clusters, densities, and internal energies of ambient water, hexagonal ice, ice III, ice VI, and ice VII phases and obtained excellent match of experimental data.

Neutron diffraction study of water freezing on aircraft engine combustor soot.

PubMed

Tishkova, V; Demirdjian, B; Ferry, D; Johnson, M

2011-12-14

The study of the formation of condensation trails and cirrus clouds on aircraft emitted soot particles is important because of its possible effects on climate. In the present work we studied the freezing of water on aircraft engine combustor (AEC) soot particles under conditions of pressure and temperature similar to the upper troposphere. The microstructure of the AEC soot was found to be heterogeneous containing both primary particles of soot and metallic impurities (Fe, Cu, and Al). We also observed various surface functional groups such as oxygen-containing groups, including sulfate ions, that can act as active sites for water adsorption. Here we studied the formation of ice on the AEC soot particles by using neutron diffraction. We found that for low amount of adsorbed water, cooling even up to 215 K did not lead to the formation of hexagonal ice. Whereas, larger amount of adsorbed water led to the coexistence of liquid water (or amorphous ice) and hexagonal ice (I(h)); 60% of the adsorbed water was in the form of ice I(h) at 255 K. Annealing of the system led to the improvement of the crystal quality of hexagonal ice crystals as demonstrated from neutron diffraction.

Phase behavior and transitions of self-assembling nano-structured materials

NASA Astrophysics Data System (ADS)

Duan, Hu

Homologous series of supramolecular nanostructures have been investigated by a combination of transmission electron microscopy (TEM), electron diffraction (ED), thermal polarized optical microscopy and X-ray diffraction (XRD). Materials include amphiphilic oligomers and polymer such as charged complexes, dipeptide dendrons semi-fluorinated dendron and polyethyleneimines. Upon microphase separation, they self-assemble into either cylindrical or spherical shapes, which co-organize into a 2D P6mm hexagonal columnar phase or 3D Pm 3¯ n and Im 3¯ m cubic phases. Correlation between the phase selection and molecular architecture is established accordingly. The order-disorder transition (ODT) is explored by rheometry and rheo-optical microscopy in a model polymeric compound poly(N-[3,4-bis(n-dodecan-1-yloxy)benzoyl]ethyleneimine). Shear alignment of the hexagonal columnar liquid crystalline phase along the velocity direction at low temperature and shear disordering in the vicinity of the ODT were observed. After cessation of shear, transformation back to the stable columnar phase follows a row-nucleation mechanism. The order-order transition process is explored in a monodendron that exhibits a hexagonal columnar and a weakly birefringent mesophase. Polarized DIC microscopy strongly supports an epitaxial relationship between them.

Self-Assembled Polystyrene Beads for Templated Covalent Functionalization of Graphitic Substrates Using Diazonium Chemistry.

PubMed

Van Gorp, Hans; Walke, Peter; Bragança, Ana M; Greenwood, John; Ivasenko, Oleksandr; Hirsch, Brandon E; De Feyter, Steven

2018-04-11

A network of self-assembled polystyrene beads was employed as a lithographic mask during covalent functionalization reactions on graphitic surfaces to create nanocorrals for confined molecular self-assembly studies. The beads were initially assembled into hexagonal arrays at the air-liquid interface and then transferred to the substrate surface. Subsequent electrochemical grafting reactions involving aryl diazonium molecules created covalently bound molecular units that were localized in the void space between the nanospheres. Removal of the bead template exposed hexagonally arranged circular nanocorrals separated by regions of chemisorbed molecules. Small molecule self-assembly was then investigated inside the resultant nanocorrals using scanning tunneling microscopy to highlight localized confinement effects. Overall, this work illustrates the utility of self-assembly principles to transcend length scale gaps in the development of hierarchically patterned molecular materials.

Ion-Specific Interfacial Crystallization of Polymer-Grafted Nanoparticles

DOE PAGES

Zhang, Honghu; Wang, Wenjie; Mallapragada, Surya; ...

2017-06-27

In this study, ion-specific effects on the assembly and crystallization of polyethylene-glycol-grafted Au nanoparticles (PEG-AuNPs) at the vapor–liquid interface are examined by surface sensitive synchrotron X-ray scattering methods. We show that monovalent salts, such as KCl and NaCl, that do not advance phase separation of pure PEG at room temperature induce two-dimensional (2D) self-assembly and crystallization of PEG-AuNPs with some distinctions. Whereas for KCl the 2D hexagonal coherence length of the PEG-AuNP superlattices is remarkably large compared to other salts (over micron-sized crystalline grains), NaCl induces coexistence of two hexagonal structures. Using various salts, we find that the value ofmore » the lattice constant is correlated to the ionic hydration entropy consistent with the Hofmeister series.« less

Domain configurations in dislocations embedded hexagonal manganite systems: From the view of graph theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, Shaobo; Zhang, Dong; Deng, Shiqing

Topological defects and their interactions often arouse multiple types of emerging phenomena from edge states in Skyrmions to disclination pairs in liquid crystals. In hexagonal manganites, partial edge dislocations, a prototype topological defect, are ubiquitous and they significantly alter the topologically protected domains and their behaviors. In this work, combining electron microscopy experiment and graph theory analysis, we report a systematic study of the connections and configurations of domains in this dislocation embedded system. Rules for domain arrangement are established. The dividing line between domains, which can be attributed by the strain field of dislocations, is accurately described by amore » genus model from a higher dimension in the graph theory. In conclusion, our results open a door for the understanding of domain patterns in topologically protected multiferroic systems.« less

Patterning monolayer graphene with zigzag edges on hexagonal boron nitride by anisotropic etching

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Guole; Wu, Shuang; Zhang, Tingting

2016-08-01

Graphene nanostructures are potential building blocks for nanoelectronic and spintronic devices. However, the production of monolayer graphene nanostructures with well-defined zigzag edges remains a challenge. In this paper, we report the patterning of monolayer graphene nanostructures with zigzag edges on hexagonal boron nitride (h-BN) substrates by an anisotropic etching technique. We found that hydrogen plasma etching of monolayer graphene on h-BN is highly anisotropic due to the inert and ultra-flat nature of the h-BN surface, resulting in zigzag edge formation. The as-fabricated zigzag-edged monolayer graphene nanoribbons (Z-GNRs) with widths below 30 nm show high carrier mobility and width-dependent energy gaps atmore » liquid helium temperature. These high quality Z-GNRs are thus ideal structures for exploring their valleytronic or spintronic properties.« less

Domain configurations in dislocations embedded hexagonal manganite systems: From the view of graph theory

DOE PAGES

Cheng, Shaobo; Zhang, Dong; Deng, Shiqing; ...

2018-04-19

Topological defects and their interactions often arouse multiple types of emerging phenomena from edge states in Skyrmions to disclination pairs in liquid crystals. In hexagonal manganites, partial edge dislocations, a prototype topological defect, are ubiquitous and they significantly alter the topologically protected domains and their behaviors. In this work, combining electron microscopy experiment and graph theory analysis, we report a systematic study of the connections and configurations of domains in this dislocation embedded system. Rules for domain arrangement are established. The dividing line between domains, which can be attributed by the strain field of dislocations, is accurately described by amore » genus model from a higher dimension in the graph theory. In conclusion, our results open a door for the understanding of domain patterns in topologically protected multiferroic systems.« less

Polypeptide Liquid Crystal Assisted Assembly of Cylindrically Symmetric Silica-Polypeptide Hybrid Microparticles

NASA Astrophysics Data System (ADS)

Russo, Paul; Rosu, Cornelia; Jacobeen, Shane; Park, Katherine; Yunker, Peter; Reichmanis, Elsa

Liquid crystals can organize dispersed particles into exotic structures. Matching the particle surface coating to the chemistry of the mesogenic phase permits a tight focus on factors such as extended particle shape. The colloidal particles developed for this work consist of a magnetic and fluorescent cylinder-like silica core. One end of the silica is rounded, almost hemispherical, giving the particles a bullet-like shape. These particles are functionalized with helical poly(γ-stearyl-L-glutamate) and dispersed, at different concentrations in cholesteric liquid crystals (ChLC) of the same polymer in tetrahydrofuran. Defects introduced by the particles to the director field of the bulk PSLG/THF host led to a variety of phases, including a quasi-hexagonal alignment of the particles. National Science Foundation.

Focal Conic Stacking in Smectic A Liquid Crystals: Smectic Flower and Apollonius Tiling

PubMed Central

Meyer, Claire; Cunff, Loic Le; Belloul, Malika; Foyart, Guillaume

2009-01-01

We investigate two different textures of smectic A liquid crystals. These textures are particularly symmetric when they are observed at crossed polars optical microscopy. For both textures, a model has been made in order to examine the link between the defective macroscopic texture and the microscopic disposition of the layers. We present in particular in the case of some hexagonal tiling of circles (similar to the Apollonius tiling) some numeric simulation in order to visualize the smectic layers. We discuss of the nature of the smectic layers, which permit to assure their continuity from one focal conic domain to another adjacent one.

Organization of Amphiphilic Molecular Disks with Branched Hydrophilic Tails and Hexa-peri-hexabenzocoronene Core

NASA Astrophysics Data System (ADS)

Lee, Myongsoo; Kim, Jung-Woo; Yoo, Yong-Sik; Peleshanko, Sergey; Larson, Kirsten; Vaknin, David; Markutsya, Sergei; Tsukruk, Vladimir V.

2002-03-01

Amphiphilic branched discotics consisting of the aromatic core and oligoethers as the branched peripheral chains have been characterized in bulk and monolayer states. The discotics based on di-branched oligoether side chains have been observed to self-organize into an ordered hexagonal columnar structure within liquid crystalline (LC) phases. The tetrabranched molecule showed only an isotropic liquid. The LC molecules with di-branched tails have been observed to form stable monolayers on the water surface in contrast to the tetra-branched tails. We suggest a crab-like molecular conformation and cluster-segregated monolayers with six-fold symmetry of face-on packing on a solid surface.

In situ SAXS study on cationic and non-ionic surfactant liquid crystals using synchrotron radiation.

PubMed

Fritscher, C; Hüsing, N; Bernstorff, S; Brandhuber, D; Koch, T; Seidler, S; Lichtenegger, H C

2005-11-01

In situ synchrotron small-angle X-ray scattering was used to investigate various surfactant/water systems with hexagonal and lamellar structures regarding their structural behaviour upon heating and cooling. Measurements of the non-ionic surfactant Triton X-45 (polyethylene glycol 4-tert-octylphenyl ether) at different surfactant concentrations show an alignment of the lamellar liquid-crystalline structure close to the wall of the glass capillaries and also a decrease in d-spacing following subsequent heating/cooling cycles. Additionally, samples were subjected to a weak magnetic field (0.3-0.7 T) during heating and cooling, but no influence of the magnetic field was observed.

Supramolecularly engineered perylene bisimide assemblies exhibiting thermal transition from columnar to multilamellar structures.

PubMed

Yagai, Shiki; Usui, Mari; Seki, Tomohiro; Murayama, Haruno; Kikkawa, Yoshihiro; Uemura, Shinobu; Karatsu, Takashi; Kitamura, Akihide; Asano, Atsushi; Seki, Shu

2012-05-09

Perylene 3,4:9,10-tetracarboxylic acid bisimide (PBI) was functionalized with ditopic cyanuric acid to organize it into complex columnar architectures through the formation of hydrogen-bonded supermacrocycles (rosette) by complexing with ditopic melamines possessing solubilizing alkoxyphenyl substituents. The aggregation study in solution using UV-vis and NMR spectroscopies showed the formation of extended aggregates through hydrogen-bonding and π-π stacking interactions. The cylindrical fibrillar nanostructures were visualized by microscopic techniques (AFM, TEM), and the formation of lyotropic mesophase was confirmed by polarized optical microscopy and SEM. X-ray diffraction study revealed that a well-defined hexagonal columnar (Col(h)) structure was formed by solution-casting of fibrillar assemblies. All of these results are consistent with the formation of hydrogen-bonded PBI rosettes that spontaneously organize into the Col(h) structure. Upon heating the Col(h) structure in the bulk state, a structural transition to a highly ordered lamellar (Lam) structure was observed by variable-temperature X-ray diffraction, differential scanning calorimetry, and AFM studies. IR study showed that the rearrangement of the hydrogen-bonding motifs occurs during the structural transition. These results suggest that such a striking structural transition is aided by the reorganization in the lowest level of self-organization, i.e., the rearrangement of hydrogen-bonded motifs from rosette to linear tape. A remarkable increase in the transient photoconductivity was observed by the flash-photolysis time-resolved microwave conductivity (FP-TRMC) measurements upon converting the Col(h) structure to the Lam structure. Transient absorption spectroscopy revealed that electron transfer from electron-donating alkoxyphenyl groups of melamine components to electron-deficient PBI moieties takes place, resulting in a higher probability of charge carrier generation in the Lam structure compared to the Col(h) structure.

The relative energy of fcc and hcp foams

NASA Astrophysics Data System (ADS)

Whyte, D.; Weaire, D.; Drenckhan, W.; Hutzler, S.

2015-06-01

The energies of face-centred cubic (fcc) and hexagonal close-packed (hcp) monodisperse foams, associated with their total surface area, are equal in the wet and dry limits, in the usual model. We prove that for all intermediate values of liquid fraction, hcp has lower energy. Energy considerations are thus not sufficient to explain the observed preference for crystallization into fcc over hcp in experiments using monodisperse bubbles.

From faceted vesicles to liquid icoshedra: Where topology and crystallography meet

DOE PAGES

Guttman, Shani; Ocko, Benjamin M.; Deutsch, Moshe; ...

2016-02-17

We study many common amphiphiles that spontaneously self-assemble in aqueous solutions, forming membranes and unilamellar vesicles. While the vesicular membranes are bilayers, with the hydrophilic moieties exposed to the solution, the structure formed by amphiphiles at the oil–water (i.e., alkane–water) interfaces, such as the surface of an oil droplet in water, is typically a monolayer. It has recently been demonstrated that these monolayers and bilayers may crystallize on cooling, with the thermodynamic conditions for this transition set by the geometry of the constituent molecules. While a planar hexagonal packing motif is particularly abundant in these crystals, a hexagonal lattice ismore » incompatible with a closed-surface topology, such as a closed vesicle or the surface of a droplet. Thus, (at least) 12 five-fold defects form, giving rise to a complex interplay between the stretching and the bending energies of these two-dimensional crystals; in addition, a central role is also played by the interfacial tension. This interplay, part of which has been theoretically studied in the past, gives rise to a range of unexpected and counterintuitive phenomena, such as the recently-observed temperature-tunable formation of stable liquid polyhedra, and a tail growing and droplet-splitting akin to the spontaneous emulsification effect.« less

The static and dynamic behaviors of the topological defects in a nematic liquid crystal reveal its material characteristics

NASA Astrophysics Data System (ADS)

Zhang, Rui; Yanagimachi, Takuya; Kumar, Nitin; Gardel, Margaret; Nealey, Paul; de Pablo, Juan

Topological defects in nematic liquid crystals (LCs) play a key role in phase transitions, domain growth, and morphology evolution. Their ability to absorb impurities offers promise for design of self-assembled, hierarchical materials. Past work has primarily studied defects in thermotropic LCs. In this work, we focus on lyotropic chromonic LCs and biopolymer LCs, and investigate how the static and dynamic properties of topological defects depend on the LC's material characteristics. Specifically, we rely on a Landau-de Gennes free energy model that accounts for variable material constants and back-flow effects, and adopt a hybrid lattice Boltzmann simulation method. We first show that the fine structure of half-charge defects is a function of the ratio of splay and bend constants. This morphological information is in turn used to infer the elasticity of an in vitro, actin-based LC suspension. We then examine the annihilation process of a defect pair of opposite topological charge. We find that the ratio of the two defect velocities is an outcome of the interplay between the LC's elastic moduli, its viscosities, and the organization of the defects. Our calculations predict a strong post-annihilation transverse flow that is further confirmed by our experiments with non-equilibrium LCs. An analysis of the asymptotic behavior of the elastic moduli allows us to elucidate the material at phase transitions. Our modelling provides a general, unified framework within which a wide class of LC materials can be understood.

Ultrasound exfoliation of inorganic analogues of graphene

PubMed Central

2014-01-01

High-intensity ultrasound exfoliation of a bulk-layered material is an attractive route for large-scale preparation of monolayers. The monolayer slices could potentially be prepared with a high yield (up to 100%) in a few minutes. Exfoliation of natural minerals (such as tungstenite and molybdenite) or bulk synthetic materials (including hexagonal boron nitride (h-BN), hexagonal boron carbon nitride (h-BCN), and graphitic carbon nitride (g-C3N4)) in liquids leads to the breakdown of the 3D graphitic structure into a 2D structure; the efficiency of this process is highly dependent upon the physical effects of the ultrasound. Atomic force microscopy (AFM), transmission electron microscopy (TEM), and selected area electron diffraction (SAED) were employed to verify the quality of the exfoliation. Herein, this new method of exfoliation with ultrasound assistance for application to mono- and bilayered materials in hydrophobic and hydrophilic environments is presented. PMID:24708572

Ultrasound exfoliation of inorganic analogues of graphene.

PubMed

Stengl, Václav; Henych, Jiří; Slušná, Michaela; Ecorchard, Petra

2014-04-05

High-intensity ultrasound exfoliation of a bulk-layered material is an attractive route for large-scale preparation of monolayers. The monolayer slices could potentially be prepared with a high yield (up to 100%) in a few minutes. Exfoliation of natural minerals (such as tungstenite and molybdenite) or bulk synthetic materials (including hexagonal boron nitride (h-BN), hexagonal boron carbon nitride (h-BCN), and graphitic carbon nitride (g-C3N4)) in liquids leads to the breakdown of the 3D graphitic structure into a 2D structure; the efficiency of this process is highly dependent upon the physical effects of the ultrasound. Atomic force microscopy (AFM), transmission electron microscopy (TEM), and selected area electron diffraction (SAED) were employed to verify the quality of the exfoliation. Herein, this new method of exfoliation with ultrasound assistance for application to mono- and bilayered materials in hydrophobic and hydrophilic environments is presented.

Evolution of Moiré Profiles from van der Waals Superstructures of Boron Nitride Nanosheets

PubMed Central

Liao, Yunlong; Cao, Wei; Connell, John W.; Chen, Zhongfang; Lin, Yi

2016-01-01

Two-dimensional (2D) van der Waals (vdW) superstructures, or vdW solids, are formed by the precise restacking of 2D nanosheet lattices, which can lead to unique physical and electronic properties that are not available in the parent nanosheets. Moiré patterns formed by the crystalline mismatch between adjacent nanosheets are the most direct features for vdW superstructures under microscopic imaging. In this article, transmission electron microscopy (TEM) observation of hexagonal Moiré patterns with unusually large micrometer-sized lateral areas (up to ~1 μm2) and periodicities (up to ~50 nm) from restacking of liquid exfoliated hexagonal boron nitride nanosheets (BNNSs) is reported. This observation was attributed to the long range crystallinity and the contaminant-free surfaces of these chemically inert nanosheets. Parallel-line-like Moiré fringes with similarly large periodicities were also observed. The simulations and experiments unambiguously revealed that the hexagonal patterns and the parallel fringes originated from the same rotationally mismatched vdW stacking of BNNSs and can be inter-converted by simply tilting the TEM specimen following designated directions. This finding may pave the way for further structural decoding of other 2D vdW superstructure systems with more complex Moiré images. PMID:27188697

Single Crystalline Film of Hexagonal Boron Nitride Atomic Monolayer by Controlling Nucleation Seeds and Domains

PubMed Central

Wu, Qinke; Park, Ji-Hoon; Park, Sangwoo; Jung, Seong Jun; Suh, Hwansoo; Park, Noejung; Wongwiriyapan, Winadda; Lee, Sungjoo; Lee, Young Hee; Song, Young Jae

2015-01-01

A monolayer hexagonal boron nitride (h-BN) film with controllable domain morphology and domain size (varying from less than 1 μm to more than 100 μm) with uniform crystalline orientation was successfully synthesized by chemical vapor deposition (CVD). The key for this extremely large single crystalline domain size of a h-BN monolayer is a decrease in the density of nucleation seeds by increasing the hydrogen gas flow during the h-BN growth. Moreover, the well-defined shape of h-BN flakes can be selectively grown by controlling Cu-annealing time under argon atmosphere prior to h-BN growth, which provides the h-BN shape varies in triangular, trapezoidal, hexagonal and complex shapes. The uniform crystalline orientation of h-BN from different nucleation seeds can be easily confirmed by polarized optical microscopy (POM) with a liquid crystal coating. Furthermore, seamlessly merged h-BN flakes without structural domain boundaries were evidence by a selective hydrogen etching after a full coverage of a h-BN film was achieved. This seamless large-area and atomic monolayer of single crystalline h-BN film can offer as an ideal and practical template of graphene-based devices or alternative two-dimensional materials for industrial applications with scalability. PMID:26537788

Single Crystalline Film of Hexagonal Boron Nitride Atomic Monolayer by Controlling Nucleation Seeds and Domains

NASA Astrophysics Data System (ADS)

Wu, Qinke; Park, Ji-Hoon; Park, Sangwoo; Jung, Seong Jun; Suh, Hwansoo; Park, Noejung; Wongwiriyapan, Winadda; Lee, Sungjoo; Lee, Young Hee; Song, Young Jae

2015-11-01

A monolayer hexagonal boron nitride (h-BN) film with controllable domain morphology and domain size (varying from less than 1 μm to more than 100 μm) with uniform crystalline orientation was successfully synthesized by chemical vapor deposition (CVD). The key for this extremely large single crystalline domain size of a h-BN monolayer is a decrease in the density of nucleation seeds by increasing the hydrogen gas flow during the h-BN growth. Moreover, the well-defined shape of h-BN flakes can be selectively grown by controlling Cu-annealing time under argon atmosphere prior to h-BN growth, which provides the h-BN shape varies in triangular, trapezoidal, hexagonal and complex shapes. The uniform crystalline orientation of h-BN from different nucleation seeds can be easily confirmed by polarized optical microscopy (POM) with a liquid crystal coating. Furthermore, seamlessly merged h-BN flakes without structural domain boundaries were evidence by a selective hydrogen etching after a full coverage of a h-BN film was achieved. This seamless large-area and atomic monolayer of single crystalline h-BN film can offer as an ideal and practical template of graphene-based devices or alternative two-dimensional materials for industrial applications with scalability.

Phase selective synthesis of quantum cutting nanophosphors and the observation of a spontaneous room temperature phase transition.

PubMed

Ghosh, Pushpal; Mudring, Anja-Verena

2016-04-21

Oxygen-free Eu(3+)-doped NaGdF4 nanocrystals with high quantum cutting efficiency are accessible at low temperatures (room temperature to 80 °C) using task-specific ionic liquids (ILs) as structure directing agents and only water as solvent. Selective tuning of the shape, morphology and, most importantly, the crystal phase of the host lattice is achieved by changing the alkyl side length, the H-bonding capabilities and the concentration of 1-alkyl-3-methylimidazolium bromide ILs, [C(n)mim]Br. When using [C2mim]Br, hexagonal NaGdF4 nanoparticles are obtained. In the case of methylimidazolium bromides with longer pendant alkyl chains such as butyl (C4), octyl (C8) or decyl (C10), extremely small nanoparticles of the cubic polymorph form, which then convert even at room temperature (RT) to the thermodynamically favored hexagonal modification. To the best of our knowledge, this kind of spontaneous phase transition is not yet reported. The hexagonal nanomaterial shows a substantial quantum cutting efficiency (154%) whilst in the cubic material, the effect is negligible (107%). The easy yet highly phase selective green synthesis of the materials promises large scale industrial application in environmentally benign energy efficient lighting.

Self-alignment of plasmonic gold nanorods in reconfigurable anisotropic fluids for tunable bulk metamaterial applications.

PubMed

Liu, Qingkun; Cui, Yanxia; Gardner, Dennis; Li, Xin; He, Sailing; Smalyukh, Ivan I

2010-04-14

We demonstrate the bulk self-alignment of dispersed gold nanorods imposed by the intrinsic cylindrical micelle self-assembly in nematic and hexagonal liquid crystalline phases of anisotropic fluids. External magnetic field and shearing allow for alignment and realignment of the liquid crystal matrix with the ensuing long-range orientational order of well-dispersed plasmonic nanorods. This results in a switchable polarization-sensitive plasmon resonance exhibiting stark differences from that of the same nanorods in isotropic fluids. The device-scale bulk nanoparticle alignment may enable optical metamaterial mass production and control of properties arising from combining the switchable nanoscale structure of anisotropic fluids with the surface plasmon resonance properties of the plasmonic nanorods.

Plasma in-liquid method for reduction of zinc oxide in zinc nanoparticle synthesis

NASA Astrophysics Data System (ADS)

Amaliyah, Novriany; Mukasa, Shinobu; Nomura, Shinfuku; Toyota, Hiromichi; Kitamae, Tomohide

2015-02-01

Metal air-batteries with high-energy density are expected to be increasingly applied in electric vehicles. This will require a method of recycling air batteries, and reduction of metal oxide by generating plasma in liquid has been proposed as a possible method. Microwave-induced plasma is generated in ethanol as a reducing agent in which zinc oxide is dispersed. Analysis by energy-dispersive x-ray spectrometry (EDS) and x-ray diffraction (XRD) reveals the reduction of zinc oxide. According to images by transmission electron microscopy (TEM), cubic and hexagonal metallic zinc particles are formed in sizes of 30 to 200 nm. Additionally, spherical fiber flocculates approximately 180 nm in diameter are present.

Transition to spatiotemporal chaos in a two-dimensional hydrodynamic system.

PubMed

Pirat, Christophe; Naso, Aurore; Meunier, Jean-Louis; Maïssa, Philippe; Mathis, Christian

2005-04-08

We study the transition to spatiotemporal chaos in a two-dimensional hydrodynamic experiment where liquid columns take place in the gravity induced instability of a liquid film. The film is formed below a plane grid which is used as a porous media and is continuously supplied with a controlled flow rate. This system can be either ordered (on a hexagonal structure) or disordered depending on the flow rate. We observe, for the first time in an initially structured state, a subcritical transition to spatiotemporal disorder which arises through spatiotemporal intermittency. Statistics of numbers, creations, and fusions of columns are investigated. We exhibit a critical behavior close to the directed percolation one.

Comparative study of crystallization process in metallic melts using ab initio molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Debela, Tekalign T.; Wang, X. D.; Cao, Q. P.; Zhang, D. X.; Jiang, J. Z.

2017-05-01

The crystallization process of liquid metals is studied using ab initio molecular dynamics simulations. The evolution of short-range order during quenching in Pb and Zn liquids is compared with body-centered cubic (bcc) Nb and V, and hexagonal closed-packed (hcp) Mg. We found that the fraction and type of the short-range order depends on the system under consideration, in which the icosahedral symmetry seems to dominate in the body-centered cubic metals. Although the local atomic structures in stable liquids are similar, liquid hcp-like Zn, bcc-like Nb and V can be deeply supercooled far below its melting point before crystallization while the supercooled temperature range in liquid Pb is limited. Further investigations into the nucleation process reveal the process of polymorph selection. In the body-centered cubic systems, the polymorph selection occurs in the supercooled state before the nucleation is initiated, while in the closed-packed systems it starts at the time of onset of crystallization. Atoms with bcc-like lattices in all studied supercooled liquids are always detected before the polymorph selection. It is also found that the bond orientational ordering is strongly correlated with the crystallization process in supercooled Zn and Pb liquids.

Atomic study on the ordered structure in Al melts induced by liquid/substrate interface with Ti solute

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, H. L.; Han, Y. F., E-mail: yfhan@sjtu.edu.cn, E-mail: bdsun@sjtu.edu.cn; Zhou, W.

2015-01-26

Atomic ordering in Al melts induced by liquid/substrate interface with Ti solute was investigated by ab initio molecular dynamics simulations and in-situ synchrotron X-ray diffraction. It is predicted that deformed nanoscale ordering Al layers with a rhombohedral-centered hexagonal structure (R3{sup ¯}m space group) instead of the intrinsic fcc structure (Fm3{sup ¯}m space group) form on substrate at temperature above Al liquids. With Al atoms stacking away from the interface, the ordering structure reaches a critical thickness, which inhibits the consecutive stacking of Al atoms on substrates. The locally stacking reconstruction induced by Ti atom relieves the accumulated elastic strain energymore » in ordered Al layers, facilitating fully heterogeneous nucleation on substrate beyond the deformed ordering Al layer around the melting point. The roles of liquid/substrate interface with Ti solute in the physical behavior of heterogeneous nucleation on substrate were discussed.« less

Identification and assessment of permeability enhancing vehicles for transdermal delivery of glucosamine hydrochloride.

PubMed

Han, In Hee; Choi, Sung-Up; Nam, Dae Young; Park, Young Mi; Kang, Myung Joo; Kang, Kyoung Hoon; Kim, Yong Min; Bae, Gunho; Oh, Il Young; Park, Jong Hyeok; Ye, Jin Soo; Choi, Yoon Bae; Kim, Duk Ki; Lee, Jaehwi; Choi, Young Wook

2010-02-01

As an initial step to develop the transdermal delivery system of glucosamine hydrochloride (GL-HCl), the permeation study across the rat skin in vitro was performed to identify the most efficient vehicle with regard to the ability to deliver GL-HCl transdermally. The GL-HCl formulations such as o/w cream, liposome suspension, liposomal gel, and liquid crystalline vehicles were prepared and compared for transdermal flux of GL-HCl. The liquid crystalline vehicles were more effective in increasing the skin permeation of GL-HCl than o/w cream and liposomal vehicles. Of the liquid crystalline vehicles tested, the permeation enhancing ability of the cubic phase was greater than that of the hexagonal phase when the nanoparticle dispersion was used. The skin permeation enhancing ability of the cubic nanoparticles for GL-HCl was further increased by employing both oleic acid and polyethylene glycol 200. Therefore, the cubic liquid crystalline nanodispersion containing oleic acid and PEG 200 can provide a possibility of clinical application of transdermal GL-HCl.

Theory of nematic order with aggregate dehydration for reversibly assembling proteins in concentrated solutions: Application to sickle-cell hemoglobin polymers

NASA Astrophysics Data System (ADS)

Hentschke, Reinhard; Herzfeld, Judith

1991-06-01

The reversible association of globular protein molecules in concentrated solution leads to highly polydisperse fibers, e.g., actin filaments, microtubules, and sickle-cell hemoglobin fibers. At high concentrations, excluded-volume interactions between the fibers lead to spontaneous alignment analogous to that in simple lyotropic liquid crystals. However, the phase behavior of reversibly associating proteins is complicated by the threefold coupling between the growth, alignment, and hydration of the fibers. In protein systems aggregates contain substantial solvent, which may cause them to swell or shrink, depending on osmotic stress. Extending previous work, we present a model for the equilibrium phase behavior of the above-noted protein systems in terms of simple intra- and interaggregate interactions, combined with equilibration of fiber-incorporated solvent with the bulk solvent. Specifically, we compare our model results to recent osmotic pressure data for sickle-cell hemoglobin and find excellent agreement. This comparison shows that particle interactions sufficient to cause alignment are also sufficient to squeeze significant amounts of solvent out of protein fibers. In addition, the model is in accord with findings from independent sedimentation and birefringence studies on sickle-cell hemoglobin.

Influence of the liquid crystal behaviour on the Langmuir and Langmuir-Blodgett film supramolecular architecture of an ionic liquid crystal.

PubMed

Pérez-Gregorio, Víctor; Giner, Ignacio; López, M Carmen; Gascón, Ignacio; Cavero, Emma; Giménez, Raquel

2012-06-01

A new luminescent ionic liquid crystal, called Ipz-2, has been synthesised and its mesophase behaviour and also at the air-liquid interface has been studied and compared with Ipz, another ionic pyrazole derivative, with a similar molecular structure, previously studied. The X-ray diffraction pattern shows that Ipz-2 exhibits hexagonal columnar mesomorphism, while Ipz adopts lamellar mesophases. Langmuir films of both compounds are flat and homogeneous at large areas per molecule, but create different supramolecular structures under further compression. Ipz-2 Langmuir films have been transferred onto solid substrates, and Atomic Force Microscopy (AFM) images of the Langmuir-Blodgett films have shown that large columnar structures hundreds of nm in diameter are formed on top of the initial monolayer, in contrast with well-defined trilayer LB films obtained for Ipz. Our results show that Ipz-2 has a tendency to stack in columnar arrangements both in liquid crystalline bulk and in Langmuir and Langmuir-Blodgett films. Copyright © 2012 Elsevier Inc. All rights reserved.

Evidence of low-density and high-density liquid phases and isochore end point for water confined to carbon nanotube

PubMed Central

Nomura, Kentaro; Kaneko, Toshihiro; Bai, Jaeil; Francisco, Joseph S.; Yasuoka, Kenji; Zeng, Xiao Cheng

2017-01-01

Possible transition between two phases of supercooled liquid water, namely the low- and high-density liquid water, has been only predicted to occur below 230 K from molecular dynamics (MD) simulation. However, such a phase transition cannot be detected in the laboratory because of the so-called “no-man’s land” under deeply supercooled condition, where only crystalline ices have been observed. Here, we show MD simulation evidence that, inside an isolated carbon nanotube (CNT) with a diameter of 1.25 nm, both low- and high-density liquid water states can be detected near ambient temperature and above ambient pressure. In the temperature–pressure phase diagram, the low- and high-density liquid water phases are separated by the hexagonal ice nanotube (hINT) phase, and the melting line terminates at the isochore end point near 292 K because of the retracting melting line from 292 to 278 K. Beyond the isochore end point (292 K), low- and high-density liquid becomes indistinguishable. When the pressure is increased from 10 to 600 MPa along the 280-K isotherm, we observe that water inside the 1.25-nm-diameter CNT can undergo low-density liquid to hINT to high-density liquid reentrant first-order transitions. PMID:28373562

Hexagonal ice in pure water and biological NMR samples.

PubMed

Bauer, Thomas; Gath, Julia; Hunkeler, Andreas; Ernst, Matthias; Böckmann, Anja; Meier, Beat H

2017-01-01

Ice, in addition to "liquid" water and protein, is an important component of protein samples for NMR spectroscopy at subfreezing temperatures but it has rarely been observed spectroscopically in this context. We characterize its spectroscopic behavior in the temperature range from 100 to 273 K, and find that it behaves like pure water ice. The interference of magic-angle spinning (MAS) as well as rf multiple-pulse sequences with Bjerrum-defect motion greatly influences the ice spectra.

Lithium ion intercalation in thin crystals of hexagonal TaSe2 gated by a polymer electrolyte

NASA Astrophysics Data System (ADS)

Wu, Yueshen; Lian, Hailong; He, Jiaming; Liu, Jinyu; Wang, Shun; Xing, Hui; Mao, Zhiqiang; Liu, Ying

2018-01-01

Ionic liquid gating has been used to modify the properties of layered transition metal dichalcogenides (TMDCs), including two-dimensional (2D) crystals of TMDCs used extensively recently in the device work, which has led to observations of properties not seen in the bulk. The main effect comes from the electrostatic gating due to the strong electric field at the interface. In addition, ionic liquid gating also leads to ion intercalation when the ion size of the gate electrolyte is small compared to the interlayer spacing of TMDCs. However, the microscopic processes of ion intercalation have rarely been explored in layered TMDCs. Here, we employed a technique combining photolithography device fabrication and electrical transport measurements on the thin crystals of hexagonal TaSe2 using multiple channel devices gated by a polymer electrolyte LiClO4/Polyethylene oxide (PEO). The gate voltage and time dependent source-drain resistances of these thin crystals were used to obtain information on the intercalation process, the effect of ion intercalation, and the correlation between the ion occupation of allowed interstitial sites and the device characteristics. We found a gate voltage controlled modulation of the charge density waves and a scattering rate of charge carriers. Our work suggests that ion intercalation can be a useful tool for layered materials engineering and 2D crystal device design.

Hierarchical self-assembly, coassembly, and self-organization of novel liquid crystalline lattices and superlattices from a twin-tapered dendritic benzamide and its four-cylinder-bundle supramolecular polymer.

PubMed

Percec, Virgil; Bera, Tushar K; Glodde, Martin; Fu, Qiongying; Balagurusamy, Venkatachalapathy S K; Heiney, Paul A

2003-02-17

The synthesis and structural analysis of the twin-dendritic benzamide 10, based on the first-generation, self-assembling, tapered dendrons 3,4,5-tris(4'-dodecyloxybenzyloxy)benzoic acid and 3,4,5-tris(4'-dodecyloxybenzyloxy)-1-aminobenzene, and the polymethacrylate, 20, which contains 10 as side groups, are presented. Benzamide 10 self-assembles into a supramolecular cylindrical dendrimer that self-organizes into a columnar hexagonal (Phi(h)) liquid crystalline (LC) phase. Polymer 20 self-assembles into an imperfect four-cylinder-bundle supramolecular dendrimer, and creates a giant vesicular supercylinder that self-organizes into a columnar nematic (N(c)) LC phase which displays short-range hexagonal order. In mixtures of 20 and 10, 10 acts as a guest and 20 as a host to create a perfect four-cylinder-bundle host-guest supramolecular dendrimer that coorganizes with 10. A diversity of Phi(h), simple rectangular columnar (Phi(r-s)) and centered rectangular columnar (Phi(r-c)), superlattices are produced at different ratios between 20 and 10. This diversity of LC lattices and superlattices is facilitated by the architecture of the twin-dendritic building block, polymethacrylate, the host-guest supramolecular assembly, and by hydrogen bonding along the center of the supramolecular cylinders generated from 10 and 20.

Structure of dental gallium alloys.

PubMed

Herø, H; Simensen, C J; Jørgensen, R B

1996-07-01

The interest in gallium alloys as a replacement for amalgam has increased in recent years due to the risk of environmental pollution from amalgam. Alloy powders with compositions close to those for alloys of amalgam are mixed with a liquid gallium alloy. The mix is condensed into a prepared cavity in much the same way as for amalgam. The aim of the present work was to study the structure of: (1) two commercial alloy powders containing mainly silver, tin and copper, and (2) the phases formed by mixing these powders with a liquid alloy of gallium, indium and tin. One of the alloy powders contained 9 wt% palladium. Cross-sections of cylindrical specimens made by these gallium mixes were investigated by scanning electron microscopy, energy dispersive spectroscopy and X-ray diffraction. Discrete grains of the following phases were found to be present in both gallium alloys: hexagonal Ag2Ga, tetragonal Cu(Pd)Ga2, cubic Ag9In4 and tetragonal beta-Sn. Indications of hexagonal or orthorhombic Ag2Sn were found in the remaining, unreacted alloy particles. In the palladium-containing alloy the X-ray reflections indicate a minor fraction of cubic Cu9Ga4 in addition to the Cu(Pd)Ga2 phase. Particles of beta-Sn are probably precipitated because Sn-Ga phases cannot be formed according to the binary phase diagram.

Long-Wavelength Rupturing Instability in Surface-Tension-Driven Benard Convection

NASA Technical Reports Server (NTRS)

Swift, J. B.; Hook, Stephen J. Van; Becerril, Ricardo; McCormick, W. D.; Swinney, H. L.; Schatz, Michael F.

1999-01-01

A liquid layer with a free upper surface and heated from below is subject to thermocapillary-induced convective instabilities. We use very thin liquid layers (0.01 cm) to significantly reduce buoyancy effects and simulate Marangoni convection in microgravity. We observe thermocapillary-driven convection in two qualitatively different modes, short-wavelength Benard hexagonal convection cells and a long-wavelength interfacial rupturing mode. We focus on the long-wavelength mode and present experimental observations and theoretical analyses of the long-wavelength instability. Depending on the depths and thermal conductivities of the liquid and the gas above it, the interface can rupture downwards and form a dry spot or rupture upwards and form a high spot. Linear stability theory gives good agreement to the experimental measurements of onset as long as sidewall effects are taken into account. Nonlinear theory correctly predicts the subcritical nature of the bifurcation and the selection between the dry spot and high spots.

Spontaneous formation and dynamics of half-skyrmions in a chiral liquid-crystal film

NASA Astrophysics Data System (ADS)

Nych, Andriy; Fukuda, Jun-Ichi; Ognysta, Uliana; Žumer, Slobodan; Muševič, Igor

2017-12-01

Skyrmions are coreless vortex-like excitations emerging in diverse condensed-matter systems, and real-time observation of their dynamics is still challenging. Here we report the first direct optical observation of the spontaneous formation of half-skyrmions. In a thin film of a chiral liquid crystal, depending on experimental conditions including film thickness, they form a hexagonal lattice whose lattice constant is a few hundred nanometres, or appear as isolated entities with topological defects compensating their charge. These half-skyrmions exhibit intriguing dynamical behaviour driven by thermal fluctuations. Numerical calculations of real-space images successfully corroborate the experimental observations despite the challenge because of the characteristic scale of the structures close to the optical resolution limit. A thin film of a chiral liquid crystal thus offers an intriguing platform that facilitates a direct investigation of the dynamics of topological excitations such as half-skyrmions and their manipulation with optical techniques.

High-resolution liquid patterns via three-dimensional droplet shape control.

PubMed

Raj, Rishi; Adera, Solomon; Enright, Ryan; Wang, Evelyn N

2014-09-25

Understanding liquid dynamics on surfaces can provide insight into nature's design and enable fine manipulation capability in biological, manufacturing, microfluidic and thermal management applications. Of particular interest is the ability to control the shape of the droplet contact area on the surface, which is typically circular on a smooth homogeneous surface. Here, we show the ability to tailor various droplet contact area shapes ranging from squares, rectangles, hexagons, octagons, to dodecagons via the design of the structure or chemical heterogeneity on the surface. We simultaneously obtain the necessary physical insights to develop a universal model for the three-dimensional droplet shape by characterizing the droplet side and top profiles. Furthermore, arrays of droplets with controlled shapes and high spatial resolution can be achieved using this approach. This liquid-based patterning strategy promises low-cost fabrication of integrated circuits, conductive patterns and bio-microarrays for high-density information storage and miniaturized biochips and biosensors, among others.

Slow molecular dynamics of water in a lyotropic complex fluid studied by deuterium conventional and spin-lattice relaxometry NMR.

PubMed

Rodríguez, C R; Pusiol, D J; Figueiredo Neto, A M; Seitter, R-O

2002-03-01

A nuclear magnetic resonance study of protons and deuterons in the mesomorphic phases of the micellar lyotropic mixture potassium laurate/1-decanol/heavy water is reported. The slow dynamical behavior of water molecules has been investigated with deuterons spin-lattice relaxation dispersion in the Larmor frequency range 10(3)

Polymorphism of POPE/cholesterol system: a 2H nuclear magnetic resonance and infrared spectroscopic investigation.

PubMed Central

Paré, C; Lafleur, M

1998-01-01

It is well established that cholesterol induces the formation of a liquid-ordered phase in phosphatidylcholine (PC) bilayers. The goal of this work is to examine the influence of cholesterol on phosphatidylethanolamine polymorphism. The behavior of 1-palmitoyl-2-oleoyl-phosphatidylethanolamine (POPE)/cholesterol mixtures was characterized using infrared and 2H nuclear magnetic resonance (NMR) spectroscopy (using POPE bearing a perdeuterated palmitoyl chain in the latter case). Our results reveal that cholesterol induces the formation of a liquid-ordered phase in POPE membranes, similar to those observed for various PC/cholesterol systems. However, the coexistence region of the gel and the liquid-ordered phases is different from that proposed for PC/cholesterol systems. The results indicate a progressive broadening of the gel-to-fluid phase transition, suggesting the absence of an eutectic. In addition, there is a progressive downshift of the end of the transition for cholesterol content higher than 10 mol %. Cholesterol has an ordering effect on the acyl chains of POPE, but it is less pronounced than for the PC equivalent. This study also shows that the cholesterol effect on the lamellar-to-hexagonal (L(alpha)-H(II)) phase transition is not monotonous. It shifts the transition toward the low temperatures between 0 and 30 mol % cholesterol but shifts it toward the high temperatures when cholesterol content is higher than 30 mol %. The change in conformational order of the lipid acyl chains, as probed by the shift of the symmetric methylene C-H stretching, shows concerted variations. Finally, we show that cholesterol maintains its chain ordering effect in the hexagonal phase. PMID:9533701

Large-Scale Structure and Hyperuniformity of Amorphous Ices

NASA Astrophysics Data System (ADS)

Martelli, Fausto; Torquato, Salvatore; Giovambattista, Nicolas; Car, Roberto

2017-09-01

We investigate the large-scale structure of amorphous ices and transitions between their different forms by quantifying their large-scale density fluctuations. Specifically, we simulate the isothermal compression of low-density amorphous ice (LDA) and hexagonal ice to produce high-density amorphous ice (HDA). Both HDA and LDA are nearly hyperuniform; i.e., they are characterized by an anomalous suppression of large-scale density fluctuations. By contrast, in correspondence with the nonequilibrium phase transitions to HDA, the presence of structural heterogeneities strongly suppresses the hyperuniformity and the system becomes hyposurficial (devoid of "surface-area fluctuations"). Our investigation challenges the largely accepted "frozen-liquid" picture, which views glasses as structurally arrested liquids. Beyond implications for water, our findings enrich our understanding of pressure-induced structural transformations in glasses.

Refusing to Twist: Demonstration of a Line Hexatic Phase in DNA Liquid Crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Strey, H. H.; NICHD/LPSB, National Institutes of Health, Building 12A/2041, Bethesda, Maryland 20892-5626; Wang, J.

2000-04-03

We report conclusive high resolution small angle x-ray scattering evidence that long DNA fragments form an untwisted line hexatic phase between the cholesteric and the crystalline phases. The line hexatic phase is a liquid-crystalline phase with long-range hexagonal bond-orientational order, long-range nematic order, but liquidlike, i.e., short-range, positional order. So far, it has not been seen in any other three dimensional system. By line-shape analysis of x-ray scattering data we found that positional order decreases when the line hexatic phase is compressed. We suggest that such anomalous behavior is a result of the chiral nature of DNA molecules. (c) 2000more » The American Physical Society.« less

Development of the ReaxFFCBN reactive force field for the improved design of liquid CBN hydrogen storage materials.

PubMed

Pai, Sung Jin; Yeo, Byung Chul; Han, Sang Soo

2016-01-21

Liquid CBN (carbon-boron-nitrogen) hydrogen-storage materials such as 3-methyl-1,2-BN-cyclopentane have the advantage of being easily accessible for use in current liquid-fuel infrastructure. To develop practical liquid CBN hydrogen-storage materials, it is of great importance to understand the reaction pathways of hydrogenation/dehydrogenation in the liquid phase, which are difficult to discover by experimental methods. Herein, we developed a reactive force field (ReaxFFCBN) from quantum mechanical (QM) calculations based on density functional theory for the storage of hydrogen in BN-substituted cyclic hydrocarbon materials. The developed ReaxFFCBN provides similar dehydrogenation pathways and energetics to those predicted by QM calculations. Moreover, molecular dynamics (MD) simulations with the developed ReaxFFCBN can predict the stability and dehydrogenation behavior of various liquid CBN hydrogen-storage materials. Our simulations reveal that a unimolecular dehydrogenation mechanism is preferred in liquid CBN hydrogen-storage materials. However, as the temperature in the simulation increases, the contribution of a bimolecular dehydrogenation mechanism also increases. Moreover, our ReaxFF MD simulations show that in terms of thermal stability and dehydrogenation kinetics, liquid CBN materials with a hexagonal structure are more suitable materials than those with a pentagonal structure. We expect that the developed ReaxFFCBN could be a useful protocol in developing novel liquid CBN hydrogen-storage materials.

Modeling of monolayer charge-stabilized colloidal crystals with static hexagonal crystal lattice

NASA Astrophysics Data System (ADS)

Nagatkin, A. N.; Dyshlovenko, P. E.

2018-01-01

The mathematical model of monolayer colloidal crystals of charged hard spheres in liquid electrolyte is proposed. The particles in the monolayer are arranged into the two-dimensional hexagonal crystal lattice. The model enables finding elastic constants of the crystals from the stress-strain dependencies. The model is based on the nonlinear Poisson-Boltzmann differential equation. The Poisson-Boltzmann equation is solved numerically by the finite element method for any spatial configuration. The model has five geometrical and electrical parameters. The model is used to study the crystal with particles comparable in size with the Debye length of the electrolyte. The first- and second-order elastic constants are found for a broad range of densities. The model crystal turns out to be stable relative to small uniform stretching and shearing. It is also demonstrated that the Cauchy relation is not fulfilled in the crystal. This means that the pair effective interaction of any kind is not sufficient to proper model the elasticity of colloids within the one-component approach.

NUCLEAR REACTOR CORE DESIGN

DOEpatents

Mahlmeister, J.E.; Peck, W.S.; Haberer, W.V.; Williams, A.C.

1960-03-22

An improved core design for a sodium-cooled, graphitemoderated nuclear reactor is described. The improved reactor core comprises a number of blocks of moderator material, each block being in the shape of a regular prism. A number of channels, extending the length of each block, are disposed around the periphery. When several blocks are placed in contact to form the reactor core, the channels in adjacent blocks correspond with each other to form closed conduits extending the length of the core. Fuel element clusters are disposed in these closed conduits, and liquid coolant is forced through the annulus between the fuel cluster and the inner surface of the conduit. In a preferred embodiment of the invention, the moderator blocks are in the form of hexagonal prisms with longitudinal channels cut into the corners of the hexagon. The main advantage of an "edge-loaded" moderator block is that fewer thermal neutrons are absorbed by the moderator cladding, as compared with a conventional centrally loaded moderator block.

Optical determination of crystal phase in semiconductor nanocrystals

PubMed Central

Lim, Sung Jun; Schleife, André; Smith, Andrew M.

2017-01-01

Optical, electronic and structural properties of nanocrystals fundamentally derive from crystal phase. This is especially important for polymorphic II–VI, III–V and I-III-VI2 semiconductor materials such as cadmium selenide, which exist as two stable phases, cubic and hexagonal, each with distinct properties. However, standard crystallographic characterization through diffraction yields ambiguous phase signatures when nanocrystals are small or polytypic. Moreover, diffraction methods are low-throughput, incompatible with solution samples and require large sample quantities. Here we report the identification of unambiguous optical signatures of cubic and hexagonal phases in II–VI nanocrystals using absorption spectroscopy and first-principles electronic-structure theory. High-energy spectral features allow rapid identification of phase, even in small nanocrystals (∼2 nm), and may help predict polytypic nanocrystals from differential phase contributions. These theoretical and experimental insights provide simple and accurate optical crystallographic analysis for liquid-dispersed nanomaterials, to improve the precision of nanocrystal engineering and improve our understanding of nanocrystal reactions. PMID:28513577

European Conference on Organized Thin Films (4th) Held in Bangor on September 10 - 12, 1992

DTIC Science & Technology

1992-09-12

Blodgett films from discotic liquid-crystalline compounds . V.V.Tsukruk, J.H. Wendorff, O.Karthaus, and H.Ringsdorf (Germany/Ukraine) DP2 Alternate...backbone and yield two different domain shapes observ, j in the LE/LC phase coexistence range: one compound exhibits a mostly hexagonal sh:.pe, since...No.: 91113 464.1- films with predetermined alternation of three or more;. /4/ Y. Lvov, 0. Decher arnd H. Mbhwald different compounds in a ABAB...CDCD

Formation of Nanostructures on the Nickel Metal Surface in Ionic Liquid under Anodizing

NASA Astrophysics Data System (ADS)

Lebedeva, O. K.; Root, N. V.; Kultin, D. Yu.; Kalmykov, K. B.; Kustov, L. M.

2018-05-01

The formation of nanostructures in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide on the surface of a nickel electrode during anodizing was studied. Hexagonal ordered surface nanostructures were found to form in a narrow range of current densities. The form of the potential transients of the nickel electrode corresponded to the morphology of the nickel surface obtained which was studied by electron microscopy. No other types of nanostructures were found under the electrosynthesis conditions under study.

Genesis of Bénard-Marangoni Patterns in Thin Liquid Films Drying into Air

NASA Astrophysics Data System (ADS)

Colinet, P.; Chauvet, F.; Dehaeck, S.

Inspired by many years of motivating collaboration between the first author and Prof. Manuel G. Velarde, in the field of surface-tension-driven instabilities, pattern formation, and transition to turbulence, this paper presents recent experimental results obtained in collaboration with the second and third authors at the TIPs laboratory in Brussels. Namely, the evolution of Bénard-like patterns is explored for pure liquid layers evaporating into air, from chaotic regimes down to more stable structures with predominant hexagonal symmetry. Drying liquid layers indeed appear as a particularly simple example of system where, due to the decreasing liquid depth, the preferred wavelength of the pattern is continuously decreased in time, hence requiring perpetual creation of new convective cells. Such pattern "genesis" appears to lead to disordered structures with interesting characteristics, whose preliminary experimental investigation is carried out here. This paper is dedicated to Prof. Manuel G. Velarde, at the occasion of his 70th birthday, as a mark of deep gratitude for all positive scientific and cultural influences he had and he still has on many young scientists.

Molecular dynamics of the water liquid-vapor interface

NASA Technical Reports Server (NTRS)

Wilson, M. A.; Pohorille, A.; Pratt, L. R.; MacElroy, R. D. (Principal Investigator)

1987-01-01

The results of molecular dynamics calculations on the equilibrium interface between liquid water and its vapor at 325 K are presented. For the TIP4P model of water intermolecular pair potentials, the average surface dipole density points from the vapor to the liquid. The most common orientations of water molecules have the C2 nu molecular axis roughly parallel to the interface. The distributions are quite broad and therefore compatible with the intermolecular correlations characteristic of bulk liquid water. All near-neighbor pairs in the outermost interfacial layers are hydrogen bonded according to the common definition adopted here. The orientational preferences of water molecules near a free surface differ from those near rigidly planar walls which can be interpreted in terms of patterns found in hexagonal ice 1. The mean electric field in the interfacial region is parallel to the mean polarization which indicates that attention cannot be limited to dipolar charge distributions in macroscopic descriptions of the electrical properties of this interface. The value of the surface tension obtained is 132 +/- 46 dyn/cm, significantly different from the value for experimental water of 68 dyn/cm at 325 K.

Synthesis of surfactant-free electrostatically stabilized gold nanoparticles by plasma-induced liquid chemistry

NASA Astrophysics Data System (ADS)

Patel, J.; Němcová, L.; Maguire, P.; Graham, W. G.; Mariotti, D.

2013-06-01

Plasma-induced non-equilibrium liquid chemistry is used to synthesize gold nanoparticles (AuNPs) without using any reducing or capping agents. The morphology and optical properties of the synthesized AuNPs are characterized by transmission electron microscopy (TEM) and ultraviolet-visible spectroscopy. Plasma processing parameters affect the particle shape and size and the rate of the AuNP synthesis process. Particles of different shapes (e.g. spherical, triangular, hexagonal, pentagonal, etc) are synthesized in aqueous solutions. In particular, the size of the AuNPs can be tuned from 5 nm to several hundred nanometres by varying the initial gold precursor (HAuCl4) concentration from 2.5 μM to 1 mM. In order to reveal details of the basic plasma-liquid interactions that lead to AuNP synthesis, we have measured the solution pH, conductivity and hydrogen peroxide (H2O2) concentration of the liquid after plasma processing, and conclude that H2O2 plays the role of the reducing agent which converts Au+3 ions to Au0 atoms, leading to nucleation growth of the AuNPs.

Broad hexagonal columnar mesophases formation in bioinspired transition-metal complexes of simple fatty acid meta-octaester derivatives of meso-tetraphenyl porphyrins.

PubMed

Wu, Bin; Chen, Keyang; Deng, Yuchen; Chen, Jian; Liu, Chengjie; Cheng, Rongshi; Chen, Dongzhong

2015-02-23

A series of meta-substituted fatty acid octaester derivatives and their transition-metal complexes of meso- tetraphenyl porphyrins (TPP-8OOCR, with R = C(n-1)H(2n-1), n = 8, 12, or 16) have been prepared through very simple synthesis protocols. The thermotropic phase behavior and the liquid crystalline (LC) organization structures of the synthesized porphyrin derivatives were systematically investigated by a combination of differential scanning calorimetry (DSC), polarized optical microscopy (POM), and variable-temperature small-angle X-ray scattering/wide-angle X-ray scattering (SAXS/WAXS) techniques. The shorter octanoic acid ester substituted porphyrin (C8-TPP) did not show liquid crystallinity and its metal porphyrins exhibited an uncommon columnar mesophase. The lauric acid octaester (C12-TPP) and the palmitic acid octaester (C16-TPP) series porphyrins generated hexagonal columnar mesophase Colh. Moreover, the metal porphyrins C12-TPPM and C16-TPPM with M = Zn, Cu, or Ni, exhibited well-organized Colh mesophases of broad LC temperature ranges increasing in the order of TPPNi

Discotic columnar liquid crystal studied in the bulk and nanoconfined states by molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Busselez, Rémi; Cerclier, Carole V.; Ndao, Makha; Ghoufi, Aziz; Lefort, Ronan; Morineau, Denis

2014-10-01

A prototypical Gay Berne discotic liquid crystal was studied by means of molecular dynamics simulations both in the bulk state and under confinement in a nanoporous channel. The phase behavior of the confined system strongly differs from its bulk counterpart: the bulk isotropic-to-columnar transition is replaced by a continuous ordering from a paranematic to a columnar phase. Moreover, a new transition is observed at a lower temperature in the confined state, which corresponds to a reorganization of the intercolumnar order. It reflects the competing effects of pore surface interaction and genuine hexagonal packing of the columns. The translational molecular dynamics in the different phases has been thoroughly studied and discussed in terms of collective relaxation modes, non-Gaussian behavior, and hopping processes.

Maxon and roton measurements in nanoconfined 4He

NASA Astrophysics Data System (ADS)

Bryan, M. S.; Sokol, P. E.

2018-05-01

We investigate the behavior of the collective excitations of adsorbed 4He in an ordered hexagonal mesopore, examining the crossover from a thin film to a confined fluid. Here, we present the inelastic scattering results as a function of filling at constant temperature. We find a monotonic transition of the maxon excitation as a function of filling. This has been interpreted as corresponding to an increasing density of the adsorbed helium, which approaches the bulk value as filling increases. The roton minimum exhibits a more complicated behavior that does not monotonically approach bulk values as filling increases. The full pore scattering resembles the bulk liquid accompanied by a layer mode. The maxon and roton scattering, taken together, at intermediate fillings does not correspond to a single bulk liquid dispersion at negative, low, or high pressure.

Facile green synthesis of silver doped fluor-hydroxyapatite/β-cyclodextrin nanocomposite in the dual acting fluorine-containing ionic liquid medium for bone substitute applications

NASA Astrophysics Data System (ADS)

Jegatheeswaran, S.; Selvam, S.; Sri Ramkumar, V.; Sundrarajan, M.

2016-05-01

A novel green route has approached for the synthesis of silver doped fluor-hydroxyapatite/β-cyclodextrin composite by the assistance of fluorine-based ionic liquid. The selected [BMIM]BF4 ionic liquid for this work plays a dual role as fluoride source and templating agent. It helps to improve the crystalline structures and the shape of the composites. The crystallinity, surface morphology, topographical studies of the synthesized composite were validated. The XRD results of the composite show typical Ag reflection peaks at 38.1°, 44.2° and 63.4°. The ionic liquid assisted composite displayed the hexagonal shaped HA particles, which are surrounded by spherical nano-Ag particles and these particles are uniformly dispersed in the β-cyclodextrin matrix in both horizontal and cross sections from surface morphology observations. The Ionic liquid assisted silver doped fluor-hydroxyapatite/β-cyclodextrin composite exhibited very good antibacterial activities against Escherichia coli, Salmonella typhi, Klebsiella pneumonia and Serratia liquefaciens pathogens. The antibacterial proficiencies were established using Confocal Laser Scanning Microscopic developed biofilms images and bacterial growth curve analysis. The cytotoxicity results of the ionic liquid assisted composite analyzed by cell proliferation in vitro studies using human osteosarcoma cell line (MG-63) and this study has shown excellent biocompatibility.

Predesigned surface patterns and topological defects control the active matter.

NASA Astrophysics Data System (ADS)

Turiv, Taras; Peng, Chenhui; Guo, Yubing; Wei, Qi-Huo; Lavrentovich, Oleg

Active matter exhibits remarkable patterns of never-ending dynamics with giant fluctuations of concentration, varying order, nucleating and annihilating topological defects. These patterns can be seen in active systems of both biological and artificial origin. A fundamental question is whether and how one can control this chaotic out-of-equilibrium behavior. We demonstrate a robust control of local concentration, trajectories of active self-propelled units and the net flows of active bacteria Bacillus Substilis by imposing pre-designed surface patterns of orientational order in a water-based lyotropic chromonic liquid crystal. The patterns force the bacteria to gather into dynamic swarms with spatially modulated concentration and well-defined polarity of motion. Topological defects produce net motion of bacteria with a unidirectional circulation, while pairs of defects induce a pumping action. The qualitative features of the dynamics can be explained by interplay of curvature and activity, in particular, by ability of mixed splay-bend curvatures to generate threshold-less active flows. The demonstrated level of control opens opportunities in engineering materials and devices that mimic rich functionality of living systems. This work was supported by NSF Grants DMR-1507637, DMS-1434185, CMMI-1436565, by the Petroleum Research Grant PRF# 56046-ND7 administered by the American Chemical Society.

Proton Diffusion through Bilayer Pores

DOE PAGES

McDaniel, Jesse G.; Yethiraj, Arun

2017-09-26

The transport of protons through channels in complex environments is important in biology and materials science. In this work, we use multistate empirical valence bond simulations to study proton transport within a well-defined bilayer pore in a lamellar L β phase lyotropic liquid crystal (LLC). The LLC is formed from the self-assembly of dicarboxylate gemini surfactants in water, and a bilayer-spanning pore of radius of approximately 3–5 Å results from the uneven partitioning of surfactants between the two leaflets of the lamella. Local proton diffusion within the pore is significantly faster than diffusion at the bilayer surface, which is duemore » to the greater hydrophobicity of the surfactant/water interface within the pore. Proton diffusion proceeds by surface transport along exposed hydrophobic pockets at the surfactant/water interface and depends on the continuity of hydronium–water hydrogen bond networks. At the bilayer surface, there is a reduced fraction of the “Zundel” intermediates that are central to the Grotthuss transport mechanism, whereas the fraction of these species within the bilayer pore is similar to that in bulk water. Our results demonstrate that the chemical nature of the confining interface, in addition to confinement length scale, is an important determiner of local proton transport in nanoconfined aqueous environments.« less

Dynamic states of swimming bacteria in a nematic liquid crystal cell with homeotropic alignment

DOE PAGES

Zhou, Shuang; Tovkach, Oleh; Golovaty, Dmitry; ...

2017-05-17

Flagellated bacteria such as Escherichia coli and Bacillus subtilis exhibit effective mechanisms for swimming in fluids and exploring the surrounding environment. In isotropic fluids such as water, the bacteria change swimming direction through the run-and-tumble process. Lyotropic chromonic liquid crystals (LCLCs) have been introduced recently as an anisotropic environment in which the direction of preferred orientation, the director, guides the bacterial trajectories. In this work, we describe the behavior of bacteria B. subtilis in a homeotropic LCLC geometry, in which the director is perpendicular to the bounding plates of a shallow cell. We demonstrate that the bacteria are capable ofmore » overcoming the stabilizing elastic forces of the LCLC and swim perpendicularly to the imposed director (and parallel to the bounding plates). The effect is explained by a finite surface anchoring of the director at the bacterial body; the role of surface anchoring is analyzed by numerical simulations of a rod realigning in an otherwise uniform director field. Shear flows produced by a swimming bacterium cause director distortions around its body, as evidenced both by experiments and numerical simulations. These distortions contribute to a repulsive force that keeps the swimming bacterium at a distance of a few micrometers away from the bounding plates. The homeotropic alignment of the director imposes two different scenarios of bacterial tumbling: one with an 180° reversal of the horizontal velocity and the other with the realignment of the bacterium by two consecutive 90° turns. Finally, in the second case, the angle between the bacterial body and the imposed director changes from 90° to 0° and then back to 90°; the new direction of swimming does not correlate with the previous swimming direction.« less

Dynamic states of swimming bacteria in a nematic liquid crystal cell with homeotropic alignment

NASA Astrophysics Data System (ADS)

Zhou, Shuang; Tovkach, Oleh; Golovaty, Dmitry; Sokolov, Andrey; Aranson, Igor S.; Lavrentovich, Oleg D.

2017-05-01

Flagellated bacteria such as Escherichia coli and Bacillus subtilis exhibit effective mechanisms for swimming in fluids and exploring the surrounding environment. In isotropic fluids such as water, the bacteria change swimming direction through the run-and-tumble process. Lyotropic chromonic liquid crystals (LCLCs) have been introduced recently as an anisotropic environment in which the direction of preferred orientation, the director, guides the bacterial trajectories. In this work, we describe the behavior of bacteria B. subtilis in a homeotropic LCLC geometry, in which the director is perpendicular to the bounding plates of a shallow cell. We demonstrate that the bacteria are capable of overcoming the stabilizing elastic forces of the LCLC and swim perpendicularly to the imposed director (and parallel to the bounding plates). The effect is explained by a finite surface anchoring of the director at the bacterial body; the role of surface anchoring is analyzed by numerical simulations of a rod realigning in an otherwise uniform director field. Shear flows produced by a swimming bacterium cause director distortions around its body, as evidenced both by experiments and numerical simulations. These distortions contribute to a repulsive force that keeps the swimming bacterium at a distance of a few micrometers away from the bounding plates. The homeotropic alignment of the director imposes two different scenarios of bacterial tumbling: one with an 180° reversal of the horizontal velocity and the other with the realignment of the bacterium by two consecutive 90° turns. In the second case, the angle between the bacterial body and the imposed director changes from 90° to 0° and then back to 90° the new direction of swimming does not correlate with the previous swimming direction.

Stabilizing the hexagonal close packed structure of hard spheres with polymers: Phase diagram, structure, and dynamics

NASA Astrophysics Data System (ADS)

Edison, John R.; Dasgupta, Tonnishtha; Dijkstra, Marjolein

2016-08-01

We study the phase behaviour of a binary mixture of colloidal hard spheres and freely jointed chains of beads using Monte Carlo simulations. Recently Panagiotopoulos and co-workers predicted [Nat. Commun. 5, 4472 (2014)] that the hexagonal close packed (HCP) structure of hard spheres can be stabilized in such a mixture due to the interplay between polymer and the void structure in the crystal phase. Their predictions were based on estimates of the free-energy penalty for adding a single hard polymer chain in the HCP and the competing face centered cubic (FCC) phase. Here we calculate the phase diagram using free-energy calculations of the full binary mixture and find a broad fluid-solid coexistence region and a metastable gas-liquid coexistence region. For the colloid-monomer size ratio considered in this work, we find that the HCP phase is only stable in a small window at relatively high polymer reservoir packing fractions, where the coexisting HCP phase is nearly close packed. Additionally we investigate the structure and dynamic behaviour of these mixtures.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zare, Bijan; Faramarzi, Mohammad Ali; Sepehrizadeh, Zargham

Highlights: ► Biosynthesis of rod shape tellurium nanoparticles with a hexagonal crystal structure. ► Extraction procedure for isolation of tellurium nanoparticles from Bacillus sp. BZ. ► Extracted tellurium nanoparticles have good bactericidal activity against some bacteria. -- Abstract: In this study, a tellurium-transforming Bacillus sp. BZ was isolated from the Caspian Sea in northern Iran. The isolate was identified by various tests and 16S rDNA analysis, and then used to prepare elemental tellurium nanoparticles. The isolate was subsequently used for the intracellular biosynthesis of elemental tellurium nanoparticles. The biogenic nanoparticles were released by liquid nitrogen and purified by an n-octylmore » alcohol water extraction system. The shape, size, and composition of the extracted nanoparticles were characterized. The transmission electron micrograph showed rod-shaped nanoparticles with dimensions of about 20 nm × 180 nm. The energy dispersive X-ray and X-ray diffraction spectra respectively demonstrated that the extracted nanoparticles consisted of only tellurium and have a hexagonal crystal structure. This is the first study to demonstrate a biological method for synthesizing rod-shaped elemental tellurium by a Bacillus sp., its extraction and its antibacterial activity against different clinical isolates.« less

Electrically insulating thermal nano-oils using 2D fillers.

PubMed

Taha-Tijerina, Jaime; Narayanan, Tharangattu N; Gao, Guanhui; Rohde, Matthew; Tsentalovich, Dmitri A; Pasquali, Matteo; Ajayan, Pulickel M

2012-02-28

Different nanoscale fillers have been used to create composite fluids for applications such as thermal management. The ever increasing thermal loads in applications now require advanced operational fluids, for example, high thermal conductivity dielectric oils in transformers. These oils require excellent filler dispersion, high thermal conduction, but also electrical insulation. Such thermal oils that conform to this thermal/electrical requirement, and yet remain in highly suspended stable state, have not yet been synthesized. We report here the synthesis and characterization of stable high thermal conductivity Newtonian nanofluids using exfoliated layers of hexagonal boron nitride in oil without compromising its electrically insulating property. Two-dimensional nanosheets of hexagonal boron nitride are liquid exfoliated in isopropyl alcohol and redispersed in mineral oil, used as standard transformer oil, forming stable nanosuspensions with high shelf life. A high electrical resistivity, even higher than that of the base oil, is maintained for the nano-oil containing small weight fraction of the filler (0.01 wt %), whereas the thermal conductivity was enhanced. The low dissipation factor and high pour point for this nano-oil suggests several applications in thermal management.

Pattern formation in a liquid-crystal light valve with feedback, including polarization, saturation, and internal threshold effects

NASA Astrophysics Data System (ADS)

Neubecker, R.; Oppo, G.-L.; Thuering, B.; Tschudi, T.

1995-07-01

The use of liquid-crystal light valves (LCLV's) as nonlinear elements in diffractive optical systems with feedback leads to the formation of a variety of optical patterns. The spectrum of possible spatial instabilities is shown to be even richer when the LCLV's capability for polarization modulation is utilized and internal threshold and saturation effects are considered. We derive a model for the feedback system based on a realistic description of the LCLV's internal function and coupling to a polarizer. Thresholds of pattern formation are compared to the common Kerr-type approximation and show transitions involving rolls, squares, hexagons, and tiled patterns. Numerical and experimental results confirm our theoretical predictions and unveil how patterns and their typical length scales can be easily controlled by changes of the parameters.

Liquid crystal alignment in electro-responsive nanostructured thermosetting materials based on block copolymer dispersed liquid crystal.

PubMed

Tercjak, A; Garcia, I; Mondragon, I

2008-07-09

Novel well-defined nanostructured thermosetting systems were prepared by modification of a diglicydylether of bisphenol-A epoxy resin (DGEBA) with 10 or 15 wt% amphiphilic poly(styrene-b-ethylene oxide) block copolymer (PSEO) and 30 or 40 wt% low molecular weight liquid crystal 4'-(hexyl)-4-biphenyl-carbonitrile (HBC) using m-xylylenediamine (MXDA) as a curing agent. The competition between well-defined nanostructured materials and the ability for alignment of the liquid crystal phase in the materials obtained has been studied by atomic and electrostatic force microscopy, AFM and EFM, respectively. Based on our knowledge, this is the first time that addition of an adequate amount (10 wt%) of a block copolymer to 40 wt% HBC-(DGEBA/MXDA) leads to a well-organized nanostructured thermosetting system (between a hexagonal and worm-like ordered structure), which is also electro-responsive with high rate contrast. This behavior was confirmed using electrostatic force microscopy (EFM), by means of the response of the HBC liquid crystal phase to the voltage applied to the EFM tip. In contrast, though materials containing 15 wt% PSEO and 30 wt% HBC also form a well-defined nanostructured thermosetting system, they do not show such a high contrast between the uncharged and charged surface.

First Principles Study for Proton Transport and Diffusion Behavior in Hydrous Hexagonal WO3

NASA Astrophysics Data System (ADS)

Liu, Chi-Ping; Zhou, Fei; Ozolins, Vidvuds; QPAM Team

2013-03-01

Proton transport is of great importance in biological species and energy storage and conversion systems. Previous studies have shown fast proton conduction in liquids and polymers but seldom in inorganic materials. In this work, first principles density functional theory (DFT) reveals that the formation of hydronium and water chains inside the hexagonal channels plays the key roles for the anomalously fast proton transport, by following modified Grotthuss mechanism. Our DFT study shows the detailed microscopic proton diffusion mechanism along the channel in hydrous WO3 with 50% water composition, which is proper for water chain formation. The water chain in the channel serves as a possible diffusion media for hydronium (H3O +) . With the continuous formation and cleavage of hydrogen bonds in the channel, the hydronium diffuses by hydrogen bonds exchange between water molecules. This mechanism is very similar with Grotthuss relay mechanism for proton transport in liquid. The possible proton diffusion were studied for hydronium is either far away from the water chain bond defect or next to H2O defect at the end of water chain. The diffusion barriers for both conditions are around 150 meV to 200 meV, and water defects reorganization in the chain is the rate-limited step for proton diffusion. These small diffusion barriers could explain the fast 1-D proton transport in hydrous WO3 channel. Further studies about fast proton transport in other inorganic materials could be an important topic in not only biochemistry but also clean energy applications like fuel cell applications.

Heating- and pressure-induced transformations in amorphous and hexagonal ice: A computer simulation study using the TIP4P/2005 model

NASA Astrophysics Data System (ADS)

Engstler, Justin; Giovambattista, Nicolas

2017-08-01

We characterize the phase behavior of glassy water by performing extensive out-of-equilibrium molecular dynamics simulations using the TIP4P/2005 water model. Specifically, we study (i) the pressure-induced transformations between low-density (LDA) and high-density amorphous ice (HDA), (ii) the pressure-induced amorphization (PIA) of hexagonal ice (Ih), (iii) the heating-induced LDA-to-HDA transformation at high pressures, (iv) the heating-induced HDA-to-LDA transformation at low and negative pressures, (v) the glass transition temperatures of LDA and HDA as a function of pressure, and (vi) the limit of stability of LDA upon isobaric heating and isothermal decompression (at negative pressures). These transformations are studied systematically, over a wide range of temperatures and pressures, allowing us to construct a P-T phase diagram for glassy TIP4P/2005 water. Our results are in qualitative agreement with experimental observations and with the P-T phase diagram obtained for glassy ST2 water that exhibits a liquid-liquid phase transition and critical point. We also discuss the mechanism for PIA of ice Ih and show that this is a two-step process where first, the hydrogen-bond network (HBN) is distorted and then the HBN abruptly collapses. Remarkably, the collapse of the HB in ice Ih occurs when the average molecular orientations order, a measure of the tetrahedrality of the HBN, is of the same order as in LDA, suggesting a common mechanism for the LDA-to-HDA and Ih-to-HDA transformations.

Heating- and pressure-induced transformations in amorphous and hexagonal ice: A computer simulation study using the TIP4P/2005 model.

PubMed

Engstler, Justin; Giovambattista, Nicolas

2017-08-21

We characterize the phase behavior of glassy water by performing extensive out-of-equilibrium molecular dynamics simulations using the TIP4P/2005 water model. Specifically, we study (i) the pressure-induced transformations between low-density (LDA) and high-density amorphous ice (HDA), (ii) the pressure-induced amorphization (PIA) of hexagonal ice (I h ), (iii) the heating-induced LDA-to-HDA transformation at high pressures, (iv) the heating-induced HDA-to-LDA transformation at low and negative pressures, (v) the glass transition temperatures of LDA and HDA as a function of pressure, and (vi) the limit of stability of LDA upon isobaric heating and isothermal decompression (at negative pressures). These transformations are studied systematically, over a wide range of temperatures and pressures, allowing us to construct a P-T phase diagram for glassy TIP4P/2005 water. Our results are in qualitative agreement with experimental observations and with the P-T phase diagram obtained for glassy ST2 water that exhibits a liquid-liquid phase transition and critical point. We also discuss the mechanism for PIA of ice I h and show that this is a two-step process where first, the hydrogen-bond network (HBN) is distorted and then the HBN abruptly collapses. Remarkably, the collapse of the HB in ice I h occurs when the average molecular orientations order, a measure of the tetrahedrality of the HBN, is of the same order as in LDA, suggesting a common mechanism for the LDA-to-HDA and I h -to-HDA transformations.

Phase- and size-controllable synthesis of hexagonal upconversion rare-earth fluoride nanocrystals through an oleic acid/ionic liquid two-phase system.

PubMed

He, Meng; Huang, Peng; Zhang, Chunlei; Ma, Jiebing; He, Rong; Cui, Daxiang

2012-05-07

Herein, we introduce a facile, user- and environmentally friendly (n-octanol-induced) oleic acid (OA)/ionic liquid (IL) two-phase system for the phase- and size-controllable synthesis of water-soluble hexagonal rare earth (RE = La, Gd, and Y) fluoride nanocrystals with uniform morphologies (mainly spheres and elongated particles) and small sizes (<50 nm). The unique role of the IL 1-butyl-3-methylimidazolium hexafluorophosphate (BmimPF(6)) and n-octanol in modulating the phase structure and particle size are discussed in detail. More importantly, the mechanism of the (n-octanol-induced) OA/IL two-phase system, the formation of the RE fluoride nanocrystals, and the distinctive size- and morphology-controlling capacity of the system are presented. BmimPF(6) is versatile in term of crystal-phase manipulation, size and shape maintenance, and providing water solubility in a one-step reaction. The luminescent properties of Er(3+)-, Ho(3+)-, and Tm(3+)-doped LaF(3), NaGdF(4), and NaYF(4) nanocrystals were also studied. It is worth noting that the as-prepared products can be directly dispersed in water due to the hydrophilic property of Bmim(+) (cationic part of the IL) as a capping agent. This advantageous feature has made the IL-capped products favorable in facile surface modifications, such as the classic Stober method. Finally, the cytotoxicity evaluation of NaYF(4):Yb,Er nanocrystals before and after silica coating was conducted for further biological applications. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and Properties of Rigid-Rod Benzobisazole Polymers Containing Benzothiazole Pendent Groups

DTIC Science & Technology

1990-11-16

crystalline phase. Poly-p- benzamides containing bulky methyl, nitro or bromo groups affects intermolecular forces to such a large extent that lyotropic...phosphate/m- cresol . Initial attempts in our laboratory involved pendent phenylation via the synthesis of a series of phenylated terphenyl diacids and...range 2.5-9.3 dL/g and exhibited partial solubility (ə%) in m- cresol /strong acid mixtures. Concentrated solutions (>5-) could not be obtained in any

Detector shape in hexagonal sampling grids

NASA Astrophysics Data System (ADS)

Baronti, Stefano; Capanni, Annalisa; Romoli, Andrea; Santurri, Leonardo; Vitulli, Raffaele

2001-12-01

Recent improvements in CCD technology make hexagonal sampling attractive for practical applications and bring a new interest on this topic. In the following the performances of hexagonal sampling are analyzed under general assumptions and compared with the performances of conventional rectangular sampling. This analysis will take into account both the lattice form (squared, rectangular, hexagonal, and regular hexagonal), and the pixel shape. The analyzed hexagonal grid will not based a-priori on a regular hexagon tessellation, i.e., no constraints will be made on the ratio between the sampling frequencies in the two spatial directions. By assuming an elliptic support for the spectrum of the signal being sampled, sampling conditions will be expressed for a generic hexagonal sampling grid, and a comaprison with the well-known sampling conditions for a comparable rectangular lattice will be performed. Further, by considering for sake of clarity a spectrum with a circular support, the comparison will be performed under the assumption of same number of pixels for unity of surface, and the particular case of regular hexagonal sampling grid will also be considered. Regular hexagonal lattice with regular hexagonal sensitivity shape of the detector elements will result as the best trade-off between the proposed sampling requirement. Concerning the detector shape, the hexagonal is more advantageous than the rectangular. To show that a figure of merit is defined which takes into account that the MTF (modulation transfer function) of a hexagonal detector is not separable, conversely from that of a rectangular detector. As a final result, octagonal shape detectors are compared to those with rectangular and hexagonal shape in the two hypotheses of equal and ideal fill factor, respectively.

The quantum phase-transitions of water

NASA Astrophysics Data System (ADS)

Fillaux, François

2017-08-01

It is shown that hexagonal ices and steam are macroscopically quantum condensates, with continuous spacetime-translation symmetry, whereas liquid water is a quantum fluid with broken time-translation symmetry. Fusion and vaporization are quantum phase-transitions. The heat capacities, the latent heats, the phase-transition temperatures, the critical temperature, the molar volume expansion of ice relative to water, as well as neutron scattering data and dielectric measurements are explained. The phase-transition mechanisms along with the key role of quantum interferences and that of Hartley-Shannon's entropy are enlightened. The notions of chemical bond and force-field are questioned.

Analysis of the OPERA 15-pin experiment with SABRE-2P. [LMFBR

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rose, S.D.; Carbajo, J.J.

The OPERA (Out-of-Pile Expulsion and Reentry Apparatus) experiment simulates the initial phase of a pump coastdown without scram of a liquid-metal fast breeder reactor, specifically the Fast Flux Test Facility. The test section is a 15-pin 60/sup 0/ triangular sector designed to simulate a full-size 61-pin hexagonal bundle. A previous study indicates this to be an adequate simulation. In this paper, experimental results from the OPERA 15-pin experiment performed at ANL in 1982 are compared to analytical calculations obtained with the SABRE-2P code at ORNL.

Low-temperature field ion microscopy of carbon nanotubes

NASA Astrophysics Data System (ADS)

Ksenofontov, V. A.; Gurin, V. A.; Gurin, I. V.; Kolosenko, V. V.; Mikhailovskij, I. M.; Sadanov, E. V.; Mazilova, T. I.; Velikodnaya, O. A.

2007-10-01

The methods of high-resolution field ion microscopy with sample cooling to liquid helium temperature are used in a study of the products of gas-phase catalytic pyrolysis of hydrocarbons in the form of graphitized fibers containing carbon nanotubes. Full atomic resolution of the end cap of closed carbon nanotubes is achieved for the first time. It is found that the atomic structure of the tops of the caps of subnanometer carbon tubes consists predominantly of hexagonal rings. A possible reason for the improvement of the resolution of field ion images of nanotubes upon deep cooling is discussed.

Lifetime of Bubble Rafts: Cooperativity and Avalanches

NASA Astrophysics Data System (ADS)

Ritacco, Hernán; Kiefer, Flavien; Langevin, Dominique

2007-06-01

We have studied the collapse of pseudo-bi-dimensional foams. These foams are made of uniformly sized soap bubbles packed in an hexagonal lattice sitting at the top of a liquid surface. The collapse process follows the sequence: (1) rupture of a first bubble, driven by thermal fluctuations and (2) a cascade of bursting bubbles. We present a simple numerical model which captures the main characteristics of the dynamics of foam collapse. We show that in a certain range of viscosities of the foaming solutions, the size distribution of the avalanches follows power laws as in self-organized criticality processes.

Lifetime of bubble rafts: cooperativity and avalanches.

PubMed

Ritacco, Hernán; Kiefer, Flavien; Langevin, Dominique

2007-06-15

We have studied the collapse of pseudo-bi-dimensional foams. These foams are made of uniformly sized soap bubbles packed in an hexagonal lattice sitting at the top of a liquid surface. The collapse process follows the sequence: (1) rupture of a first bubble, driven by thermal fluctuations and (2) a cascade of bursting bubbles. We present a simple numerical model which captures the main characteristics of the dynamics of foam collapse. We show that in a certain range of viscosities of the foaming solutions, the size distribution of the avalanches follows power laws as in self-organized criticality processes.

Neutrally Charged Gas/Liquid Interface by a Catanionic Langmuir Monolayer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vaknin, David; Bu, Wei

Surface-sensitive synchrotron X-ray scattering and spectroscopic experiments were performed to explore the characteristics of Langmuir monolayers of oppositely charged mixed amphiphiles. A premixed (molar 1:1 stearic acid/stearylamine) solution was spread as a monolayer at the gas/liquid interface on pure water and on mono- and divalent salt solutions, revealing that the negatively charged carboxyl groups and positively charged amine groups are miscible into one another and tend to bond together to form a nearly neutral surface. Similar control experiments on pure stearic acid (SA) and stearylamine (ST) were also conducted for comparison. Due to the strong bonding, hexagonal structures in smallmore » domains with acyl-chains normal to the liquid surface are formed at zero surface pressures, that is, at molecular areas much larger than those of the densely packed acyl chains. In-plane X-ray diffraction indicates that the catanionic surface is highly ordered and modifies the structure of the water surface and thus can serve as a model system for interactions of an amino acid template with solutes.« less

Stacking faults and mechanisms strain-induced transformations of hcp metals (Ti, Mg) during mechanical activation in liquid hydrocarbons

NASA Astrophysics Data System (ADS)

Lubnin, A. N.; Dorofeev, G. A.; Nikonova, R. M.; Mukhgalin, V. V.; Lad'yanov, V. I.

2017-11-01

The evolution of the structure and substructure of metals Ti and Mg with hexagonal close-packed (hcp) lattice is studied during their mechanical activation in a planetary ball mill in liquid hydrocarbons (toluene, n-heptane) and with additions of carbon materials (graphite, fullerite, nanotubes) by X-ray diffraction, scanning electron microscopy, and chemical analysis. The temperature behavior and hydrogen-accumulating properties of mechanocomposites are studied. During mechanical activation of Ti and Mg, liquid hydrocarbons decay, metastable nanocrystalline titanium carbohydride Ti(C,H) x and magnesium hydride β-MgH2 are formed, respectively. The Ti(C,H) x and MgH2 formation mechanisms during mechanical activation are deformation ones and are associated with stacking faults accumulation, and the formation of face-centered cubic (fcc) packing of atoms. Metastable Ti(C,H)x decays at a temperature of 550°C, the partial reverse transformation fcc → hcp occurs. The crystalline defect accumulation (nanograin boundaries, stacking faults), hydrocarbon destruction, and mechanocomposite formation leads to the enhancement of subsequent magnesium hydrogenation in the Sieverts reactor.

The ab initio simulation of the Earth's core.

PubMed

Alfè, D; Gillan, M J; Vocadlo, L; Brodholt, J; Price, G D

2002-06-15

The Earth has a liquid outer and solid inner core. It is predominantly composed of Fe, alloyed with small amounts of light elements, such as S, O and Si. The detailed chemical and thermal structure of the core is poorly constrained, and it is difficult to perform experiments to establish the properties of core-forming phases at the pressures (ca. 300 GPa) and temperatures (ca. 5000-6000 K) to be found in the core. Here we present some major advances that have been made in using quantum mechanical methods to simulate the high-P/T properties of Fe alloys, which have been made possible by recent developments in high-performance computing. Specifically, we outline how we have calculated the Gibbs free energies of the crystalline and liquid forms of Fe alloys, and so conclude that the inner core of the Earth is composed of hexagonal close packed Fe containing ca. 8.5% S (or Si) and 0.2% O in equilibrium at 5600 K at the boundary between the inner and outer cores with a liquid Fe containing ca. 10% S (or Si) and 8% O.

Evaluation of New Reverse Osmosis Membranes for the Separation of Toxic Compounds from Wastewater

DTIC Science & Technology

1976-06-01

limited theoretical work being done regarding the separation of inorganic salts. Glueckauf (1967) has analyzed the repulsive forces between ions and a... inorganic ions by cellulose acetate membrane is in the order of the lyotropic series of ions. However, this criterion of separation has a few...12). The objective of this work was to study the criterion for the separa- tion of inorganic ions with the NS-1O0 membrane. Hopefully, it can be used

Wafer-Scale and Wrinkle-Free Epitaxial Growth of Single-Orientated Multilayer Hexagonal Boron Nitride on Sapphire.

PubMed

Jang, A-Rang; Hong, Seokmo; Hyun, Chohee; Yoon, Seong In; Kim, Gwangwoo; Jeong, Hu Young; Shin, Tae Joo; Park, Sung O; Wong, Kester; Kwak, Sang Kyu; Park, Noejung; Yu, Kwangnam; Choi, Eunjip; Mishchenko, Artem; Withers, Freddie; Novoselov, Kostya S; Lim, Hyunseob; Shin, Hyeon Suk

2016-05-11

Large-scale growth of high-quality hexagonal boron nitride has been a challenge in two-dimensional-material-based electronics. Herein, we present wafer-scale and wrinkle-free epitaxial growth of multilayer hexagonal boron nitride on a sapphire substrate by using high-temperature and low-pressure chemical vapor deposition. Microscopic and spectroscopic investigations and theoretical calculations reveal that synthesized hexagonal boron nitride has a single rotational orientation with AA' stacking order. A facile method for transferring hexagonal boron nitride onto other target substrates was developed, which provides the opportunity for using hexagonal boron nitride as a substrate in practical electronic circuits. A graphene field effect transistor fabricated on our hexagonal boron nitride sheets shows clear quantum oscillation and highly improved carrier mobility because the ultraflatness of the hexagonal boron nitride surface can reduce the substrate-induced degradation of the carrier mobility of two-dimensional materials.

Highly concentrated collagen solutions leading to transparent scaffolds of controlled three-dimensional organizations for corneal epithelial cell colonization.

PubMed

Tidu, Aurélien; Ghoubay-Benallaoua, Djida; Teulon, Claire; Asnacios, Sophie; Grieve, Kate; Portier, François; Schanne-Klein, Marie-Claire; Borderie, Vincent; Mosser, Gervaise

2018-05-29

This study aimed at controlling both the organization and the transparency of dense collagen scaffolds making use of the lyotropic mesogen properties of collagen. Cholesteric or plywood-like liquid crystal phases were achieved using mixtures of acetic and hydrochloric acids as solvents. The critical pH at which the switch between the two phases occurred was around pH = 3. The use of the two acids led to fibrillated collagen I scaffolds, whose visual aspect ranged from opaque to transparent. Rheological investigations showed that viscoelastic properties of the plywood-like solutions were optimized for molding due to faster recovery. They also confirmed the correlation between the elastic modulus and the diameter of collagen fibrils obtained after fibrillogenesis under ammonia vapor. Human corneal epithelial cells, grown from donor limbal explants, were cultured both on transparent plywood-like matrices and on human amniotic membranes for 14 days. The development of corneal epithelium and the preservation of epithelial stem cells were checked by optical microscopy, colony formation assay, immuno-fluorescence and quantitative polymerase chain reaction. A higher level of amplification of limbal stem cells was obtained with collagen matrices compared with amniotic membranes, showing the high biocompatibility of our scaffolds. We therefore suggest that collagen solutions presenting both plywood-like organization and transparency might be of interest for biomedical applications in ophthalmology.

Structural Physics of Bee Honeycomb

NASA Astrophysics Data System (ADS)

Kaatz, Forrest; Bultheel, Adhemar; Egami, Takeshi

2008-03-01

Honeybee combs have aroused interest in the ability of honeybees to form regular hexagonal geometric constructs since ancient times. Here we use a real space technique based on the pair distribution function (PDF) and radial distribution function (RDF), and a reciprocal space method utilizing the Debye-Waller Factor (DWF) to quantify the order for a range of honeycombs made by Apis mellifera. The PDFs and RDFs are fit with a series of Gaussian curves. We characterize the order in the honeycomb using a real space order parameter, OP3, to describe the order in the combs and a two-dimensional Fourier transform from which a Debye-Waller order parameter, u, is derived. Both OP3 and u take values from [0, 1] where the value one represents perfect order. The analyzed combs have values of OP3 from 0.33 to 0.60 and values of u from 0.83 to 0.98. RDF fits of honeycomb histograms show that naturally made comb can be crystalline in a 2D ordered structural sense, yet is more `liquid-like' than cells made on `foundation' wax. We show that with the assistance of man-made foundation wax, honeybees can manufacture highly ordered arrays of hexagonal cells.

Pressure-dependent structure of the null-scattering alloy Ti 0.676 Zr 0.324

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zeidler, Anita; Guthrie, Malcolm; Salmon, Philip S.

2015-05-13

The room temperature structure of the alloy Ti0.676Zr0.324Ti0.676Zr0.324 was measured by X-ray diffraction under compression at pressures up to ~30GPa. This alloy is used as a construction material in high pressure neutron-scattering research and has a mean coherent neutron scattering length of zero, that is, it is a so-called null-scattering alloy. A broad phase transition was observed from a hexagonal close-packed α-phase to a hexagonal ω-phase, which started at a pressure of ≲12GPa≲12GPa and was completed by ~25GPa. The data for the α-phase were fitted by using a third-order Birch–Murnaghan equation of state, giving an isothermal bulk modulus B0=87(4)GPaB0=87(4)GPa andmore » pressure derivative B'0=6.6(8)B0'=6.6(8). The results will help to ensure that accurate structural information can be gained from in situ high pressure neutron diffraction work on amorphous and liquid materials where the Ti0.676Zr0.324Ti0.676Zr0.324 alloy is used as a gasket material.« less

Tetrahedral Arrangements of Perylene Bisimide Columns via Supramolecular Orientational Memory.

PubMed

Sahoo, Dipankar; Peterca, Mihai; Aqad, Emad; Partridge, Benjamin E; Heiney, Paul A; Graf, Robert; Spiess, Hans W; Zeng, Xiangbing; Percec, Virgil

2017-01-24

Chiral, shape, and liquid crystalline memory effects are well-known to produce commercial macroscopic materials with important applications as springs, sensors, displays, and memory devices. A supramolecular orientational memory effect that provides complex nanoscale arrangements was only recently reported. This supramolecular orientational memory was demonstrated to preserve the molecular orientation and packing within supramolecular units of a self-assembling cyclotriveratrylene crown at the nanoscale upon transition between its columnar hexagonal and Pm3̅n cubic periodic arrays. Here we report the discovery of supramolecular orientational memory in a dendronized perylene bisimide (G2-PBI) that self-assembles into tetrameric crowns and subsequently self-organizes into supramolecular columns and spheres. This supramolecular orientation memory upon transition between columnar hexagonal and body-centered cubic (BCC) mesophases preserves the 3-fold cubic [111] orientations rather than the 4-fold [100] axes, generating an unusual tetrahedral arrangement of supramolecular columns. These results indicate that the supramolecular orientational memory concept may be general for periodic arrays of self-assembling dendrons and dendrimers as well as for other periodic and quasiperiodic nanoscale organizations comprising supramolecular spheres, generated from other organized complex soft matter including block copolymers and surfactants.

Many-body Effect, Carrier Mobility, and Device Performance of Hexagonal Arsenene and Antimonene

NASA Astrophysics Data System (ADS)

Wang, Yangyang; Ye, Meng; Quhe, Ruge; Huang, Pu; Lu, Jing

Monolayer (ML) arsenene and antimonene, as new members of group V-enes, have attracted great interest. Experimentally, multilayer arsenene/antimonene nanoribbons have been fabricated on an InAs/InSb substrate. ML and multilayer antimonene have been isolated by mechanical exfoliation and liquid-phase exfoliation. More importantly, they are highly stable under ambient condition. Together with their wide band gaps predicted by the HSE theory, arsenene and antimonene are very attractive for nanoscale optoelectronic and electronic devices. We investigate the many-body effect and device performance of ML hexagonal arsenene and antimonene using ab initio GW, GW plus Bethe-Salpeter equation and nonequilibrium Green's function approach. The quasi-particle and optical band gaps are calculated in ML arsenene and antimonene for the first time. Low (21/66 cm2/V .s for electron/hole) and moderate carrier mobilities (150/510 cm2/V .s for electron/hole) are obtained, for arsenene and antimonene, respectively. Quantum transport simulation reveals that the performance limits of sub-10 nm ML arsenene and antimonene FETs can satisfy both low power and high performance requirements of the ITRS target in the next decade. National Natural Science Foundation of China (No. 11274016/11474012/11674005/11274233).

Controlling the Mesostructure Formation within the Shell of Novel Cubic/Hexagonal Phase Cetyltrimethylammonium Bromide-Poly(acrylamide-acrylic acid) Capsules for pH Stimulated Release.

PubMed

Tangso, Kristian J; Patel, Hetika; Lindberg, Seth; Hartley, Patrick G; Knott, Robert; Spicer, Patrick T; Boyd, Ben J

2015-11-11

The self-assembly of ordered structures in mixtures of oppositely charged surfactant and polymer systems has been exploited in various cleaning and pharmaceutical applications and continue to attract much interest since their discovery in the late twentieth century. The ability to control the electrostatic and hydrophobic interactions that dictate the formation of liquid crystalline phases in these systems is advantageous in manipulation of structure and rendering them responsive to external stimuli. Nanostructured capsules comprised of the cationic surfactant, cetyltrimethylammonium bromide (CTAB), and the diblock copolymer poly(acrylamide-acrylic acid) (PAAm-AA) were prepared to assess their potential as pH responsive nanomaterials. Crossed-polarizing light microscopy (CPLM) and small-angle X-ray scattering (SAXS) identified coexisting Pm3n cubic and hexagonal phases at the surfactant-polymer interface. The hydrophobic and electrostatic interactions between the oppositely charged components were studied by varying temperature and solution pH, respectively, and were found to influence the liquid crystalline nanostructure formed. The lattice parameter of the mesophases and the fraction of cubic phase in the system decreased upon heating. Acidic conditions resulted in the loss of the highly ordered structures due to protonation of the carboxylic acid group, and subsequent reduction of attractive forces previously present between the oppositely charged molecules. The rate of release of the model hydrophilic drug, Rhodamine B (RhB), from nanostructured macro-sized capsules significantly increased when the pH of the solution was adjusted from pH 7 to pH 2. This allowed for immediate release of the compound of interest "on demand", opening new options for structured materials with increased functionality over typical layer-by-layer capsules.

Classical and quantum theories of proton disorder in hexagonal water ice

NASA Astrophysics Data System (ADS)

Benton, Owen; Sikora, Olga; Shannon, Nic

2016-03-01

It has been known since the pioneering work of Bernal, Fowler, and Pauling that common, hexagonal (Ih) water ice is the archetype of a frustrated material: a proton-bonded network in which protons satisfy strong local constraints (the "ice rules") but do not order. While this proton disorder is well established, there is now a growing body of evidence that quantum effects may also have a role to play in the physics of ice at low temperatures. In this paper, we use a combination of numerical and analytic techniques to explore the nature of proton correlations in both classical and quantum models of ice Ih. In the case of classical ice Ih, we find that the ice rules have two, distinct, consequences for scattering experiments: singular "pinch points," reflecting a zero-divergence condition on the uniform polarization of the crystal, and broad, asymmetric features, coming from its staggered polarization. In the case of the quantum model, we find that the collective quantum tunneling of groups of protons can convert states obeying the ice rules into a quantum liquid, whose excitations are birefringent, emergent photons. We make explicit predictions for scattering experiments on both classical and quantum ice Ih, and show how the quantum theory can explain the "wings" of incoherent inelastic scattering observed in recent neutron scattering experiments [Bove et al., Phys. Rev. Lett. 103, 165901 (2009), 10.1103/PhysRevLett.103.165901]. These results raise the intriguing possibility that the protons in ice Ih could form a quantum liquid at low temperatures, in which protons are not merely disordered, but continually fluctuate between different configurations obeying the ice rules.

Glyceryl monooleyl ether-based liquid crystalline nanoparticles as a transdermal delivery system of flurbiprofen: characterization and in vitro transport.

PubMed

Uchino, Tomonobu; Murata, Akiko; Miyazaki, Yasunori; Oka, Toshihiko; Kagawa, Yoshiyuki

2015-01-01

Liquid crystalline nanoparticles (LCNs) were prepared using glyceryl monooleyl ether (GME) by the modified film rehydration method. Hydrogenated lecithin (HL), 1,3-butylene glycol (1,3-BG), and Poloxamer 407 were used as additives. The prepared LCN formulations were evaluated based on particle size, small-angle X-ray diffraction (SAXS) analysis, (1)H- and (19)F-NMR spectra, and in vitro skin permeation across Yucatan micropig skin. The composition (weight percent) of the LCN formulations were GME-HL-1,3-BG (4 : 1 : 15), 4% GME-based LCN and GME-HL-1,3-BG (8 : 1 : 15), 8% GME-based LCN and their mean particle sizes were 130-175 nm. Flurbiprofen 5 and 10 mg was loaded into 4% GME-based LCN and 8% GME-based LCN systems, respectively. The results of SAXS and NMR suggested that both flurbiprofen-loaded formulations consist of particles with reverse type hexagonal phase (formation of hexosome) and flurbiprofen molecules were localized in the lipid domain through interaction of flurbiprofen with the lipid components. Flurbiprofen transport from the LCN systems across the Yucatan micropig skin was increased compared to flurbiprofen in citric buffer (pH=3.0). The 8% GME-based LCN systems was superior to the 4% GME-based LCN for flurbiprofen transport. Since the internal hexagonal phase in the 8% GME-based LCN systems had a higher degree of order compared to the 4% GME-based LCN in SAXS patterns, the 8% GME-based LCN system had a larger surface area, which might influence flurbiprofen permeation. These results indicated that the GME-based LCN system is effective in improving the skin permeation of flurbiprofen across the skin.

Absence of Jahn-Teller transition in the hexagonal Ba 3CuSb 2O 9 single crystal

DOE PAGES

Katayama, Naoyuki; Kimura, Kenta; Han, Yibo; ...

2015-07-13

With decreasing temperature, liquids generally freeze into a solid state, losing entropy in the process. However, exceptions to this trend exist, such as quantum liquids, which may remain unfrozen down to absolute zero owing to strong quantum entanglement effects that stabilize a disordered state with zero entropy. Examples of such liquids include Bose-Einstein condensation of cold atoms, superconductivity, quantum Hall state of electron systems, and quantum spin liquid state in the frustrated magnets. Furthermore, recent studies have clarified the possibility of another exotic quantum liquid state based on the spin-orbital entanglement in FeSc2S4. To confirm this exotic ground state, experimentsmore » based on single-crystalline samples are essential. However, no such single-crystal study has been reported to date. Here, we report, to our knowledge, the first single-crystal study on the spin-orbital liquid candidate, 6H-Ba3CuSb2O9, and we have confirmed the absence of an orbital frozen state. In strongly correlated electron systems, orbital ordering usually appears at high temperatures in a process accompanied by a lattice deformation, called a static Jahn-Teller distortion. By combining synchrotron X-ray diffraction, electron spin resonance, Raman spectroscopy, and ultrasound measurements, we find that the static Jahn-Teller distortion is absent in the present material, which indicates that orbital ordering is suppressed down to the lowest temperatures measured. Lastly, we discuss how such an unusual feature is realized with the help of spin degree of freedom, leading to a spin-orbital entangled quantum liquid state.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Chunya; Skelton, Adam A.; Chen, Mingjun

Here the binding of a negatively charged residue, aspartic acid (Asp) in tripeptide arginine-glycine-aspartic acid, onto a negatively charged hydroxylated rutile (110) surface in aqueous solution, containing divalent (Mg 2+, Ca 2+, or Sr 2+) or monovalent (Na +, K +, or Rb +) cations, was studied by molecular dynamics (MD) simulations. The results indicate that ionic radii and charges will significantly affect the hydration, adsorption geometry, and distance of cations from the rutile surface, thereby regulating the Asp/rutile binding mode. The adsorption strength of monovalent cations on the rutile surface in the order Na + > K + >more » Rb + shows a “reverse” lyotropic trend, while the divalent cations on the same surface exhibit a “regular” lyotropic behavior with decreasing crystallographic radii (the adsorption strength of divalent cations: Sr 2+ > Ca 2+ > Mg 2+). The Asp side chain in NaCl, KCl, and RbCl solutions remains stably H-bonded to the surface hydroxyls and the inner-sphere adsorbed compensating monovalent cations act as a bridge between the COO – group and the rutile, helping to “trap” the negatively charged Asp side chain on the negatively charged surface. In contrast, the mediating divalent cations actively participate in linking the COO– group to the rutile surface; thus the Asp side chain can remain stably on the rutile (110) surface, even if it is not involved in any hydrogen bonds with the surface hydroxyls. Inner- and outer-sphere geometries are all possible mediation modes for divalent cations in bridging the peptide to the rutile surface.« less

Molecular Simulations of the Synthesis of Periodic Mesoporous Silica Phases at High Surfactant Concentrations

DOE PAGES

Chien, Szu-Chia; Pérez-Sánchez, Germán; Gomes, José R. B.; ...

2017-02-17

Molecular dynamics simulations of a coarse-grained model are used to study the formation mechanism of periodic mesoporous silica over a wide range of cationic surfactant concentrations. This follows up on an earlier study of systems with low surfactant concentrations. We started by studying the phase diagram of the surfactant–water system and found that our model shows good qualitative agreement with experiments with respect to the surfactant concentrations where various phases appear. We then considered the impact of silicate species upon the morphologies formed. We have found that even in concentrated surfactant systems—in the concentration range where pure surfactant solutions yieldmore » a liquid crystal phase—the liquid-crystal templating mechanism is not viable because the preformed liquid crystal collapses as silica monomers are added into the solution. Upon the addition of silica dimers, a new phase-separated hexagonal array is formed. The preformed liquid crystals were found to be unstable in the presence of monomeric silicates. In addition, the silica dimer is found to be essential for mesoscale ordering at both low and high surfactant concentrations. Our results support the view that a cooperative interaction of anionic silica oligomers and cationic surfactants determines the mesostructure formation in the M41S family of materials.« less

Rotating non-Boussinesq convection: oscillating hexagons

NASA Astrophysics Data System (ADS)

Moroz, Vadim; Riecke, Hermann; Pesch, Werner

2000-11-01

Within weakly nonlinear theory hexagon patterns are expected to undergo a Hopf bifurcation to oscillating hexagons when the chiral symmetry of the system is broken. Quite generally, the oscillating hexagons are expected to exhibit bistability of spatio-temporal defect chaos and periodic dynamics. This regime is described by the complex Ginzburg-Landau equation, which has been investigated theoretically in great detail. Its complex dynamics have, however, not been observed in experiments. Starting from the Navier-Stokes equations with realistic boundary conditions, we derive the three coupled real Ginzburg-Landau equations describing hexagons in rotating non-Boussinesq convection. We use them to provide quantitative results for the wavenumber range of stability of the stationary hexagons as well as the range of existence and stability of the oscillating hexagons. Our investigation is complemented by direct numerical simulations of the Navier-Stokes equations.

Development of Low-cost, High Energy-per-unit-area Solar Cell Modules

NASA Technical Reports Server (NTRS)

Jones, G. T.; Chitre, S.; Rhee, S. S.

1978-01-01

The development of two hexagonal solar cell process sequences, a laserscribing process technique for scribing hexagonal and modified hexagonal solar cells, a large through-put diffusion process, and two surface macrostructure processes suitable for large scale production is reported. Experimental analysis was made on automated spin-on anti-reflective coating equipment and high pressure wafer cleaning equipment. Six hexagonal solar cell modules were fabricated. Also covered is a detailed theoretical analysis on the optimum silicon utilization by modified hexagonal solar cells.

Observations on infiltration of silicon carbide compacts with an aluminium alloy

NASA Technical Reports Server (NTRS)

Asthana, R.; Rohatgi, P. K.

1992-01-01

The melt infiltration of ceramic particulates permits an opportunity to observe such fundamental materials phenomena as nucleation, dynamic wetting and growth in constrained environments. Experimental observations are presented on the infiltration behavior and matrix microstructures that form when porous compacts of platelet-shaped single crystals of alpha- (hexagonal) silicon carbide are infiltrated with a liquid 2014 Al alloy. The infiltration process involved counter gravity infiltration of suitably tamped and preheated compacts of silicon carbide platelets under an external pressure in a special pressure chamber for a set period, then by solidification of the infiltrant metal in the interstices of the bed at atmospheric pressure.

Liquid petroleum gas sensing application of ZnO/CdO:ZnO nanocomposites at low temperature

NASA Astrophysics Data System (ADS)

Rajput, Jeevitesh K.; Pathak, T. K.; Kumar, V.; Swart, H. C.; Purohit, L. P.

2018-04-01

ZnO and CdO:ZnO nanoparticles are synthesized by sol-gel precipitation method. The structural analysis shows composite structure for CdO:ZnO nanoparticles with (002) and (111) phase. The SEM images show wedge like morphology and 3-D hexagonal morphology with ˜110 nm in size. The uniform growth of CdO:ZnO nanoparticles were observed in EDS element mapping image. LPG sensing was observed for CdO:ZnO nanoparticle with rapid sensing response 8.69% at operating temperature 50°C. This sensing response can be accounted due by absorption ions reactions at low operating temperature.

Dynamical behavior of Borospherene: A Nanobubble

PubMed Central

Martínez-Guajardo, Gerardo; Luis Cabellos, José; Díaz-Celaya, Andres; Pan, Sudip; Islas, Rafael; Chattaraj, Pratim K.; Heine, Thomas; Merino, Gabriel

2015-01-01

The global minimum structure of borospherene (B40) is a cage, comprising two hexagonal and four heptagonal rings. Born-Oppenheimer Molecular Dynamics simulations show that continuous conversions in between six and seven membered rings take place. The activation energy barrier for such a transformation is found to be 14.3 kcal·mol−1. The completely delocalized σ- and π-frameworks, as well as the conservation of the bonding pattern during rearrangement, facilitate the dynamical behavior of B40. B40 is predicted to act as a support-free spherical two-dimensional liquid at moderate temperature. In other words, B40 could be called as a nanobubble. PMID:26096039

Tubular growth and bead formation in the lyotropic lamellar phase of a lipid.

PubMed

Bhatia, Tripta; Hatwalne, Yashodhan; Madhusudana, N V

2015-07-28

We use fluorescence confocal polarised microscopy (FCPM) to study tubular growth upon hydration of dry DOPC (1,2-dioleoyl-sn-glycero-3-phosphocholine) in water and water-glycerol mixtures. We have developed a model to relate the FCPM intensity profiles to the multilamellar structures of the tubules. Insertion of an additional patch inside a tubule produces a beaded structure, while a straight configuration is retained if the growth is on the outside. We use a simple model to suggest that reduction in overall curvature energy drives bead formation.

Chain hexagonal cacti with the extremal eccentric distance sum.

PubMed

Qu, Hui; Yu, Guihai

2014-01-01

Eccentric distance sum (EDS), which can predict biological and physical properties, is a topological index based on the eccentricity of a graph. In this paper we characterize the chain hexagonal cactus with the minimal and the maximal eccentric distance sum among all chain hexagonal cacti of length n, respectively. Moreover, we present exact formulas for EDS of two types of hexagonal cacti.

Water polygons in high-resolution protein crystal structures.

PubMed

Lee, Jonas; Kim, Sung-Hou

2009-07-01

We have analyzed the interstitial water (ISW) structures in 1500 protein crystal structures deposited in the Protein Data Bank that have greater than 1.5 A resolution with less than 90% sequence similarity with each other. We observed varieties of polygonal water structures composed of three to eight water molecules. These polygons may represent the time- and space-averaged structures of "stable" water oligomers present in liquid water, and their presence as well as relative population may be relevant in understanding physical properties of liquid water at a given temperature. On an average, 13% of ISWs are localized enough to be visible by X-ray diffraction. Of those, averages of 78% are water molecules in the first water layer on the protein surface. Of the localized ISWs beyond the first layer, almost half of them form water polygons such as trigons, tetragons, as well as expected pentagons, hexagons, higher polygons, partial dodecahedrons, and disordered networks. Most of the octagons and nanogons are formed by fusion of smaller polygons. The trigons are most commonly observed. We suggest that our observation provides an experimental basis for including these water polygon structures in correlating and predicting various water properties in liquid state.

Water polygons in high-resolution protein crystal structures

PubMed Central

Lee, Jonas; Kim, Sung-Hou

2009-01-01

We have analyzed the interstitial water (ISW) structures in 1500 protein crystal structures deposited in the Protein Data Bank that have greater than 1.5 Å resolution with less than 90% sequence similarity with each other. We observed varieties of polygonal water structures composed of three to eight water molecules. These polygons may represent the time- and space-averaged structures of “stable” water oligomers present in liquid water, and their presence as well as relative population may be relevant in understanding physical properties of liquid water at a given temperature. On an average, 13% of ISWs are localized enough to be visible by X-ray diffraction. Of those, averages of 78% are water molecules in the first water layer on the protein surface. Of the localized ISWs beyond the first layer, almost half of them form water polygons such as trigons, tetragons, as well as expected pentagons, hexagons, higher polygons, partial dodecahedrons, and disordered networks. Most of the octagons and nanogons are formed by fusion of smaller polygons. The trigons are most commonly observed. We suggest that our observation provides an experimental basis for including these water polygon structures in correlating and predicting various water properties in liquid state. PMID:19551896

Tunable liquid microlens array driven by pyroelectric effect: full interferometric characterization

NASA Astrophysics Data System (ADS)

Miccio, Lisa; Grilli, Simonetta; Vespini, Veronica; Ferraro, Pietro

2008-09-01

Liquid lenses with adjustable focal length are of great interest in the field of microfluidic devices. They are, usually, realized by electrowetting effect after electrodes patterning on a hydrofobic substrate. Applications are possible in many fields ranging from commercial products such as digital cameras to biological cell sorting. We realized an open array of liquid lenses with adjustable focal length without electrode patterning. We used a z-cut Lithium Niobate crystal (LN) as substrate and few microliters of an oily substance to obtain the droplets array. The spontaneous polarization of LN crystals is reversed by the electric field poling process, thus enabling the realization of periodically poled LN (PPLN) crystals. The substrate consists of a two-dimensional square array of reversed domains with a period around 200 μm. Each domain presents an hexagonal geometry due to the crystal structure. PPLN is first covered by a thin and homogeneous layer of the above mentioned liquid and therefore its temperature is changed by means of a digitally controlled hot plate. During heating and cooling process there is a rearrangement of the liquid layer until it reaches the final topography. Lenses formation is due to the superficial tension changing at the liquid-solid interface by means of the pyroelectric effect. Such effect allows to create a two-dimensional lens pattern of tunable focal length without electrodes. The temporal evolution of both shape and focal length lenses are quantitatively measured by Digital Holographic Microscopy. Array imaging properties and quantitative analysis of the lenses features and aberrations are presented.

An Explanation for Saturn's Hexagon

NASA Astrophysics Data System (ADS)

Kohler, Susanna

2015-08-01

For over three decades, weve been gathering observations of the mysterious hexagonal cloud pattern encircling Saturns north pole. Now, researchers believe they have a model that can better explain its formation.Fascinating GeometrySaturns northern Hexagon is a cloud band circling Saturns north pole at 78 N, first observed by the Voyager flybys in 198081. This remarkable pattern has now persisted for more than a Saturn year (29.5 Earth years).Eight frames demonstrating the motion within Saturns Hexagon. Click to watch the animation! The view is from a reference frame rotating with Saturn. [NASA/JPL-Caltech/SSI/Hampton University]Observations by Voyager and, more recently, Cassini have helped to identify many key characteristics of this bizarre structure. Two interesting things weve learned are:The Hexagon is associated with an eastward zonal jet moving at more than 200 mph.The cause of the Hexagon is believed to be a jet stream, similar to the ones that we experience on Earth. The path of the jet itself appears to follow the hexagons outline.The Hexagon rotates at roughly the same rate as Saturns overall rotation.While we observe individual storms and cloud patterns moving at different speeds within the Hexagon, the vertices of the Hexagon move at almost exactly the same rotational speed as that of Saturn itself.Attempts to model the formation of the Hexagon with a jet stream have yet to fully reproduce all of the observed features and behavior. But now, a team led by Ral Morales-Juberas of the New Mexico Institute of Mining and Technology believes they have created a model that better matches what we see.Simulating a Meandering JetThe team ran a series of simulations of an eastward, Gaussian-profile jet around Saturns pole. They introduced small perturbations to the jet and demonstrated that, as a result of the perturbations, the jet can meander into a hexagonal shape. With the initial conditions of the teams model, the meandering jet is able to settle into a stable hexagonal shape that rotates with very nearly the same period as Saturns rotational period.The formation of this hexagon depends on factors such as the initial amplitude and curvature of the jet. The models treatment of the wind profile within Saturns atmosphere is another key component that allowed them to match the observed characteristics of the Hexagon, such as its shape, vorticity behavior, temperature gradient, and seasonal stability.BonusThe gif below shows part of an animation the authors produced of the jet evolution in their model. You can see a hexagon begin to develop at around 230 days into the simulation, and by about 400 days it becomes stable and non-rotating (were looking at it from a reference frame rotating with Saturn). The full animation can be viewed here. [Morales-Juberas et al., 2015]CitationR. Morales-Juberas et al.2015 ApJ 806 L18 doi:10.1088/2041-8205/806/1/L18

Metronidazole-Loaded Polyethyleneimine and Chitosan-Based Liquid Crystalline System for Treatment of Staphylococcal Skin Infections.

PubMed

Victorelli, Francesca Damiani; Calixto, Giovana Maria Fioramonti; Ramos, Matheus Aparecido Dos Santos; Bauab, Taís Maria; Chorilli, Marlus

2018-01-01

Staphylococcus aureus is a common gram-positive bacterium of the human skin microbiota. It is also a dangerous pathogen that can cause serious and even lethal skin infections. The topical administration of metronidazole via nanotechnology-based drug delivery systems, such as liquid crystalline systems, can modulate both the drug permeation and activity, decreasing its side effects and increasing the drug potent activity against the gram-positive bacteria. This study aimed at: (1) structurally developing and characterizing a liquid crystalline systems composed of chitosan and polyethyleneimine dispersion as the aqueous phase, oleic acid as the oily phase, and ethoxylated and propoxylated cetyl alcohol as the surfactant (FPC) for metronidazole incorporation (0.5% w/w); (2) evaluating the in vitro release and skin permeation and retention properties of the metronidazole-loaded liquid crystalline systems (FPC-M); (3) investigating the in vitro antibacterial activity of FPC-M against Staphylococcus aureus. Polarised light microscopy indicated that both FPC and FPC-M are hexagonal systems. Rheological, texture, and bioadhesion assays showed that both are elastic and bioadhesive systems. According to the results of the in vitro release, permeation, and retention assays, FPC can modulate metronidazole release and allow metronidazole to stay for a longer time on the skin. The determination of FPC-M activity against Staphylococcus aureus showed that it could target the bacterial cell. In conclusion, the liquid crystalline systems developed in this study can improve the clinical performance of metronidazole in the treatment of staphylococcal skin infections.

Functionalized mesoporous silica supported copper(II) and nickel(II) catalysts for liquid phase oxidation of olefins.

PubMed

Nandi, Mahasweta; Roy, Partha; Uyama, Hiroshi; Bhaumik, Asim

2011-12-14

Highly ordered 2D-hexagonal mesoporous silica has been functionalized with 3-aminopropyltriethoxysilane (3-APTES). This is followed by its condensation with a dialdehyde, 4-methyl-2,6-diformylphenol to produce an immobilized Schiff-base ligand (I). This material is separately treated with methanolic solution of copper(II) chloride and nickel(II) chloride to obtain copper and nickel anchored mesoporous materials, designated as Cu-AMM and Ni-AMM, respectively. The materials have been characterized by Fourier transform infrared (FT-IR) and UV-vis diffuse reflectance (DRS) spectroscopy, powder X-ray diffraction (XRD), transmission electron microscopy (TEM), N(2) adsorption-desorption studies and (13)C CP MAS NMR spectroscopy. The metal-grafted mesoporous materials have been used as catalysts for the efficient and selective epoxidation of alkenes, viz. cyclohexene, trans-stilbene, styrene, α-methyl styrene, cyclooctene and norbornene to their corresponding epoxides in the presence of tert-butyl hydroperoxide (TBHP) as the oxidant under mild liquid phase conditions.

Orientation-dependent integral equation theory for a two-dimensional model of water

NASA Astrophysics Data System (ADS)

Urbič, T.; Vlachy, V.; Kalyuzhnyi, Yu. V.; Dill, K. A.

2003-03-01

We develop an integral equation theory that applies to strongly associating orientation-dependent liquids, such as water. In an earlier treatment, we developed a Wertheim integral equation theory (IET) that we tested against NPT Monte Carlo simulations of the two-dimensional Mercedes Benz model of water. The main approximation in the earlier calculation was an orientational averaging in the multidensity Ornstein-Zernike equation. Here we improve the theory by explicit introduction of an orientation dependence in the IET, based upon expanding the two-particle angular correlation function in orthogonal basis functions. We find that the new orientation-dependent IET (ODIET) yields a considerable improvement of the predicted structure of water, when compared to the Monte Carlo simulations. In particular, ODIET predicts more long-range order than the original IET, with hexagonal symmetry, as expected for the hydrogen bonded ice in this model. The new theoretical approximation still errs in some subtle properties; for example, it does not predict liquid water's density maximum with temperature or the negative thermal expansion coefficient.

Template-free solution approach to synthesize CdS dendrites with SCN based ionic liquid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Kangfeng; Li, Jiajia; Cheng, Xianyi

2011-07-15

Highlights: {yields} Template-free solution approach to synthesize CdS hierarchical dendrites. {yields} The 1-butyl-3-methlyimidazole thiocyanate ([BMIM][SCN]) plays doubly functional roles in the progress. {yields} The CdS hierarchical dendrites exhibit a more intense emission at 710 nm belongs to infrared band. -- Abstract: Cadmium sulfide dendrites were synthesized by a facile hydrothermal treatment from CdCl{sub 2} and ionic liquid 1-butyl-3-methlyimidazole thiocyanate acted both as sulfur source and surfactant. The product was characterized by means of X-ray powder diffraction and scanning electron microscopy. X-ray powder diffraction studies indicated that the product was well-crystallized hexagonal phase of CdS, and the scanning electron microscopy imagesmore » showed that the obtained powders consisted of a wealth of well-defined CdS dendritic microstructures with a pronounced trunk and highly ordered branches. The UV-Vis and photoluminescence spectroscopy measurements were taken as well. The possible formation mechanism of CdS dendrites was simply proposed in the end.« less

In situ GISAXS study of a Si-containing block copolymer under solvent vapor annealing: Effects of molecular weight and solvent vapor composition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bai, W.; Yager, K. G.; Ross, C. A.

The room-temperature solvent vapor annealing of polystyrene-b-polydimethylsiloxane (PS-b-PDMS) block copolymer films was studied in situ by grazing incidence small-angle X-ray scattering. Films of cylinder-forming PS-b-PDMS with molecular weight 16 kg/mol and 12.2 kg/mol, annealed under vapors of toluene:heptane with varying composition, exhibited swelling-ratio-dependent evolution of microdomain spacing and orientation. In a vapor made from a toluene:heptane 5:1 volumetric ratio liquid mixture, or from pure toluene, cylindrical microdomains reoriented from majority out-of-plane to in-plane during annealing, while drying led to shrinkage along the film normal and a large distortion of the hexagonal lattice of in-plane cylinders. As a result, annealing undermore » vapor from a toluene:heptane 1:5 volumetric ratio liquid produced a non-bulk lamellar structure in the 16 kg/mol PS-b-PDMS.« less

In situ GISAXS study of a Si-containing block copolymer under solvent vapor annealing: Effects of molecular weight and solvent vapor composition

DOE PAGES

Bai, W.; Yager, K. G.; Ross, C. A.

2016-08-19

The room-temperature solvent vapor annealing of polystyrene-b-polydimethylsiloxane (PS-b-PDMS) block copolymer films was studied in situ by grazing incidence small-angle X-ray scattering. Films of cylinder-forming PS-b-PDMS with molecular weight 16 kg/mol and 12.2 kg/mol, annealed under vapors of toluene:heptane with varying composition, exhibited swelling-ratio-dependent evolution of microdomain spacing and orientation. In a vapor made from a toluene:heptane 5:1 volumetric ratio liquid mixture, or from pure toluene, cylindrical microdomains reoriented from majority out-of-plane to in-plane during annealing, while drying led to shrinkage along the film normal and a large distortion of the hexagonal lattice of in-plane cylinders. As a result, annealing undermore » vapor from a toluene:heptane 1:5 volumetric ratio liquid produced a non-bulk lamellar structure in the 16 kg/mol PS-b-PDMS.« less

Effect of platform connection and abutment material on stress distribution in single anterior implant-supported restorations: a nonlinear 3-dimensional finite element analysis.

PubMed

Carvalho, Marco Aurélio; Sotto-Maior, Bruno Salles; Del Bel Cury, Altair Antoninha; Pessanha Henriques, Guilherme Elias

2014-11-01

Although various abutment connections and materials have recently been introduced, insufficient data exist regarding the effect of stress distribution on their mechanical performance. The purpose of this study was to investigate the effect of different abutment materials and platform connections on stress distribution in single anterior implant-supported restorations with the finite element method. Nine experimental groups were modeled from the combination of 3 platform connections (external hexagon, internal hexagon, and Morse tapered) and 3 abutment materials (titanium, zirconia, and hybrid) as follows: external hexagon-titanium, external hexagon-zirconia, external hexagon-hybrid, internal hexagon-titanium, internal hexagon-zirconia, internal hexagon-hybrid, Morse tapered-titanium, Morse tapered-zirconia, and Morse tapered-hybrid. Finite element models consisted of a 4×13-mm implant, anatomic abutment, and lithium disilicate central incisor crown cemented over the abutment. The 49 N occlusal loading was applied in 6 steps to simulate the incisal guidance. Equivalent von Mises stress (σvM) was used for both the qualitative and quantitative evaluation of the implant and abutment in all the groups and the maximum (σmax) and minimum (σmin) principal stresses for the numerical comparison of the zirconia parts. The highest abutment σvM occurred in the Morse-tapered groups and the lowest in the external hexagon-hybrid, internal hexagon-titanium, and internal hexagon-hybrid groups. The σmax and σmin values were lower in the hybrid groups than in the zirconia groups. The stress distribution concentrated in the abutment-implant interface in all the groups, regardless of the platform connection or abutment material. The platform connection influenced the stress on abutments more than the abutment material. The stress values for implants were similar among different platform connections, but greater stress concentrations were observed in internal connections. Copyright © 2014 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Strong 3D and 1D magnetism in hexagonal Fe-chalcogenides FeS and FeSe vs. weak magnetism in hexagonal FeTe

DOE Office of Scientific and Technical Information (OSTI.GOV)

Parker, David S.

2017-06-13

We present a comparative theoretical study of the hexagonal forms of the Fe-chalcogenides FeS, FeSe and FeTe with their better known tetragonal forms. While the tetragonal forms exhibit only an incipient antiferromagnetism and experimentally show superconductivity when doped, the hexagonal forms of FeS and FeSe display a robust magnetism. We show that this strong magnetism arises from a van Hove singularity associated with the direct Fe-Fe c-axis chains in the generally more three-dimensional NiAs structure. We also find that hexagonal FeTe is much less magnetic than the other two hexagonal materials, so that unconventional magnetically-mediated superconductivity is possible, although amore » large T c value is unlikely.« less

Controlling insulin release from reverse hexagonal (HII) liquid crystalline mesophase by enzymatic lipolysis.

PubMed

Mishraki-Berkowitz, Tehila; Cohen, Guy; Aserin, Abraham; Garti, Nissim

2018-01-01

In the present study we aimed to control insulin release from the reverse hexagonal (H II ) mesophase using Thermomyces lanuginosa lipase (TLL) in the environment (outer TLL) or within the H II cylinders (inner TLL). Two insulin-loaded systems differing by the presence (or absence) of phosphatidylcholine (PC) were examined. In general, incorporation of PC into the H II interface (without TLL) increased insulin release, as a more cooperative system was formed. Addition of TLL to the systems' environments resulted in lipolysis of the H II structure. In the absence of PC, the lipolysis was more dominant and led to a significant increase in insulin release (50% after 8h). However, the presence of PC stabilized the interface, hindering the lipolysis, and therefore no impact on the release profile was detected during the first 8h. Entrapment of TLL within the H II cylinders (with and without PC) drastically increased insulin release in both systems up to 100%. In the presence of PC insulin released faster and the structure was more stable. Consequently, the presence of lipases (inner or outer) both enhanced the destruction of the carrier, and provided sustained release of the entrapped insulin. Copyright © 2017 Elsevier B.V. All rights reserved.

Silicon Nitride Equation of State

NASA Astrophysics Data System (ADS)

Swaminathan, Pazhayannur; Brown, Robert

2015-06-01

This report presents the development a global, multi-phase equation of state (EOS) for the ceramic silicon nitride (Si3N4) . Structural forms include amorphous silicon nitride normally used as a thin film and three crystalline polymorphs. Crystalline phases include hexagonal α-Si3N4, hexagonalβ-Si3N4, and the cubic spinel c-Si3N4. Decomposition at about 1900 °C results in a liquid silicon phase and gas phase products such as molecular nitrogen, atomic nitrogen, and atomic silicon. The silicon nitride EOS was developed using EOSPro which is a new and extended version of the PANDA II code. Both codes are valuable tools and have been used successfully for a variety of material classes. Both PANDA II and EOSPro can generate a tabular EOS that can be used in conjunction with hydrocodes. The paper describes the development efforts for the component solid phases and presents results obtained using the EOSPro phase transition model to investigate the solid-solid phase transitions in relation to the available shock data. Furthermore, the EOSPro mixture model is used to develop a model for the decomposition products and then combined with the single component solid models to study the global phase diagram. Sponsored by the NASA Goddard Space Flight Center Living With a Star program office.

Technique for the control of the crystal habit of ultrafine particles in the gas-evaporation technique

NASA Astrophysics Data System (ADS)

Kasukabe, S.; Mihama, K.

1986-12-01

Magnesium ultrafine particles have clear-cut habits such as hexagonal plates and polyhedra. When magnesium is evaporated downwards using a tube with holes at the bottom, hexagonal plates are formed exclusively throughout the smoke. Their size is controlled by selecting an inert gas. The growth process of an hexagonal plate can be considered to be a coalescent growth of other hexagonal plates.

Thermal conductivity of hexagonal Si, Ge, and Si1-xGex alloys from first-principles

NASA Astrophysics Data System (ADS)

Gu, Xiaokun; Zhao, C. Y.

2018-05-01

Hexagonal Si and Ge with a lonsdaleite crystal structure are allotropes of silicon and germanium that have recently been synthesized. These materials as well as their alloys are promising candidates for novel applications in optoelectronics. In this paper, we systematically study the phonon transport and thermal conductivity of hexagonal Si, Ge, and their alloys by using the first-principle-based Peierls-Boltzmann transport equation approach. Both three-phonon and four-phonon scatterings are taken into account in the calculations as the phonon scattering mechanisms. The thermal conductivity anisotropy of these materials is identified. While the thermal conductivity parallel to the hexagonal plane for hexagonal Si and Ge is found to be larger than that perpendicular to the hexagonal plane, alloying effectively tunes the thermal conductivity anisotropy by suppressing the thermal conductivity contributions from the middle-frequency phonons. The importance of four-phonon scatterings is assessed by comparing the results with the calculations without including four-phonon scatterings. We find that four-phonon scatterings cannot be ignored in hexagonal Si and Ge as the thermal conductivity would be overestimated by around 10% (40%) at 300 K (900) K. In addition, the phonon mean free path distribution of hexagonal Si, Ge, and their alloys is also discussed.

Honeycomb-like thin films of polystyrene-block-poly(2-vinylpyridine) embedded with gold or silver nanoparticles formed at the planer liquid/liquid interface.

PubMed

Wang, Di; Ma, Huihui; Chu, Chunxiao; Hao, Jingcheng; Liu, Hong-Guo

2013-07-15

Composite thin films of polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) decorated with Au or Ag nanoclusters and nanoparticles were fabricated at the interfaces of chloroform solution of PS-b-P2VP and aqueous solutions of HAuCl4 or AgNO3. Transmission electron microscopy (TEM) investigations indicated that large area of a single-layer honeycomb structure was formed, which is composed of polygons (most of them are hexagons) whose walls look like spindles with the length of several hundreds of nanometers. Large amount of Au or Ag nanoparticles are embedded in the walls and the undersides of the honeycomb structures. The formation of these novel composite structures was attributed to the adsorption of block copolymer molecules and inorganic species of AuCl4(-) and Ag(+) ions at the liquid-liquid interface, the combination of the polymer molecules and the inorganic ions, and the self-assembly of the composite molecules. After UV-light irradiation and KBH4 aqueous solution treatment, the inorganic species were reduced completely, as confirmed by UV-vis spectra and X-ray photoelectron spectra. These composite films exhibited high catalytic activities for the reduction of 4-nitrophenol (4-NP) by KBH4 in aqueous solutions. Copyright © 2013 Elsevier Inc. All rights reserved.

Liquid Crystalline Systems Based on Glyceryl Monooleate and Penetration Enhancers for Skin Delivery of Celecoxib: Characterization, In Vitro Drug Release, and In Vivo Studies.

PubMed

Dante, Mariane de Cássia Lima; Borgheti-Cardoso, Livia Neves; Fantini, Marcia Carvalho de Abreu; Praça, Fabíola Silva Garcia; Medina, Wanessa Silva Garcia; Pierre, Maria Bernadete Riemma; Lara, Marilisa Guimarães

2018-03-01

Celecoxib (CXB) is a widely used anti-inflammatory drug that also acts as a chemopreventive agent against several types of cancer, including skin cancer. As the long-term oral administration of CXB has been associated with severe side effects, the skin delivery of this drug represents a promising alternative for the treatment of skin inflammatory conditions and chemoprevention of skin cancer. We prepared and characterized liquid crystalline systems based on glyceryl monooleate and water containing penetration enhancers which were primarily designed to promote skin delivery of CXB. Analysis of their phase behavior revealed the formation of cubic and hexagonal phases depending on the systems' composition. The systems' structure and composition markedly affected the in vitro CXB release profile. Oleic acid reduced CXB release rate, but association oleic acid/propylene glycol increased the drug release rate. The developed systems significantly reduced inflammation in an aerosil-induced rat paw edema model. The systems' composition and liquid crystalline structure influenced their anti-inflammatory potency. Cubic phase systems containing oleic acid/propylene glycol association reduced edema in a sustained manner, indicating that they modulate CXB release and permeation. Our findings demonstrate that the developed liquid crystalline systems are potential carriers for the skin delivery of CXB. Copyright © 2018 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Microplasma-liquid interactions for nanomaterials synthesis

NASA Astrophysics Data System (ADS)

Patel, Jenish; Maguire, Paul; Mariotti, Davide

2012-10-01

Interactions of microplasmas with solid, liquid and/or gas precursors provide new pathways for the synthesis and surface-engineering of nanomaterials. This study is focused on the plasma-induced non-euqilibrium liquid-chemistry (PiLC) as an effective approach to synthesize colloidal metal nanoparticles without using any reducing/capping agents. Highly dispersed gold and silver nanoparticles (NPs) were synthesized in aqueous solutions without any capping agents which explore the opportunities to functionalize the surface of these surfactant-free metal NPs for a better device applications. In particular, various sizes (5 nm to 100 nm) and shapes (e.g. spherical, hexagonal, pentagonal, triangular, etc.) of the gold nanoparticles (AuNPs) were formed with different concentrations of gold precursor. Moreover, conductivity, pH and temperature of the solutions were measured before and after the plasma processing, in order to realize the basic chemistry initiated by plasma in/at liquid surface. Especially, to understand the basic reduction process of AuNPs synthesis by plasma, we measured the presence the of hydrogen peroxide (H2O2) which is believed to be a strong reductant for gold and for the first time we demonstrated experimentally that H2O2 is the key factor that reduces the gold precursor to AuNPs. These investigations create the opportunities to understand how these microplasmas can be effectively explored to other materials synthesis/processing.

Anatomy of triply-periodic network assemblies: characterizing skeletal and inter-domain surface geometry of block copolymer gyroids.

PubMed

Prasad, Ishan; Jinnai, Hiroshi; Ho, Rong-Ming; Thomas, Edwin L; Grason, Gregory M

2018-05-09

Triply-periodic networks (TPNs), like the well-known gyroid and diamond network phases, abound in soft matter assemblies, from block copolymers (BCPs), lyotropic liquid crystals and surfactants to functional architectures in biology. While TPNs are, in reality, volume-filling patterns of spatially-varying molecular composition, physical and structural models most often reduce their structure to lower-dimensional geometric objects: the 2D interfaces between chemical domains; and the 1D skeletons that thread through inter-connected, tubular domains. These lower-dimensional structures provide a useful basis of comparison to idealized geometries based on triply-periodic minimal, or constant-mean curvature surfaces, and shed important light on the spatially heterogeneous packing of molecular constituents that form the networks. Here, we propose a simple, efficient and flexible method to extract a 1D skeleton from 3D volume composition data of self-assembled networks. We apply this method to both self-consistent field theory predictions as well as experimental electron microtomography reconstructions of the double-gyroid phase of an ABA triblock copolymer. We further demonstrate how the analysis of 1D skeleton, 2D inter-domain surfaces, and combinations therefore, provide physical and structural insight into TPNs, across multiple length scales. Specifically, we propose and compare simple measures of network chirality as well as domain thickness, and analyze their spatial and statistical distributions in both ideal (theoretical) and non-ideal (experimental) double gyroid assemblies.

Application of positron annihilation lifetime spectroscopy (PALS) to study the nanostructure in amphiphile self-assembly materials: phytantriol cubosomes and hexosomes.

PubMed

Dong, Aurelia W; Fong, Celesta; Waddington, Lynne J; Hill, Anita J; Boyd, Ben J; Drummond, Calum J

2015-01-21

Self-assembled amphiphile nanostructures of colloidal dimensions such as cubosomes and hexosomes are of interest as delivery vectors in pharmaceutical and nanomedicine applications. Translation would be assisted through a better of understanding of the effects of drug loading on the internal nanostructure, and the relationship between this nanostructure and drug release profile. Positron annihilation lifetime spectroscopy (PALS) is sensitive to local microviscosity and is used as an in situ molecular probe to examine the Q2 (cubosome) → H2 (hexosome) → L2 phase transitions of the pharmaceutically relevant phytantriol-water system in the presence of a model hydrophobic drug, vitamin E acetate (VitEA). It is shown that the ortho-positronium lifetime (τ) is sensitive to molecular packing and mobility and this has been correlated with the rheological properties of individual lyotropic liquid crystalline mesophases. Characteristic PALS lifetimes for L2 (τ4∼ 4 ns) ∼ H2 (τ4∼ 4 ns) > Q(2 Pn3m) (τ4∼ 2.2 ns) are observed for the phytantriol-water system, with the addition of VitEA yielding a gradual increase in τ from τ∼ 2.2 ns for cubosomes to τ∼ 3.5 ns for hexosomes. The dynamic chain packing at higher temperatures and in the L2 and H2 phases is qualitatively less "viscous", consistent with rheological measurements. This information offers increased understanding of the relationship between internal nanostructure and species permeability.

Comparison of presumptive blood test kits including hexagon OBTI.

PubMed

Johnston, Emma; Ames, Carole E; Dagnall, Kathryn E; Foster, John; Daniel, Barbara E

2008-05-01

Four presumptive blood tests, Hexagon OBTI, Hemastix(R), Leucomalachite green (LMG), and Kastle-Meyer (KM) were compared for their sensitivity in the identification of dried bloodstains. Stains of varying blood dilutions were subjected to each presumptive test and the results compared. The Hexagon OBTI buffer volume was also reduced to ascertain whether this increased the sensitivity of the kit. The study found that Hemastix(R) was the most sensitive test for trace blood detection. Only with the reduced buffer volume was the Hexagon OBTI kit as sensitive as the LMG and KM tests. However, the Hexagon OBTI kit has the advantage of being a primate specific blood detection kit. This study also investigated whether the OBTI buffer within the kit could be utilized for DNA profiling after presumptive testing. The results show that DNA profiles can be obtained from the Hexagon OBTI kit buffer directly.

Synthesis, analysis and processing of novel materials in the yttrium oxide-aluminum oxide system

NASA Astrophysics Data System (ADS)

Marchal, Julien Claudius

In the current work, liquid feed flame spray pyrolysis (LF-FSP) was used to create three novel nanopowders in the Y2O3-Al 2O3 system: alpha-Al2O3, YAG (garnet Y3Al5O12) and hexagonal Y3Al 5O12. For example, LF-FSP combustion of metalloorganic yttrium and aluminum precursors in a 3/5 ratio forms hexagonal Y3Al5O 12, a newly discovered crystalline phase detailed in this work. The resulting 15-35 nm average particle size, single crystal nanopowders were characterized by TGA-DTA, XRD, HR-TEM, electron diffraction and FTIR. The data was used to establish a model for the crystal structure of this new phase (hexagonal, with crystal parameter of a = 0.736 nm, c = 1.052) consisting of a superlattice of substituted hexagonal YAlO3. YAG has been extensively investigated for its applications as scintillators, phosphors and as a laser host. Fully dispersible, unaggregated single crystal YAG nanopowders with average particle sizes of 35-50 nm were obtained from hexagonal Y3Al5O12 after annealing at 850°C-1200°C (for 2h-8d). The resulting YAG nanopowder was processed into green bodies using cold isostatic pressing after adding binders. 99%+ dense monoliths were obtained after sintering at 1400°C in vacuum (6-8 h), while maintaining grain sizes < 500 nm. The ability to sinter while keeping sub-micron grains differs from present techniques (where translucency is obtained through exaggerated grain growth to 5-10 microns) reported in the literature for sintering polycrystalline YAG, and is the first step for improving polycrystalline YAG laser host optical properties. LF-FSP processing of transition Al2O3 nanopowders converts them to single crystal alpha-Al2O3 nanopowders, previously thought impossible to obtain. The alpha-Al2O 3 nanopowders thus obtained, consist of unaggregated 30-40 nm single particles. These nanopowders were characterized by XRD, HR-TEM, SEM, DLS, FTIR. Green bodies of alpha-Al2O3 nanopowders were sintered to 99% density without sintering aids at 1400°C (6-8 h). After HIPing at 1400°C and 138 MPa, the pellets exhibited some transparency. LF-FSP thus allows synthesis of large quantities of previously unavailable alpha-Al 2O3 nanopowders necessary for developing nanograined alpha-Al 2O3 ceramic monoliths for transparent armors, polycrystalline laser hosts and prosthetic implants. Most importantly, it demonstrates the use of LF-FSP to modify the crystalline phase of nanopowders, without causing aggregation.

Metastable phases of silver and gold in hexagonal structure

NASA Astrophysics Data System (ADS)

Jona, F.; Marcus, P. M.

2004-07-01

Metastable phases of silver and gold in hexagonal close-packed structures are investigated by means of first-principles total-energy calculations. Two different methods are employed to find the equilibrium states: determination of the minima along the hexagonal epitaxial Bain path, and direct determination of minima of the total energy by a new minimum-path procedure. Both metals have two equilibrium states at different values of the hexagonal axial ratio c/a. For both metals, the elastic constants show that the high-c/a states are stable, hence, since the ground states are face-centred cubic, these states represent hexagonal close-packed metastable phases. The elastic constants of the low-c/a states show that they are unstable.

Synthesis of hexagonal wurtzite Cu{sub 2}ZnSnS{sub 4} prisms by an ultrasound-assisted microwave solvothermal method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Long, Fei, E-mail: long.drf@gmail.com; Chi, Shangsen; Institute of Advanced Materials and Technology, University of Science and Technology Beijing, Beijing 100083

Wurtzite Cu{sub 2}ZnSnS{sub 4} (CZTS) hexagonal prisms were synthesized by a simple ultrasound-microwave solvothermal method. The product was characterized by XRD, FESEM, EDS, TEM, Raman and UV–vis spectrometer. The hexagonal prisms were 0.5–2 μm wide and 5–12 μm long. The PVP played an important role in the formation of the CZTS hexagonal prisms. In addition, the ultrasound-assisted microwave process was helpful for synthesis of wurtzite rather than kesterite phase CZTS. A nucleation–dissolution–recrystallization mechanism was also proposed to explain the growth of the CZTS hexagonal prisms. - Graphical abstract: Wurtzite Cu{sub 2}ZnSnS{sub 4} hexagonal prisms were synthesized by ultrasound-microwave solvothermal method.more » The ultrasound-assisted microwave process and PVP were useful to the growth of CZTS. A nucleation–dissolution–recrystallization growth mechanism was also proposed. - Highlights: • Wurtzite Cu{sub 2}ZnSnS{sub 4} was prepared by ultrasound-assisted microwave solvothermal method. • The wurtzite CZTS hexagonal prisms are demonstrated a band gap of 1.49 eV. • Synergistic effect of ultrasound and microwave is helpful to prepare Wurtzite CZTS. • PVP plays an important role in the formation of the CZTS hexagonal prisms. • Nucleation–dissolution–recrystallization growth mechanism of the CZTS was proposed.« less

Research on the comparison of extension mechanism of cellular automaton based on hexagon grid and rectangular grid

NASA Astrophysics Data System (ADS)

Zhai, Xiaofang; Zhu, Xinyan; Xiao, Zhifeng; Weng, Jie

2009-10-01

Historically, cellular automata (CA) is a discrete dynamical mathematical structure defined on spatial grid. Research on cellular automata system (CAS) has focused on rule sets and initial condition and has not discussed its adjacency. Thus, the main focus of our study is the effect of adjacency on CA behavior. This paper is to compare rectangular grids with hexagonal grids on their characteristics, strengths and weaknesses. They have great influence on modeling effects and other applications including the role of nearest neighborhood in experimental design. Our researches present that rectangular and hexagonal grids have different characteristics. They are adapted to distinct aspects, and the regular rectangular or square grid is used more often than the hexagonal grid. But their relative merits have not been widely discussed. The rectangular grid is generally preferred because of its symmetry, especially in orthogonal co-ordinate system and the frequent use of raster from Geographic Information System (GIS). However, in terms of complex terrain, uncertain and multidirectional region, we have preferred hexagonal grids and methods to facilitate and simplify the problem. Hexagonal grids can overcome directional warp and have some unique characteristics. For example, hexagonal grids have a simpler and more symmetric nearest neighborhood, which avoids the ambiguities of the rectangular grids. Movement paths or connectivity, the most compact arrangement of pixels, make hexagonal appear great dominance in the process of modeling and analysis. The selection of an appropriate grid should be based on the requirements and objectives of the application. We use rectangular and hexagonal grids respectively for developing city model. At the same time we make use of remote sensing images and acquire 2002 and 2005 land state of Wuhan. On the base of city land state in 2002, we make use of CA to simulate reasonable form of city in 2005. Hereby, these results provide a proof of concept for hexagonal which has great dominance.

Novel high pressure hexagonal OsB2 by mechanochemistry

NASA Astrophysics Data System (ADS)

Xie, Zhilin; Graule, Moritz; Orlovskaya, Nina; Andrew Payzant, E.; Cullen, David A.; Blair, Richard G.

2014-07-01

Hexagonal OsB2, a theoretically predicted high-pressure phase, has been synthesized for the first time by a mechanochemical method, i.e., high energy ball milling. X-ray diffraction indicated that formation of hexagonal OsB2 begins after 2.5 h of milling, and the reaction reaches equilibrium after 18 h of milling. Rietveld refinement of the powder data indicated that hexagonal OsB2 crystallizes in the P63/mmc space group (No. 194) with lattice parameters of a=2.916 Å and c=7.376 Å. Transmission electron microscopy confirmed the appearance of the hexagonal OsB2 phase after high energy ball milling. in situ X-ray diffraction experiments showed that the phase is stable from -225 °C to 1050 °C. The hexagonal OsB2 powder was annealed at 1050 °C for 6 days in vacuo to improve crystallinity and remove strain induced during the mechanochemical synthesis. The structure partially converted to the orthorhombic phase (20 wt%) after fast current assisted sintering of hexagonal OsB2 at 1500 °C for 5 min. Mechanochemical approaches to the synthesis of hard boride materials allow new phases to be produced that cannot be prepared using conventional methods.

How faceted liquid droplets grow tails: from surface topology to active motion

NASA Astrophysics Data System (ADS)

Sloutskin, Eli

Among all possible shapes of a volume V, a sphere has the smallest surface area A. Therefore, liquid droplets are spherical, minimizing their interfacial energy γA for a given interfacial tension γ > 0 . This talk will demonstrate that liquid oil (alkane) droplets in water, stabilized by a common surfactant can be temperature-tuned to adopt icosahedral and other faceted shapes, above the bulk melting temperature of the oil. Although emulsions have been studied for centuries no faceted liquid droplets have ever been reported. The formation of an icosahedral shape is attributed to the interplay between γ and the elastic properties of the interfacial monomolecular layer, which crystallizes here 10-15K above bulk melting, leaving the droplet's bulk liquid. The icosahedral symmetry is dictated by twelve five-fold topological defects, forming within the hexagonally-packed interfacial crystalline monolayer. Moreover, we demonstrate that upon further cooling this `interfacial freezing' effect makes γ transiently switch its sign, leading to a spontaneous splitting of droplets and an active growth of their surface area, reminiscent of the classical spontaneous emulsification, yet driven by completely different physics. The observed phenomena allow deeper insights to be gained into the fundamentals of molecular elasticity and open new vitas for a wide range of novel nanotechnological applications, from self-assembly of complex shapes to new delivery strategies in bio-medicine. Acknowledgment is made to the Donors of the American Chemical Society Petroleum Research Fund for support of this research and to the Kahn Foundation for the purchase of equipment.

Transmission X-ray scattering as a probe for complex liquid-surface structures

DOE PAGES

Fukuto, Masafumi; Yang, Lin; Nykypanchuk, Dmytro; ...

2016-01-28

The need for functional materials calls for increasing complexity in self-assembly systems. As a result, the ability to probe both local structure and heterogeneities, such as phase-coexistence and domain morphologies, has become increasingly important to controlling self-assembly processes, including those at liquid surfaces. The traditional X-ray scattering methods for liquid surfaces, such as specular reflectivity and grazing-incidence diffraction, are not well suited to spatially resolving lateral heterogeneities due to large illuminated footprint. A possible alternative approach is to use scanning transmission X-ray scattering to simultaneously probe local intermolecular structures and heterogeneous domain morphologies on liquid surfaces. To test the feasibilitymore » of this approach, transmission small- and wide-angle X-ray scattering (TSAXS/TWAXS) studies of Langmuir films formed on water meniscus against a vertically immersed hydrophilic Si substrate were recently carried out. First-order diffraction rings were observed in TSAXS patterns from a monolayer of hexagonally packed gold nanoparticles and in TWAXS patterns from a monolayer of fluorinated fatty acids, both as a Langmuir monolayer on water meniscus and as a Langmuir–Blodgett monolayer on the substrate. The patterns taken at multiple spots have been analyzed to extract the shape of the meniscus surface and the ordered-monolayer coverage as a function of spot position. These results, together with continual improvement in the brightness and spot size of X-ray beams available at synchrotron facilities, support the possibility of using scanning-probe TSAXS/TWAXS to characterize heterogeneous structures at liquid surfaces.« less

Three-gradient regular solution model for simple liquids wetting complex surface topologies

PubMed Central

Akerboom, Sabine; Kamperman, Marleen

2016-01-01

Summary We use regular solution theory and implement a three-gradient model for a liquid/vapour system in contact with a complex surface topology to study the shape of a liquid drop in advancing and receding wetting scenarios. More specifically, we study droplets on an inverse opal: spherical cavities in a hexagonal pattern. In line with experimental data, we find that the surface may switch from hydrophilic (contact angle on a smooth surface θY < 90°) to hydrophobic (effective advancing contact angle θ > 90°). Both the Wenzel wetting state, that is cavities under the liquid are filled, as well as the Cassie–Baxter wetting state, that is air entrapment in the cavities under the liquid, were observed using our approach, without a discontinuity in the water front shape or in the water advancing contact angle θ. Therefore, air entrapment cannot be the main reason why the contact angle θ for an advancing water front varies. Rather, the contact line is pinned and curved due to the surface structures, inducing curvature perpendicular to the plane in which the contact angle θ is observed, and the contact line does not move in a continuous way, but via depinning transitions. The pinning is not limited to kinks in the surface with angles θkink smaller than the angle θY. Even for θkink > θY, contact line pinning is found. Therefore, the full 3D-structure of the inverse opal, rather than a simple parameter such as the wetting state or θkink, determines the final observed contact angle. PMID:27826512

Pyramidal dislocation induced strain relaxation in hexagonal structured InGaN/AlGaN/GaN multilayer

NASA Astrophysics Data System (ADS)

Yan, P. F.; Du, K.; Sui, M. L.

2012-10-01

Due to the special dislocation slip systems in hexagonal lattice, dislocation dominated deformations in hexagonal structured multilayers are significantly different from that in cubic structured systems. In this work, we have studied the strain relaxation mechanism in hexagonal structured InGaN/AlGaN/GaN multilayers with transmission electron microscopy. Due to lattice mismatch, the strain relaxation was found initiated with the formation of pyramidal dislocations. Such dislocations locally lie at only one preferential slip direction in the hexagonal lattice. This preferential slip causes a shear stress along the basal planes and consequently leads to dissociation of pyramidal dislocations and operation of the basal plane slip system. The compressive InGaN layers and "weak" AlGaN/InGaN interfaces stimulate the dissociation of pyramidal dislocations at the interfaces. These results enhance the understanding of interactions between dislocations and layer interfaces and shed new lights on deformation mechanism in hexagonal-lattice multilayers.

Electronic properties of two-dimensional zinc oxide in hexagonal, (4,4)-tetragonal, and (4,8)-tetragonal structures by using Hybrid Functional calculation

NASA Astrophysics Data System (ADS)

Supatutkul, C.; Pramchu, S.; Jaroenjittichai, A. P.; Laosiritaworn, Y.

2017-09-01

This work reports the structures and electronic properties of two-dimensional (2D) ZnO in hexagonal, (4,8)-tetragonal, and (4,4)-tetragonal monolayer using GGA and HSE-hybrid functional. The calculated results show that the band gaps of 2D ZnO sheets are wider than those of the bulk ZnO. The hexagonal and (4,8)-tetragonal phases yield direct band gaps, which are 4.20 eV, and 4.59 eV respectively, while the (4,4)-tetragonal structure has an indirect band gap of 3.02 eV. The shrunken Zn-O bond lengths in the hexagonal and (4,8)-tetragonal indicate that they become more ionic in comparison with the bulk ZnO. In addition, the hexagonal ZnO sheet is the most energetically favourable. The total energy differences of (4,8)-tetragonal and (4,4)-tetragonal sheets from that of hexagonal monolayer (per formula unit) are 197 meV and 318 meV respectively.

Alumina nanowire growth by water decomposition and the peritectic reaction of decagonal Al{sub 65}Cu{sub 15}Co{sub 20} quasicrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Téllez-Vázquez, J.O., E-mail: oswald.tellez@gmail.com; Patiño-Carachure, C., E-mail: cpatino@pampano.unacar.mx; Rosas, G., E-mail: grtrejo@yahoo07.com.mx

2016-02-15

In this paper, the results of the Al{sub 2}O{sub 3} nanowires' growth through a chemical reaction between Al and water vapor at 1050 °C are presented. Our approach is based on two primary considerations. First, at room temperature, the Al{sub 65}Cu{sub 15}Co{sub 20} alloy is affected by the following mechanism: 2Al (s) + 3H{sub 2}O (g) → Al{sub 2}O{sub 3} (s) + H{sub 2} (g). In this reaction, the released hydrogen induces cleavage fracture of the material to form small particles. Second, the Al{sub 65}Cu{sub 15}Co{sub 20} quasicrystalline phase is transformed on heating to liquid + Al (Cu, Co) cubicmore » phase through a peritectic reaction at 1050 °C. The Al-rich liquid then reacts with water vapor, forming Al{sub 2}O{sub 3} nanowires. X-ray diffraction (XRD) analysis shows that the formed nanowires have a hexagonal structure, and infrared analysis further confirms the presence of α-Al{sub 2}O{sub 3} phase in the final products. Transmission electron microscopy observations show that nanoparticles are present at the end of nanowires, suggesting the VLS growth mechanism. Elemental analysis by energy dispersive spectroscopy (EDS) indicates that the particles at the tip of the nanowires are mainly formed by Co and Cu alloying elements and small amounts of Al. Electron microscopy observations showed nanowires with diameters ranging from 20 to 70 nm; the average diameter was 37 nm and the nanowire lengths were up to several micrometers. - Highlights: • Hexagonal alumina nanowires are grown at 1050 °C through the VLS process. • Alumina nanowires are obtained by the decomposition of decagonal quasicrystalline phase. • The decagonal phase decomposition follows a peritectic reaction at 1030 °C. • Nanoparticles are obtained by hydrogen embrittlement mechanism. • The nanoparticles catalyze the water decomposition to form wires.« less

Survival and failure modes: platform-switching for internal and external hexagon cemented fixed dental prostheses.

PubMed

Anchieta, Rodolfo B; Machado, Lucas S; Hirata, Ronaldo; Coelho, Paulo G; Bonfante, Estevam A

2016-10-01

This study evaluated the probability of survival (reliability) of platform-switched fixed dental prostheses (FDPs) cemented on different implant-abutment connection designs. Eighty-four-three-unit FDPs (molar pontic) were cemented on abutments connected to two implants of external or internal hexagon connection. Four groups (n = 21 each) were established: external hexagon connection and regular platform (ERC); external hexagon connection and switched platform (ESC); internal hexagon and regular platform (IRC); and internal hexagon and switched platform (ISC). Prostheses were subjected to step-stress accelerated life testing in water. Weibull curves and probability of survival for a mission of 100,000 cycles at 400 N (two-sided 90% CI) were calculated. The beta values of 0.22, 0.48, 0.50, and 1.25 for groups ERC, ESC, IRC, and ISC, respectively, indicated a limited role of fatigue in damage accumulation, except for group ISC. Survival decreased for both platform-switched groups (ESC: 74%, and ISC: 59%) compared with the regular matching platform counterparts (ERC: 95%, and IRC: 98%). Characteristic strength was higher only for ERC compared with ESC, but not different between internal connections. Failures chiefly involved the abutment screw. Platform switching decreased the probability of survival of FDPs on both external and internal connections. The absence in loss of characteristic strength observed in internal hexagon connections favor their use compared with platform-switched external hexagon connections. © 2016 Eur J Oral Sci.

Capillary-Force-Assisted Clean-Stamp Transfer of Two-Dimensional Materials.

PubMed

Ma, Xuezhi; Liu, Qiushi; Xu, Da; Zhu, Yangzhi; Kim, Sanggon; Cui, Yongtao; Zhong, Lanlan; Liu, Ming

2017-11-08

A simple and clean method of transferring two-dimensional (2D) materials plays a critical role in the fabrication of 2D electronics, particularly the heterostructure devices based on the artificial vertical stacking of various 2D crystals. Currently, clean transfer techniques rely on sacrificial layers or bulky crystal flakes (e.g., hexagonal boron nitride) to pick up the 2D materials. Here, we develop a capillary-force-assisted clean-stamp technique that uses a thin layer of evaporative liquid (e.g., water) as an instant glue to increase the adhesion energy between 2D crystals and polydimethylsiloxane (PDMS) for the pick-up step. After the liquid evaporates, the adhesion energy decreases, and the 2D crystal can be released. The thin liquid layer is condensed to the PDMS surface from its vapor phase, which ensures the low contamination level on the 2D materials and largely remains their chemical and electrical properties. Using this method, we prepared graphene-based transistors with low charge-neutral concentration (3 × 10 10 cm -2 ) and high carrier mobility (up to 48 820 cm 2 V -1 s -1 at room temperature) and heterostructure optoelectronics with high operation speed. Finally, a capillary-force model is developed to explain the experiment.

Defect chaos of oscillating hexagons in rotating convection

PubMed

Echebarria; Riecke

2000-05-22

Using coupled Ginzburg-Landau equations, the dynamics of hexagonal patterns with broken chiral symmetry are investigated, as they appear in rotating non-Boussinesq or surface-tension-driven convection. We find that close to the secondary Hopf bifurcation to oscillating hexagons the dynamics are well described by a single complex Ginzburg-Landau equation (CGLE) coupled to the phases of the hexagonal pattern. At the band center these equations reduce to the usual CGLE and the system exhibits defect chaos. Away from the band center a transition to a frozen vortex state is found.

Structure and energetics of carbon, hexagonal boron nitride, and carbon/hexagonal boron nitride single-layer and bilayer nanoscrolls

NASA Astrophysics Data System (ADS)

Siahlo, Andrei I.; Poklonski, Nikolai A.; Lebedev, Alexander V.; Lebedeva, Irina V.; Popov, Andrey M.; Vyrko, Sergey A.; Knizhnik, Andrey A.; Lozovik, Yurii E.

2018-03-01

Single-layer and bilayer carbon and hexagonal boron nitride nanoscrolls as well as nanoscrolls made of bilayer graphene/hexagonal boron nitride heterostructure are considered. Structures of stable states of the corresponding nanoscrolls prepared by rolling single-layer and bilayer rectangular nanoribbons are obtained based on the analytical model and numerical calculations. The lengths of nanoribbons for which stable and energetically favorable nanoscrolls are possible are determined. Barriers to rolling of single-layer and bilayer nanoribbons into nanoscrolls and barriers to nanoscroll unrolling are calculated. Based on the calculated barriers nanoscroll lifetimes in the stable state are estimated. Elastic constants for bending of graphene and hexagonal boron nitride layers used in the model are found by density functional theory calculations.

Thermal conductivity of hexagonal Si and hexagonal Si nanowires from first-principles

NASA Astrophysics Data System (ADS)

Raya-Moreno, Martí; Aramberri, Hugo; Seijas-Bellido, Juan Antonio; Cartoixà, Xavier; Rurali, Riccardo

2017-07-01

We calculate the thermal conductivity, κ, of the recently synthesized hexagonal diamond (lonsdaleite) Si using first-principles calculations and solving the Boltzmann Transport Equation. We find values of κ which are around 40% lower than in the common cubic diamond polytype of Si. The trend is similar for [111] Si nanowires, with reductions of the thermal conductivity that are even larger than in the bulk in some diameter range. The Raman active modes are identified, and the role of mid-frequency optical phonons that arise as a consequence of the reduced symmetry of the hexagonal lattice is discussed. We also show briefly that popular classic potentials used in molecular dynamics might not be suited to describe hexagonal polytypes, discussing the case of the Tersoff potential.

Engineering and Localization of Quantum Emitters in Large Hexagonal Boron Nitride Layers.

PubMed

Choi, Sumin; Tran, Toan Trong; Elbadawi, Christopher; Lobo, Charlene; Wang, Xuewen; Juodkazis, Saulius; Seniutinas, Gediminas; Toth, Milos; Aharonovich, Igor

2016-11-02

Hexagonal boron nitride is a wide-band-gap van der Waals material that has recently emerged as a promising platform for quantum photonics experiments. In this work, we study the formation and localization of narrowband quantum emitters in large flakes (up to tens of micrometers wide) of hexagonal boron nitride. The emitters can be activated in as-grown hexagonal boron nitride by electron irradiation or high-temperature annealing, and the emitter formation probability can be increased by ion implantation or focused laser irradiation of the as-grown material. Interestingly, we show that the emitters are always localized at the edges of the flakes, unlike most luminescent point defects in three-dimensional materials. Our results constitute an important step on the roadmap of deploying hexagonal boron nitride in nanophotonics applications.

Na(+) transport, and the E(1)P-E(2)P conformational transition of the Na(+)/K(+)-ATPase.

PubMed Central

Babes, A; Fendler, K

2000-01-01

We have used admittance analysis together with the black lipid membrane technique to analyze electrogenic reactions within the Na(+) branch of the reaction cycle of the Na(+)/K(+)-ATPase. ATP release by flash photolysis of caged ATP induced changes in the admittance of the compound membrane system that are associated with partial reactions of the Na(+)/K(+)-ATPase. Frequency spectra and the Na(+) dependence of the capacitive signal are consistent with an electrogenic or electroneutral E(1)P <--> E(2)P conformational transition which is rate limiting for a faster electrogenic Na(+) dissociation reaction. We determine the relaxation rate of the rate-limiting reaction and the equilibrium constants for both reactions at pH 6.2-8.5. The relaxation rate has a maximum value at pH 7.4 (approximately 320 s(-1)), which drops to acidic (approximately 190 s(-1)) and basic (approximately 110 s(-1)) pH. The E(1)P <--> E(2)P equilibrium is approximately at a midpoint position at pH 6.2 (equilibrium constant approximately 0.8) but moves more to the E(1)P side at basic pH 8.5 (equilibrium constant approximately 0.4). The Na(+) affinity at the extracellular binding site decreases from approximately 900 mM at pH 6.2 to approximately 200 mM at pH 8.5. The results suggest that during Na(+) transport the free energy supplied by the hydrolysis of ATP is mainly used for the generation of a low-affinity extracellular Na(+) discharge site. Ionic strength and lyotropic anions both decrease the relaxation rate. However, while ionic strength does not change the position of the conformational equilibrium E(1)P <--> E(2)P, lyotropic anions shift it to E(1)P. PMID:11053130

General and simple approach for control cage and cylindrical mesopores, and thermal/hydrothermal stable frameworks.

PubMed

El-Safty, Sherif A; Mizukami, Fujio; Hanaoka, Takaaki

2005-05-19

Highly ordered cage and cylindrical mesoporeous silica monoliths (HOM) with 2- and 3-dimensional (2D and 3D, respectively) structures, mesopore/micropore volumes, and thick-walled frameworks were successfully fabricated by instant direct templating of lyotropic phases of copolymer (EO(m)-PO(n)-EO(m)) surfactants. Large cage-like pores with uniform constriction sizes up to 10 nm and open cylindrical channel-like mesopores can be easily achieved by this simple and efficient synthesis design. Our results show that the cage-like pores could be fabricated at relatively lower copolymer concentrations used in the lyotropic phase domains at copolymer/TMOS ratios of 35 wt %. These ordered cage pore architectures underwent transition to open-cylindrical pores by increasing the copolymer concentration. High EO/PO block copolymers, in general, were crucially affected on the increase of the interior cavity sizes and on the stability of the cage mesopore characters. However, for F108 (EO(141)PO(44)EO(141)) systems, the fabrication of ordered and stable cage pore monoliths was achieved with significantly higher copolymer concentrations up to 90 wt %. Interestingly, the effective copolymer molecular nature was also observed in the ability to design various ordered mesophase geometries in large domain sizes. Our findings here show evidence that the synthetic strategy provides realistic control over a wide range of mesostructured phase geometries and their extended long-range ordering in the final replicas of the silica monolith frameworks. In addition, the HOM silica monoliths exhibited considerable structural stability against higher thermal temperature (up to 1000 degrees C) and longer hydrothermal treatment times under boiling water and steam. The remarkable structural findings of 3D frameworks, transparent monoliths, and micropores combined with large cage- and cylindrical-like mesopores are expected to find promising uses in materials chemistry.

Silicon supported lipid-DNA thin film structures at varying temperature studied by energy dispersive X-ray diffraction and neutron reflectivity.

PubMed

Domenici, F; Castellano, C; Dell'Unto, F; Albinati, A; Congiu, A

2011-11-01

Non-viral gene transfection by means of lipid-based nanosystems, such as solid supported lipid assemblies, is often limited due to their lack of stability and the consequent loss of efficiency. Therefore not only a detailed thermo-lyotropic study of these DNA-lipid complexes is necessary to understand their interaction mechanisms, but it can also be considered as a first step in conceiving and developing new transfection biosystems. The aim of our study is a structural characterization of 1,2-dioleoyl-sn-glycero-3-phosphatidylcholine (DOPC)-dimethyl-dioctadecyl-ammonium bromide (DDAB)-DNA complex at varying temperature using the energy dispersive X-ray diffraction (EDXD) and neutron reflectivity (NR) techniques. We have shown the formation of a novel thermo-lyotropic structure of DOPC/DDAB thin film self-organized in multi-lamellar planes on (100)-oriented silicon support by spin coating, thus enlightening its ability to include DNA strands. Our NR measurements indicate that the DOPC/DDAB/DNA complex forms temperature-dependent structures. At 65°C and relative humidity of 100% DNA fragments are buried between single lamellar leaflets constituting the hydrocarbon core of the lipid bilayers. This finding supports the consistency of the hydrophobic interaction model, which implies that the coupling between lipid tails and hypo-hydrated DNA single strands could be the driving force of DNA-lipid complexation. Upon cooling to 25°C, EDXD analysis points out that full-hydrated DOPC-DDAB-DNA can switch in a different metastable complex supposed to be driven by lipid heads-DNA electrostatic interaction. Thermotropic response analysis also clarifies that DOPC has a pivotal role in promoting the formation of our observed thermophylic silicon supported lipids-DNA assembly. Copyright © 2011 Elsevier B.V. All rights reserved.

Dynamics of Ice/Water Confined in Nanoporous Alumina.

PubMed

Suzuki, Yasuhito; Steinhart, Martin; Graf, Robert; Butt, Hans-Jürgen; Floudas, George

2015-11-19

Dielectric (DS), IR spectroscopy, and (1)H MAS NMR are employed in the study of ice/water confined in nanoporous alumina with pore diameters ranging from 400 nm down to 25 nm. Within nanoporous alumina there is a transformation from heterogeneous nucleation of hexagonal ice in the larger pores to homogeneous nucleation of cubic ice in the smaller pores. DS and IR show excellent agreement in the temperature interval and pore size dependence of the transformation. DS further revealed two dynamic processes under confinement. The "fast" and "slow" processes with an Arrhenius temperature dependence are attributed to ice and supercooled water relaxation, respectively. The main relaxation process of ice under confinement ("slow" process) has an activation energy of 44 ± 2 kJ/mol. The latter is in agreement with the reported relaxation times and activation energy of cubic ice prepared following a completely different route (by pressure). (1)H MAS NMR provided new insight in the state of ice structures as well as of supercooled water. Under confinement, a layer of liquid-like water coexists with ice structures. In addition, both ice structures under confinement appear to be more ordered than bulk hexagonal ice. Supercooled water in the smaller pores is different from bulk water. It shows a shift of the signal toward higher chemical shift values which may suggest stronger hydrogen bonding between the water molecules or increasing interactions with the AAO walls.

Thermal effects on the structural properties of tungsten oxide nanoparticles

NASA Astrophysics Data System (ADS)

Yang, Tsung-Yeh; Wu, Chung-Yi; Tsai, Meng-Hung; Lin, Hong-Ming; Tsai, Wen-Li; Hwu, Yeukuang

2004-06-01

Tungsten oxide nanoparticles are prepared by evaporating and oxidizing the tungsten boat in helium and oxygen atmosphere and then quenched to the liquid nitrogen temperature. The as-prepared tungsten oxide nanoparticles are porous-free with uniform size. The morphology and particle size distribution of the as-prepared and after sinter treatments tungsten oxide nanoparticles are revealed by TEM and AFM. The long-range order of these nanoparticles can be examined by X-ray diffraction technique. The as-prepared nanoparticles exhibit a mixture structure of monoclinic and hexagonal crystals. Preliminary X-ray diffraction results indicate that the hexagonal structure is transformed to monoclinic structure after annealing to above 600°C. In order to better distinguish the structural properties of the tungsten oxide (WO3- x) nanoparticles before and after annealing, the X-ray absorption spectrum technique is utilized; thus, the detailed local atomic arrangement of oxygen and/or tungsten can be determined. According to the XAS result, the shape of the W L3-edge undergoes no considerable changes. This infers that structural transformation of tungsten oxide nanoparticle may be caused by the migration of oxygen after sintering. From the O K-edge of absorption spectrum, it suggests that a mixture phase structure is obtained when sintered below 300°C. And this result indicates that heat treatment to approximately 600°C produces a stable structure of a monoclinic crystal of WO3.

Silicon nitride equation of state

NASA Astrophysics Data System (ADS)

Brown, Robert C.; Swaminathan, Pazhayannur K.

2017-01-01

This report presents the development of a global, multi-phase equation of state (EOS) for the ceramic silicon nitride (Si3N4).1 Structural forms include amorphous silicon nitride normally used as a thin film and three crystalline polymorphs. Crystalline phases include hexagonal α-Si3N4, hexagonal β-Si3N4, and the cubic spinel c-Si3N4. Decomposition at about 1900 °C results in a liquid silicon phase and gas phase products such as molecular nitrogen, atomic nitrogen, and atomic silicon. The silicon nitride EOS was developed using EOSPro which is a new and extended version of the PANDA II code. Both codes are valuable tools and have been used successfully for a variety of material classes. Both PANDA II and EOSPro can generate a tabular EOS that can be used in conjunction with hydrocodes. The paper describes the development efforts for the component solid phases and presents results obtained using the EOSPro phase transition model to investigate the solid-solid phase transitions in relation to the available shock data that have indicated a complex and slow time dependent phase change to the c-Si3N4 phase. Furthermore, the EOSPro mixture model is used to develop a model for the decomposition products; however, the need for a kinetic approach is suggested to combine with the single component solid models to simulate and further investigate the global phase coexistences.

Sticking properties of ice grains

NASA Astrophysics Data System (ADS)

Jongmanns, M.; Kumm, M.; Wurm, G.; Wolf, D. E.; Teiser, J.

2017-06-01

We study the size dependence of pull-off forces of water ice in laboratory experiments and numerical simulations. To determine the pull-off force in our laboratory experiments, we use a liquid nitrogen cooled centrifuge. Depending on its rotation frequency, spherical ice grains detach due to the centrifugal force which is related to the adhesive properties. Numerical simulations are conducted by means of molecular dynamics simulations of hexagonal ice using a standard coarse-grained water potential. The pull-off force of a single contact between two spherical ice grains is measured due to strain controlled simulations. Both, the experimental study and the simulations reveal a dependence between the pull-off force and the (reduced) particle radii, which differ significantly from the linear dependence of common contact theories.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adidharma, Hertanto, E-mail: adidharm@uwyo.edu; Tan, Sugata P.

Canonical Monte Carlo simulations on face-centered cubic (FCC) and hexagonal closed packed (HCP) Lennard-Jones (LJ) solids are conducted at very low temperatures (0.10 ≤ T{sup ∗} ≤ 1.20) and high densities (0.96 ≤ ρ{sup ∗} ≤ 1.30). A simple and robust method is introduced to determine whether or not the cutoff distance used in the simulation is large enough to provide accurate thermodynamic properties, which enables us to distinguish the properties of FCC from that of HCP LJ solids with confidence, despite their close similarities. Free-energy expressions derived from the simulation results are also proposed, not only to describe themore » properties of those individual structures but also the FCC-liquid, FCC-vapor, and FCC-HCP solid phase equilibria.« less

Gas-exfoliated porous monolayer boron nitride for enhanced aerobic oxidative desulfurization performance.

PubMed

Wu, Yingcheng; Wu, Peiwen; Chao, Yanhong; He, Jing; Li, Hongping; Lu, Linjie; Jiang, Wei; Zhang, Beibei; Li, Huaming; Zhu, Wenshuai

2018-01-12

Hexagonal boron nitride has been regarded to be an efficient catalyst in aerobic oxidation fields, but limited by the less-exposed active sites. In this contribution, we proposed a simple green liquid nitrogen gas exfoliation strategy for preparation of porous monolayer nanosheets (BN-1). Owing to the reduced layer numbers, decreased lateral sizes and artificially-constructed pores, increased exposure of active sites was expected, further contributed to an enhanced aerobic oxidative desulfurization (ODS) performance up to ∼98% of sulfur removal, achieving ultra-deep desulfurization. This work not only introduced an excellent catalyst for aerobic ODS, but also provided a strategy for construction of some other highly-efficient monolayer two-dimensional materials for enhanced catalytic performance.

Self-Assembly in Systems Containing Silicone Compounds

NASA Astrophysics Data System (ADS)

Ferreira, Maira Silva; Loh, Watson

2009-01-01

Chemical systems formed by silicone solvents and surfactants have potential applications in a variety of industrial products. In spite of their technological relevance, there are few reports on the scientific literature that focus on characterizing such ternary systems. In this work, we have aimed to develop a general, structural investigation on the phase diagram of one system that typically comprises silicone-based chemicals, by means of the SAXS (small-angle X-ray scattering) technique. Important features such as the presence of diverse aggregation states in the overall system, either on their own or in equilibrium with other structures, have been detected. As a result, optically isotropic chemical systems (direct and/or reversed microemulsions) and liquid crystals with lamellar or hexagonal packing have been identified and characterized.

Morphology- and orientation-controlled gallium arsenide nanowires on silicon substrates.

PubMed

Ihn, Soo-Ghang; Song, Jong-In; Kim, Tae-Wook; Leem, Dong-Seok; Lee, Takhee; Lee, Sang-Geul; Koh, Eui Kwan; Song, Kyung

2007-01-01

GaAs nanowires were epitaxially grown on Si(001) and Si(111) substrates by using Au-catalyzed vapor-liquid-solid (VLS) growth in a solid source molecular beam epitaxy system. Scanning electron microscopy analysis revealed that almost all the GaAs nanowires were grown along <111> directions on both Si substrates for growth conditions investigated. The GaAs nanowires had a very uniform diameter along the growth direction. X-ray diffraction data and transmission electron microscopy analysis revealed that the GaAs<111> nanowires had a mixed crystal structure of the hexagonal wurtzite and the cubic zinc-blende. Current-voltage characteristics of junctions formed by the epitaxially grown GaAs nanowires and the Si substrate were investigated by using a current-sensing atomic force microscopy.

Gas-exfoliated porous monolayer boron nitride for enhanced aerobic oxidative desulfurization performance

NASA Astrophysics Data System (ADS)

Wu, Yingcheng; Wu, Peiwen; Chao, Yanhong; He, Jing; Li, Hongping; Lu, Linjie; Jiang, Wei; Zhang, Beibei; Li, Huaming; Zhu, Wenshuai

2018-01-01

Hexagonal boron nitride has been regarded to be an efficient catalyst in aerobic oxidation fields, but limited by the less-exposed active sites. In this contribution, we proposed a simple green liquid nitrogen gas exfoliation strategy for preparation of porous monolayer nanosheets (BN-1). Owing to the reduced layer numbers, decreased lateral sizes and artificially-constructed pores, increased exposure of active sites was expected, further contributed to an enhanced aerobic oxidative desulfurization (ODS) performance up to ˜98% of sulfur removal, achieving ultra-deep desulfurization. This work not only introduced an excellent catalyst for aerobic ODS, but also provided a strategy for construction of some other highly-efficient monolayer two-dimensional materials for enhanced catalytic performance.

Development of pharmaceutical clear gel based on Peceol®, lecithin, ethanol and water: Physicochemical characterization and stability study.

PubMed

Mouri, Abdelkader; Diat, Olivier; El Ghzaoui, Abdeslam; Ly, Isabelle; Dorandeu, Christophe; Maurel, Jean Claude; Devoisselle, Jean-Marie; Legrand, Philippe

2015-11-01

The phase behavior of the four-components Peceol®/lecithin/ethanol/water system has been studied in a part of the phase diagram poor in water and varying the lecithin/Peceol® ratio. Using several complementary techniques such as Karl Fischer titration, rheology, polarized microscopy and SAXS measurements several nanostructures of the complex systems were identified. W/O microemulsion (L2) as well as an inverted hexagonal (H2) liquid-crystal phase were studied. The analysis of the different phase transitions allows us to understand the effect of lecithin on the water solubilization efficiency of this clear gel and to show its pharmaceutical interest among lecithin organogels. Copyright © 2015 Elsevier Inc. All rights reserved.

Sodium-Doped Mesoporous Ni2P2O7 Hexagonal Tablets for High-Performance Flexible All-Solid-State Hybrid Supercapacitors.

PubMed

Wei, Chengzhen; Cheng, Cheng; Wang, Shanshan; Xu, Yazhou; Wang, Jindi; Pang, Huan

2015-08-01

A simple hydrothermal method has been developed to prepare hexagonal tablet precursors, which are then transformed into porous sodium-doped Ni2P2O7 hexagonal tablets by a simple calcination method. The obtained samples were evaluated as electrode materials for supercapacitors. Electrochemical measurements show that the electrode based on the porous sodium-doped Ni2P2O7 hexagonal tablets exhibits a specific capacitance of 557.7 F g(-1) at a current density of 1.2 A g(-1) . Furthermore, the porous sodium-doped Ni2P2O7 hexagonal tablets were successfully used to construct flexible solid-state hybrid supercapacitors. The device is highly flexible and achieves a maximum energy density of 23.4 Wh kg(-1) and a good cycling stability after 5000 cycles, which confirms that the porous sodium-doped Ni2P2 O7 hexagonal tablets are promising active materials for flexible supercapacitors. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-temperature molecular dynamics simulation of aragonite.

PubMed

Miyake, Akira; Kawano, Jun

2010-06-09

For molecular dynamics simulations using aragonite structure as the initial state, a new phase of space group P6₃22 (hexagonal aragonite) appeared at temperatures above 510 K at a pressure of 1 atm. It was a first-order phase transition which occurs metastably within the stable region of calcite and the dT/dP slope of the phase boundary between orthorhombic and hexagonal aragonite was about 1.25 × 10³ K GPa⁻¹. In the hexagonal aragonite structure, CO₃ groups were rotated by 30° around the c axis and move up and down along the c axis from their position in aragonite, and Ca ions were six-coordinated as they are in calcite. The CaO₆ octahedron of hexagonal aragonite was strongly distorted, whereas in the calcite structure it is an almost ideal octahedron. The transition between hexagonal and orthorhombic aragonite involves only small movements of CO₃ groups. Therefore, it is possible that hexagonal aragonite plays an important part in the metastable formation of aragonite within the stability field of calcite and in the development of sector trilling in aragonite.

Three-dimensional finite amplitude electroconvection in dielectric liquids

NASA Astrophysics Data System (ADS)

Luo, Kang; Wu, Jian; Yi, Hong-Liang; Tan, He-Ping

2018-02-01

Charge injection induced electroconvection in a dielectric liquid lying between two parallel plates is numerically simulated in three dimensions (3D) using a unified lattice Boltzmann method (LBM). Cellular flow patterns and their subcritical bifurcation phenomena of 3D electroconvection are numerically investigated for the first time. A unit conversion is also derived to connect the LBM system to the real physical system. The 3D LBM codes are validated by three carefully chosen cases and all results are found to be highly consistent with the analytical solutions or other numerical studies. For strong injection, the steady state roll, polygon, and square flow patterns are observed under different initial disturbances. Numerical results show that the hexagonal cell with the central region being empty of charge and centrally downward flow is preferred in symmetric systems under random initial disturbance. For weak injection, the numerical results show that the flow directly passes from the motionless state to turbulence once the system loses its linear stability. In addition, the numerically predicted linear and finite amplitude stability criteria of different flow patterns are discussed.

Micro-structure and motion of two-dimensional dense short spherocylinder liquids

NASA Astrophysics Data System (ADS)

Wang, Wen; Lin, Jyun-Ting; Su, Yen-Shuo; I, Lin

2018-03-01

We numerically investigate the micro-structure and motion of 2D liquids composed of dense short spherocylinders, by reducing the shape aspect ratio from 3. It is found that reducing shape aspect ratio from 3 causes a smooth transition from heterogeneous structures composed of crystalline ordered domains with good tetratic alignment order to those with good hexagonal bond-orientational order at an aspect ratio equaling 1.35. In the intermediate regime, both structural orders are strongly deteriorated, and the translational hopping rate reaches a maximum due to the poor particle interlocking of the disordered structure. Shortening rod length allows easier rotation, induces monotonic increase of rotational hopping rates, and resumes the separation of rotational and translational hopping time scales at the small aspect ratio end, after the crossover of their rates in the intermediate regime. At the large shape aspect ratio end, the poor local tetratic order has the same positive effects on facilitating local rotational and translational hopping. In contrast, at the small shape aspect ratio end, the poor local bond orientational order has the opposite effects on facilitating local rotational and translational hopping.

Effect of intermolecular dipole-dipole interactions on interfacial supramolecular structures of C3-symmetric hexa-peri-hexabenzocoronene derivatives.

PubMed

Mu, Zhongcheng; Shao, Qi; Ye, Jun; Zeng, Zebing; Zhao, Yang; Hng, Huey Hoon; Boey, Freddy Yin Chiang; Wu, Jishan; Chen, Xiaodong

2011-02-15

Two-dimensional (2D) supramolecular assemblies of a series of novel C(3)-symmetric hexa-peri-hexabenzocoronene (HBC) derivatives bearing different substituents adsorbed on highly oriented pyrolytic graphite were studied by using scanning tunneling microscopy at a solid-liquid interface. It was found that the intermolecular dipole-dipole interactions play a critical role in controlling the interfacial supramolecular assembly of these C(3)-symmetric HBC derivatives at the solid-liquid interface. The HBC molecule bearing three -CF(3) groups could form 2D honeycomb structures because of antiparallel dipole-dipole interactions, whereas HBC molecules bearing three -CN or -NO(2) groups could form hexagonal superstructures because of a special trimeric arrangement induced by dipole-dipole interactions and weak hydrogen bonding interactions ([C-H···NC-] or [C-H···O(2)N-]). Molecular mechanics and dynamics simulations were performed to reveal the physics behind the 2D structures as well as detailed functional group interactions. This work provides an example of how intermolecular dipole-dipole interactions could enable fine control over the self-assembly of disklike π-conjugated molecules.

Nanophosphor CaSO4:Eu2+ for photoluminescence liquid crystal display (PLLCD)

NASA Astrophysics Data System (ADS)

Patle, Anita; Patil, R. R.; Moharil, S. V.

2018-05-01

In this work PL enhancement of CaSO4:Eu2+ nanophosphor which was synthesized with 0.01M molarity by co-precipitation method is presented. Synthesized phosphor was characterized by XRD, SEM, TEM and PL measurements. Average particle size is found to be in the range 80-100nm with Hexagonal morphology and PL studies showed emission peaks at 380nm, when samples were excited by 254nm. The observed PL emission is characteristic emission of Eu2+ similar to that observed in bulk CaSO4:Eu2. However under identical condition it is observed that intensity of emission get enhanced for 0.01M size which is doubled to that of 0.1M with similar emission at 380nm. A phosphor with narrow emission band around 390 nm is desirable, since at this wavelength the transmission of standard glass, polarizing plastic, other coating and LCD material is at acceptable level. Strong Eu2+ emission is observed in CaSO4:Eu nanophosphor which finds applications for PLLCD (photoluminescent liquid crystal display).

Controlling domain orientation of liquid crystalline block copolymer in thin films through tuning mesogenic chemical structures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xie, He-Lou; Li, Xiao; Ren, Jiaxing

Controlling the macroscopic orientation of nanoscale periodic structures of amphiphilic liquid crystalline block copolymers (LC BCPs) is important to a variety of technical applications (e.g., lithium conducting polymer electrolytes). To study LC BCP domain orientation, a series of LC BCPs containing a poly(ethylene oxide) (PEO) block as a conventional hydrophilic coil block and LC blocks containing azobenzene mesogens is designed and synthesized. LC ordering in thin films of the BCP leads to the formation of highly ordered, microphase-separated nanostructures, with hexagonally arranged PEO cylinders. Substitution on the tail of the azobenzene mesogen is shown to control the orientation of themore » PEO cylinders. When the substitution on the mesogenic tails is an alkyl chain, the PEO cylinders have a perpendicular orientation to the substrate surface, provided the thin film is above a critical thickness value. In contrast, when the substitution on the mesogenic tails has an ether group the PEO cylinders assemble parallel to the substrate surface regardless of the film thickness value.« less

Influence of the height of the external hexagon and surface treatment on fatigue life of commercially pure titanium dental implants.

PubMed

Gil, Francisco Javier; Aparicio, Conrado; Manero, Jose M; Padros, Alejandro

2009-01-01

This study evaluated the effect of external hexagon height and commonly applied surface treatments on the fatigue life of titanium dental implants. Electropolished commercially pure titanium dental implants (seven implants per group) with three different external hexagon heights (0.6, 1.2, and 1.8 mm) and implants with the highest external hexagon height (1.8 mm) and different surface treatments (electropolishing, grit blasting with aluminium oxide, and acid etching with sulfuric acid) were tested to evaluate their mechanical fatigue life. To do so, 10-Hz triangular flexural load cycles were applied at 37 degrees C in artificial saliva, and the number of load cycles until implant fracture was determined. Tolerances of the hexagon/abutment fit and implant surface roughness were analyzed by scanning electron microscopy and light interferometry. Transmission electron microscopy and electron diffraction analyses of titanium hydrides were performed. First, the fatigue life of implants with the highest hexagon (8,683 +/- 978 load cycles) was more than double that of the implants with the shortest hexagons (3,654 +/- 789 load cycles) (P < .02). Second, the grit-blasted implants had the longest fatigue life of the tested materials (21,393 +/- 2,356 load cycles), which was significantly greater than that of the other surfaces (P < .001). The compressive surface residual stresses induced when blasting titanium are responsible for this superior mechanical response. Third, precipitation of titanium hydrides in grain boundaries of titanium caused by hydrogen adsorption from the acid solution deteriorates the fatigue life of acid-etched titanium dental implants. These implants had the shortest fatigue life (P < .05). The fatigue life of threaded root-form dental implants varies with the height of the external hexagon and/or the surface treatment of the implant. An external hexagon height of 1.8 mm and/or a blasting treatment appear to significantly increase fatigue life of dental implants.

The influence of abutment screw tightening on screw joint configuration.

PubMed

Lang, Lisa A; Wang, Rui-Feng; May, Kenneth B

2002-01-01

Limiting abutment-to-implant hexagonal discrepancies and rotational movement of the abutment around the implant to less than 5 degrees would result in a more stable screw joint. However, the exact relationship after abutment screw tightening is unknown, as is the effect of a counter-torque device in limiting abutment movement during screw tightening. This study examined the orientation of the abutment hexagon to the implant hexagon after tightening of the abutment screw for several abutment systems with and without the use of a counter-torque device. Thirty conical self-tapping implants (3.75 x 10.0 mm) and 10 wide-platform Brånemark System implants (5.0 x 10.0 mm), along with 10 abutment specimens from the CeraOne, Estheticone, Procera, and AuraAdapt systems, were selected for this investigation. The implants were placed in a holding device prior to tightening of the abutments. When the tightening torque recommended for each abutment system was reached with the use of a torque controller, each implant abutment specimen was removed from the holding device and embedded in a hard resin medium. The specimens were sectioned in a horizontal direction at the level of the hexagons and cleansed of debris prior to examination. The hexagon orientations were assessed as the degree and direction of rotation of the abutment hexagon around the implant hexagon. The range of the maximum degrees of rotation for all 4 abutment groups tightened with or without the counter-torque device was slightly more than 3.53 degrees. The absolute degrees of rotation for all 4 abutment groups were less than 1.50 degrees with or without the use of the counter-torque device. The hexagon-to-hexagon orientation measured as rotational fit on all abutment systems was below the 5 degrees suggested as optimal for screw joint stability. The absolute degrees of rotation for all 4 abutment groups were less than 1.50 degrees regardless of whether the counter-torque device was used.

Fabrication of nickel hydroxide electrodes with open-ended hexagonal nanotube arrays for high capacitance supercapacitors.

PubMed

Wu, Mao-Sung; Huang, Kuo-Chih

2011-11-28

A nickel hydroxide electrode with open-ended hexagonal nanotube arrays, prepared by hydrolysis of nickel chloride in the presence of hexagonal ZnO nanorods, shows a very high capacitance of 1328 F g(-1) at a discharge current density of 1 A g(-1) due to the significantly improved ion transport.

The bridging conformations of double-end anchored polymer-surfactants destabilize a hydrogel of lipid membranes

NASA Astrophysics Data System (ADS)

Slack, N. L.; Davidson, P.; Chibbaro, M. A.; Jeppesen, C.; Eiselt, P.; Warriner, H. E.; Schmidt, H.-W.; Pincus, P.; Safinya, C. R.

2001-10-01

Double-end-anchored poly-ethylene-glycol-surfactants (DEA-PEG-surfactants) induce the gelation of lyotropic lamellar Lα phases stabilized by undulation forces. The physical hydrogel (Lα,g) derives its viscoelasticity from the proliferation of defects at a mesoscopic level. The DEA-PEG-surfactants assume both looping and bridging conformations. The existence of novel bridging conformations is indicated by the coexistence of two lamellar phases and the limited swelling of the Lα and Lα,g phases. Modeling of the polymer decorated membranes demonstrates the existence of bridging and yields a rapidly decreasing density of bridging conformations with increasing interlayer spacing.

Control of the anisotropic shape of cobalt nanorods in the liquid phase: from experiment to theory... and back

NASA Astrophysics Data System (ADS)

Atmane, Kahina Aït; Michel, Carine; Piquemal, Jean-Yves; Sautet, Philippe; Beaunier, Patricia; Giraud, Marion; Sicard, Mickaël; Nowak, Sophie; Losno, Rémi; Viau, Guillaume

2014-02-01

The polyol process is one of the few methods allowing the preparation of metal nanoparticles in solution. Hexagonal close packed monocrystalline Co nanorods are easily obtained in basic 1,2-butanediol at 448 K after a few minutes using a Co(ii) dicarboxylate precursor. By using a combined experimental and theoretical approach, this study aims at a better understanding of the growth of anisotropic cobalt ferromagnetic nanoparticles by the polyol process. The growth of Co nanorods along the c axis of the hexagonal system was clearly evidenced by transmission electron microscopy, while the mean diameter was found to be almost constant at about 15 nm. Powder X-ray diffraction data showed that metallic cobalt was generated at the expense of a non-reduced solid lamellar intermediate phase which can be considered as a carboxylate ligand reservoir. Density functional theory calculations combined with a thermodynamic approach unambiguously showed that the main parameter governing the shape of the objects is the chemical potential of the carboxylate ligand: the crystal habit was deeply modified from rods to platelets when increasing the concentration of the ligand, i.e. its chemical potential. The approach presented in this study could be extended to a large number of particle types and growth conditions, where ligands play a key role in determining the particle shape.The polyol process is one of the few methods allowing the preparation of metal nanoparticles in solution. Hexagonal close packed monocrystalline Co nanorods are easily obtained in basic 1,2-butanediol at 448 K after a few minutes using a Co(ii) dicarboxylate precursor. By using a combined experimental and theoretical approach, this study aims at a better understanding of the growth of anisotropic cobalt ferromagnetic nanoparticles by the polyol process. The growth of Co nanorods along the c axis of the hexagonal system was clearly evidenced by transmission electron microscopy, while the mean diameter was found to be almost constant at about 15 nm. Powder X-ray diffraction data showed that metallic cobalt was generated at the expense of a non-reduced solid lamellar intermediate phase which can be considered as a carboxylate ligand reservoir. Density functional theory calculations combined with a thermodynamic approach unambiguously showed that the main parameter governing the shape of the objects is the chemical potential of the carboxylate ligand: the crystal habit was deeply modified from rods to platelets when increasing the concentration of the ligand, i.e. its chemical potential. The approach presented in this study could be extended to a large number of particle types and growth conditions, where ligands play a key role in determining the particle shape. Electronic supplementary information (ESI) available: Gas chromatograms of: (i) the as-received 1,2-butanediol solvent, (ii) the solvent treated under reflux in air after 24 h and (iii) the liquid phase after 10 min reaction at 448 K; theoretical results showing that the Co (011&cmb.macr;0) surface restructures itself into a Co (101&cmb.macr;0) surface for a 12-layer slab; adsorption modes of 1,2-butanediol on Co (101&cmb.macr;0) and (0001) surfaces. See DOI: 10.1039/c3nr03686c

Hexagon solar power panel

NASA Technical Reports Server (NTRS)

Rubin, I. (Inventor)

1978-01-01

A solar energy panel support is described upon which silicon cells are arrayed. The cells are wafer thin and of two geometrical types, both of the same area and electrical rating, namely hexagon cells and hourglass cells. The hourglass cells are composites of half hexagons. A near perfect nesting relationship of the cells achieves a high density packing whereby optimum energy production per panel area is achieved.

Non-Reciprocal on Wafer Microwave Devices

DTIC Science & Technology

2015-05-27

filter uses a barium hexagonal ferrite film incorporated into the dielectric layer of a microstrip transmission line. The zero-field operational...Fal,, Robert E. Camley. Millimeter wave phase shifter based on ferromagnetic resonancein a hexagonal barium ferrite thin film, Applied Physics...materials for on-wafer microwave devices concentrated on barium hexagonal ferrite (BaM) films grown on Si because these material is a good candidate

Hexagon solar power panel

DOEpatents

Rubin, Irwin

1978-01-01

A solar energy panel comprises a support upon which silicon cells are arrayed. The cells are wafer thin and of two geometrical types, both of the same area and electrical rating, namely hexagon cells and hourglass cells. The hourglass cells are composites of half hexagons. A near perfect nesting relationship of the cells achieves a high density packing whereby optimum energy production per panel area is achieved.

Self-Assembly of a [1+1] Ionic Hexagonal Macrocycle and its Antiproliferative Activity

NASA Astrophysics Data System (ADS)

Singh, Khushwant; Gangrade, Ankit; Bhowmick, Sourav; Jana, Achintya; Mandal, Biman B.; Das, Neeladri

2018-04-01

A unique irregular hexagon was self-assembled using an organic donor clip (bearing terminal pyridyl units) and a complementary organometallic acceptor clip. The resulting metallamacrocycle was characterized by multinuclear NMR, mass spectrometry, and elemental analyses. Molecular modeling confirmed hexagonal shaped cavity for this metallamacrocycle which is a unique example of a discrete hexagonal framework self-assembled from only two building blocks. Cytotoxicity of the Pt-based acceptor tecton and the self-assembled PtII-based macrocycle was evaluated using three cancer cell lines and results were compared with cisplatin. Results confirmed a positive effect of the metallamacrocycle formation on cell growth inhibition.

Van der Waals epitaxy and photoresponse of hexagonal tellurium nanoplates on flexible mica sheets.

PubMed

Wang, Qisheng; Safdar, Muhammad; Xu, Kai; Mirza, Misbah; Wang, Zhenxing; He, Jun

2014-07-22

Van der Waals epitaxy (vdWE) is of great interest due to its extensive applications in the synthesis of ultrathin two-dimensional (2D) layered materials. However, vdWE of nonlayered functional materials is still not very well documented. Here, although tellurium has a strong tendency to grow into one-dimensional nanoarchitecture due to its chain-like structure, we successfully realize 2D hexagonal tellurium nanoplates on flexible mica sheets via vdWE. Chemically inert mica surface is found to be crucial for the lateral growth of hexagonal tellurium nanoplates since it (1) facilitates the migration of tellurium adatoms along mica surface and (2) allows a large lattice mismatch. Furthermore, 2D tellurium hexagonal nanoplates-based photodetectors are in situ fabricated on flexible mica sheets. Efficient photoresponse is obtained even after bending the device for 100 times, indicating 2D tellurium hexagonal nanoplates-based photodetectors on mica sheets have a great application potential in flexible and wearable optoelectronic devices. We believe the fundamental understanding of vdWE effect on the growth of 2D tellurium hexagonal nanoplate can pave the way toward leveraging vdWE as a useful channel to realize the 2D geometry of other nonlayered materials.

Controllable growth of shaped graphene domains by atmospheric pressure chemical vapour deposition

NASA Astrophysics Data System (ADS)

Fan, Lili; Li, Zhen; Li, Xiao; Wang, Kunlin; Zhong, Minlin; Wei, Jinquan; Wu, Dehai; Zhu, Hongwei

2011-12-01

Graphene domains in different shapes have been grown on copper substrates via atmospheric pressure chemical vapour deposition by controlling the growth process parameters. Under stabilized conditions, graphene domains tend to be six-fold symmetric hexagons under low flow rate methane with some domains in an irregular hexagonal shape. After further varying the growth duration, methane flow rate, and temperature, graphene domains have developed shapes from hexagon to shovel and dendrite. Two connecting modes, through overlap and merging of adjacent graphene domains, are proposed.Graphene domains in different shapes have been grown on copper substrates via atmospheric pressure chemical vapour deposition by controlling the growth process parameters. Under stabilized conditions, graphene domains tend to be six-fold symmetric hexagons under low flow rate methane with some domains in an irregular hexagonal shape. After further varying the growth duration, methane flow rate, and temperature, graphene domains have developed shapes from hexagon to shovel and dendrite. Two connecting modes, through overlap and merging of adjacent graphene domains, are proposed. Electronic supplementary information (ESI) available: Schematics of CVD setups for graphene growth, Raman spectra and SEM images. See DOI: 10.1039/c1nr11480h

Grid cell hexagonal patterns formed by fast self-organized learning within entorhinal cortex.

PubMed

Mhatre, Himanshu; Gorchetchnikov, Anatoli; Grossberg, Stephen

2012-02-01

Grid cells in the dorsal segment of the medial entorhinal cortex (dMEC) show remarkable hexagonal activity patterns, at multiple spatial scales, during spatial navigation. It has previously been shown how a self-organizing map can convert firing patterns across entorhinal grid cells into hippocampal place cells that are capable of representing much larger spatial scales. Can grid cell firing fields also arise during navigation through learning within a self-organizing map? This article describes a simple and general mathematical property of the trigonometry of spatial navigation which favors hexagonal patterns. The article also develops a neural model that can learn to exploit this trigonometric relationship. This GRIDSmap self-organizing map model converts path integration signals into hexagonal grid cell patterns of multiple scales. GRIDSmap creates only grid cell firing patterns with the observed hexagonal structure, predicts how these hexagonal patterns can be learned from experience, and can process biologically plausible neural input and output signals during navigation. These results support an emerging unified computational framework based on a hierarchy of self-organizing maps for explaining how entorhinal-hippocampal interactions support spatial navigation. Copyright © 2010 Wiley Periodicals, Inc.

STIR: Novel Electronic States by Gating Strongly Correlated Materials

DTIC Science & Technology

2016-03-01

plan built on my group’s recent demonstration of electrolyte gating in Strontium Titanate, using an atomically thin hexagonal Boron Nitride barrier to...demonstration of electrolyte gating in Strontium Titanate, using an atomically thin hexagonal Boron Nitride barrier to prevent disorder and chemical...techniques and learned to apply thin hexagonal Boron Nitride to single crystals of materials expected to show some of the most exciting correlated

WE-G-204-03: Photon-Counting Hexagonal Pixel Array CdTe Detector: Optimal Resampling to Square Pixels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shrestha, S; Vedantham, S; Karellas, A

Purpose: Detectors with hexagonal pixels require resampling to square pixels for distortion-free display of acquired images. In this work, the presampling modulation transfer function (MTF) of a hexagonal pixel array photon-counting CdTe detector for region-of-interest fluoroscopy was measured and the optimal square pixel size for resampling was determined. Methods: A 0.65mm thick CdTe Schottky sensor capable of concurrently acquiring up to 3 energy-windowed images was operated in a single energy-window mode to include ≥10 KeV photons. The detector had hexagonal pixels with apothem of 30 microns resulting in pixel spacing of 60 and 51.96 microns along the two orthogonal directions.more » Images of a tungsten edge test device acquired under IEC RQA5 conditions were double Hough transformed to identify the edge and numerically differentiated. The presampling MTF was determined from the finely sampled line spread function that accounted for the hexagonal sampling. The optimal square pixel size was determined in two ways; the square pixel size for which the aperture function evaluated at the Nyquist frequencies along the two orthogonal directions matched that from the hexagonal pixel aperture functions, and the square pixel size for which the mean absolute difference between the square and hexagonal aperture functions was minimized over all frequencies up to the Nyquist limit. Results: Evaluation of the aperture functions over the entire frequency range resulted in square pixel size of 53 microns with less than 2% difference from the hexagonal pixel. Evaluation of the aperture functions at Nyquist frequencies alone resulted in 54 microns square pixels. For the photon-counting CdTe detector and after resampling to 53 microns square pixels using quadratic interpolation, the presampling MTF at Nyquist frequency of 9.434 cycles/mm along the two directions were 0.501 and 0.507. Conclusion: Hexagonal pixel array photon-counting CdTe detector after resampling to square pixels provides high-resolution imaging suitable for fluoroscopy.« less

Biologically active compounds to develop bioelectronics and bio photonics

NASA Astrophysics Data System (ADS)

Mishra, Ashok Kumar; Tiwari, Satya Prakash

2018-05-01

Recent reports on biomaterials and biological systems at nano scale provide researchers with a fertile ground with regard to materials, enabling bioelectronics, bio sensing and new nanotechnologies that cover a wide range of applications. The signal transductions have been reported for many biological phenomenons and new field of biophysics namely Biosensors and Bioelectronics have been emerged out. The advances in the study of various aspects of bio molecules like electrical, optical, thermal etc has established the interesting area of research like biophotonics, nanobiotechnology, molecular solid, molecular liquids, bio instrumentation etc. The present study discusses the some aspects and applications of the bioprocess yields nanostructures that are nearly flawless in composition, stereo specific in structure, and flexible. Furthermore, these biomaterials are environment friendly because they are biodegradable in nature. Biological compounds are self assembled into complex nanostructures and behave like a system possessing long range hierarchical nanoscale order. In addition, chemical modification and genetic engineering can be used to modify bio materials to enhance a specific property. Various biomaterials have been reported which allow nanostructure control for nano photonic applications. The dielectric and conduction properties of the bio molecules have been the subject of many investigations. As a result, there exist a wealth of valuable information on the charge transport and rotational properties of many bio molecules. Amino acids and proteins, nucleic acids, lipids, cell and tissues have been characterized over a wide frequency spectrum ranging from a few hertz to Giga hertz. In certain cases, dielectric measurements have been exploited to probe the physical changes taking place in biologically important structures, for example, in lipid phase transition process in membrane. The phase transition in membrane may be analyzed by applying the theory for lyotropic phase transition in liquid crystals. The photosynthesis property in plant systems may be well interpreted by exploiting the theory for excitonic process taking place in organic semiconductors for electroluminescence and photovoltaic. The biosensor for the measurement of compatibility of a graft union based on electrical measurements has been reported. The present paper discusses the some aspects of recent advances in biomaterials research and correlates it as a basis of emergence of a new discipline namely Bioelectronics and Bio photonics.

Room-temperature ionic liquids and composite materials: platform technologies for CO(2) capture.

PubMed

Bara, Jason E; Camper, Dean E; Gin, Douglas L; Noble, Richard D

2010-01-19

Clean energy production has become one of the most prominent global issues of the early 21st century, prompting social, economic, and scientific debates regarding energy usage, energy sources, and sustainable energy strategies. The reduction of greenhouse gas emissions, specifically carbon dioxide (CO(2)), figures prominently in the discussions on the future of global energy policy. Billions of tons of annual CO(2) emissions are the direct result of fossil fuel combustion to generate electricity. Producing clean energy from abundant sources such as coal will require a massive infrastructure and highly efficient capture technologies to curb CO(2) emissions. Current technologies for CO(2) removal from other gases, such as those used in natural gas sweetening, are also capable of capturing CO(2) from power plant emissions. Aqueous amine processes are found in the vast majority of natural gas sweetening operations in the United States. However, conventional aqueous amine processes are highly energy intensive; their implementation for postcombustion CO(2) capture from power plant emissions would drastically cut plant output and efficiency. Membranes, another technology used in natural gas sweetening, have been proposed as an alternative mechanism for CO(2) capture from flue gas. Although membranes offer a potentially less energy-intensive approach, their development and industrial implementation lags far behind that of amine processes. Thus, to minimize the impact of postcombustion CO(2) capture on the economics of energy production, advances are needed in both of these areas. In this Account, we review our recent research devoted to absorptive processes and membranes. Specifically, we have explored the use of room-temperature ionic liquids (RTILs) in absorptive and membrane technologies for CO(2) capture. RTILs present a highly versatile and tunable platform for the development of new processes and materials aimed at the capture of CO(2) from power plant flue gas and in natural gas sweetening. The desirable properties of RTIL solvents, such as negligible vapor pressures, thermal stability, and a large liquid range, make them interesting candidates as new materials in well-known CO(2) capture processes. Here, we focus on the use of RTILs (1) as absorbents, including in combination with amines, and (2) in the design of polymer membranes. RTIL amine solvents have many potential advantages over aqueous amines, and the versatile chemistry of imidazolium-based RTILs also allows for the generation of new types of CO(2)-selective polymer membranes. RTIL and RTIL-based composites can compete with, or improve upon, current technologies. Moreover, owing to our experience in this area, we are developing new imidazolium-based polymer architectures and thermotropic and lyotropic liquid crystals as highly tailorable materials based on and capable of interacting with RTILs.

Anomalous fast dynamics of adsorbate overlayers near an incommensurate structural transition.

PubMed

Granato, Enzo; Ying, S C; Elder, K R; Ala-Nissila, T

2013-09-20

We investigate the dynamics of a compressively strained adsorbed layer on a periodic substrate via a simple two-dimensional model that admits striped and hexagonal incommensurate phases. We show that the mass transport is superfast near the striped-hexagonal phase boundary and in the hexagonal phase. For an initial step profile separating a bare substrate region (or "hole") from the rest of a striped incommensurate phase, the superfast domain wall dynamics leads to a bifurcation of the initial step profile into two interfaces or profiles propagating in opposite directions with a hexagonal phase in between. This yields a theoretical understanding of the recent experiments for the Pb/Si(111) system.

Experimental static aerodynamics of a regular hexagonal prism in a low density hypervelocity flow

NASA Technical Reports Server (NTRS)

Guy, R. W.; Mueller, J. N.; Lee, L. P.

1972-01-01

A regular hexagonal prism, having a fineness ratio of 1.67, has been tested in a wind tunnel to determine its static aerodynamic characteristics in a low-density hypervelocity flow. The prism tested was a 1/4-scale model of the graphite heat shield which houses the radioactive fuel for the Viking spacecraft auxiliary power supply. The basic hexagonal prism was also modified to simulate a prism on which ablation of one of the six side flats had occurred. This modified hexagonal prism was tested to determine the effects on the aerodynamic characteristics of a shape change caused by ablation during a possible side-on stable reentry.

Effect of hexagonal hillock on luminescence characteristic of multiple quantum wells structure

NASA Astrophysics Data System (ADS)

Du, Jinjuan; Xu, Shengrui; Li, Peixian; Zhang, Jincheng; Zhao, Ying; Peng, Ruoshi; Fan, Xiaomeng; Hao, Yue

2018-04-01

GaN based ultraviolet multiple quantum well structures grown on a c-plane sapphire substrate by metal organic chemical deposition showed a microstructure with a large amount of huge hexagonal hillocks. The polarity of the sample is confirmed by etching with sodium hydroxide solution. The luminous intensity distribution of a typical hexagonal hillock was investigated by the phototluminescent mapping and the luminous intensity at hillock top regions was found to be 15 times higher than that of the regions around hillocks. The reduction of dislocations, the decreasing of the quantum confirmed stack effect caused by semipolar plane and the inclination of the sidewalls of the hexagonal hillock were responsible for the enhancement of luminous intensity.

Variability of Young’s modulus and Poisson’s ratio of hexagonal crystals

NASA Astrophysics Data System (ADS)

Komarova, M. A.; Gorodtsov, V. A.; Lisovenko, D. S.

2018-04-01

In this paper, the variability of elastic characteristics (Young’s modulus and Poisson’s ratio) of hexagonal crystals has been studied. Analytic expressions for Young’s modulus and Poisson’s ratio are obtained. Stationary values for these elastic characteristics are found. Young’s modulus has three stationary values, and Poisson’s ratio has eight stationary values. Numerical analysis of these elastic characteristics for hexagonal crystals is given based on the experimental data from the Landolt-Börnstein handbook. Global extrema of Young’s modulus and Poisson’s ratio for hexagonal crystals are found. Crystals are found in which the maximum values exceeds the upper limit for isotropic materials.

Lipid-based liquid crystalline nanoparticles as oral drug delivery vehicles for poorly water-soluble drugs: cellular interaction and in vivo absorption

PubMed Central

Zeng, Ni; Gao, Xiaoling; Hu, Quanyin; Song, Qingxiang; Xia, Huimin; Liu, Zhongyang; Gu, Guangzhi; Jiang, Mengyin; Pang, Zhiqing; Chen, Hongzhuan; Chen, Jun; Fang, Liang

2012-01-01

Background Lipid-based liquid crystalline nanoparticles (LCNPs) have attracted growing interest as novel drug-delivery systems for improving the bioavailability of both hydrophilic and hydrophobic drugs. However, their cellular interaction and in vivo behavior have not been fully developed and characterized. Methods In this study, self-assembled LCNPs prepared from soy phosphatidylcholine and glycerol dioleate were developed as a platform for oral delivery of paclitaxel. The particle size of empty LCNPs and paclitaxel-loaded LCNPs was around 80 nm. The phase behavior of the liquid crystalline matrix was characterized using crossed polarized light microscopy and small-angle X-ray scattering, and showed both reversed cubic and hexagonal phase in the liquid crystalline matrix. Transmission electron microscopy and cryofield emission scanning electron microscopy analysis revealed an inner winding water channel in LCNPs and a “ ball-like”/“hexagonal” morphology. Results Cellular uptake of LCNPs in Caco-2 cells was found to be concentration-dependent and time-dependent, with involvement of both clathrin and caveolae/lipid raft-mediated endocytosis. Under confocal laser scanning microscopy, soy phosphatidylcholine was observed to segregate from the internalized LCNPs and to fuse with the cell membrane. An in vivo pharmacokinetic study showed that the oral bioavailability of paclitaxel-loaded LCNPs (13.16%) was 2.1 times that of Taxol® (the commercial formulation of paclitaxel, 6.39%). Conclusion The findings of this study suggest that this LCNP delivery system may be a promising candidate for improving the oral bioavailability of poorly water-soluble agents. PMID:22888230

Muon spin rotation study of spin dimers on a triangular lattice in Ba3 MRu2 O9

NASA Astrophysics Data System (ADS)

Ziat, Djamel; Verrier, Aimé; Quilliam, Jeffrey; Aczel, Adam; Sinclair, Ryan; Chen, Qiang; Zhou, Haidong

The family of hexagonal perovskites, Ba3 MA2 O9 has recently been proven to be fertile ground for the discovery of new, exotic magnetic phases, including several quantum spin liquid candidates. The 6H-perovskites can also accommodate spin dimers on a triangular lattice, as in the ruthenate materials Ba3MRu2O9. We will present measurements on materials containing M3 + (M = Y, La, Lu, In), which give rise to mixed valence Ru4.5 + ions wherein the orbital and charge degrees of freedom must also be considered. In particular, muon spin rotation (µSR) experiments, have allowed us to probe the nature of the magnetically ordered ground state of these materials at low temperatures.

Temperature Dependence of Morphology and Growth Mechanism of Vapor-Grown Cd crystals as Affected by Bi Impurities

NASA Astrophysics Data System (ADS)

Yumoto, Hisami; Hasiguti, Ryukiti R.

1984-07-01

Hexagonal prismatic Cd crystals having {10\\bar{1}0} prismatic planes, or occasionally having {11\\bar{2}0} prismatic planes, were grown as high-temperature-type Cd crystals by the thin layer VLS mechanism at Ts (growth temperature) ≥ Tt (transition temperature range: 250-260°C). Pencil-shaped Cd crystals (low-temperature-type Cd crystals) were grown, having {10\\bar{1}0} and {11\\bar{2}0} prismatic planes and {10\\bar{1}1} pyramidal planes by the mixed-type VLS mechanism at Ts≤Tt. When the growth temperature was decreased below Tt, the shape of the solid-liquid interface changed from rounded to faceted. Three processes for the termination of the mixed-type VLS growth are proposed.

Selenium quantum dots: Preparation, structure, and properties

NASA Astrophysics Data System (ADS)

Qian, Fuli; Li, Xueming; Tang, Libin; Lai, Sin Ki; Lu, Chaoyu; Lau, Shu Ping

2017-01-01

An interesting class of low-dimensional nanomaterials, namely, selenium quantum dots (SeQDs), which are composed of nano-sized selenium particles, is reported in this study. The SeQDs possess a hexagonal crystal structure. They can be synthesized in large quantity by ultrasound liquid-phase exfoliation using NbSe2 powders as the source material and N-Methyl-2-pyrrolidone (NMP) as the dispersant. During sonication, the Nb-Se bonds dissociate; the SeQDs are formed, while niobium is separated by centrifugation. The SeQDs have a narrow diameter distribution from 1.9 to 4.6 nm and can be dispersed with high stability in NMP without the need for passivating agents. They exhibit photoluminescence properties that are expected to find useful applications in bioimaging, optoelectronics, as well as nanocomposites.

Ionic depletion at the crystalline Gibbs layer of PEG-capped gold nanoparticle brushes at aqueous surfaces

NASA Astrophysics Data System (ADS)

Wang, Wenjie; Zhang, Honghu; Mallapragada, Surya; Travesset, Alex; Vaknin, David

2017-12-01

In situ surface-sensitive x-ray diffraction and grazing incidence x-ray fluorescence spectroscopy (GIXFS) methods are combined to determine the ionic distributions across the liquid/vapor interfaces of thiolated-polyethylene-glycol-capped gold nanoparticle (PEG-AuNP) solutions. Induced by the addition of salts (i.e., Cs2SO4 ) to PEG-AuNPs solutions, two-dimensional hexagonal lattices of PEG-AuNPs form spontaneously at the aqueous surfaces, as is demonstrated by x-ray reflectivity and grazing incidence small-angle x-ray scattering. By taking advantage of element specificity with the GIXFS method, we find that the cation Cs+ concentration at the crystalline film is significantly reduced in parts of the PEG-AuNP film compared with that in the bulk.

Structure and free energy of cholesteric DNA droplets

NASA Astrophysics Data System (ADS)

Strey, Helmut; Hong, Helen; Easwar, Nalini

2000-03-01

Liquid crystals of DNA are the simplest model systems for DNA packing in cell nuclei or in phage heads. With increasing concentration DNA solutions exhibit the following phases: hexagonal, line hexatic, cholesteric, blue phases. We will present measurements of defect structure and pitch of cholesteric spherulites of short fragment DNA (146 base pairs). DNA concentration as well as salt concentrations are controlled by bathing the spherulites in poly (ethylene glycol) (MW 35,000u) solutions of known osmotic pressure. Combining polarizing microscopy and x-ray scattering with the osmotic stress method allows us to monitor the cholesteric structure and pitch as a function of interaxial distance between DNA molecules as well as salt concentration and type. In particular, we present data on how the DNA cholesteric pitch unwinds when the line hexatic phase is approached.

Ice Surfaces.

PubMed

Shultz, Mary Jane

2017-05-05

Ice is a fundamental solid with important environmental, biological, geological, and extraterrestrial impact. The stable form of ice at atmospheric pressure is hexagonal ice, I h . Despite its prevalence, I h remains an enigmatic solid, in part due to challenges in preparing samples for fundamental studies. Surfaces of ice present even greater challenges. Recently developed methods for preparation of large single-crystal samples make it possible to reproducibly prepare any chosen face to address numerous fundamental questions. This review describes preparation methods along with results that firmly establish the connection between the macroscopic structure (observed in snowflakes, microcrystallites, or etch pits) and the molecular-level configuration (detected with X-ray or electron scattering techniques). Selected results of probing interactions at the ice surface, including growth from the melt, surface vibrations, and characterization of the quasi-liquid layer, are discussed.

Measurement of temperature and concentration influence on the dispersion of fused silica glass photonic crystal fiber infiltrated with water-ethanol mixture

NASA Astrophysics Data System (ADS)

Van, Hieu Le; Buczynski, Ryszard; Long, Van Cao; Trippenbach, Marek; Borzycki, Krzysztof; Manh, An Nguyen; Kasztelanic, Rafal

2018-01-01

We present experimental and simulation results of the zero-dispersion shift in photonics crystal fibers infiltrated with water-ethanol mixture. The fiber based on the fused silica glass with a hexagonal lattice consists of seven rings of air-holes filled by liquid. We show that it is possible to shift the zero-dispersion wavelength by 35 ps/nm/km when changing the temperature by 60 °C, and by 42 ps/nm/km when changing the concentration of ethanol from 0 to 100%. The results also show that for the optical fiber filed with pure ethanol the flattened part of the dispersion shifts from anomalous to the normal regime at temperatures below -70 °C.

Optical Properties of CdS Nanobelts and Nanosaws Synthesized by Thermal Evaporation Method

NASA Astrophysics Data System (ADS)

Peng, Zhi-wei; Zou, Bing-suo

2012-04-01

By a simple one-step H2-assisted thermal evaporation method, high quality CdS nanostructures have been successfully fabricated on Au coated Si substrates in large scale. The as-synthesized CdS nanostructures consisted of sword-like nanobelts and toothed nanosaws with a single-crystal hexagonal wurtzite structure. The deposition temperature played an important role in determining the size and morphology of the CdS nanostructures. A combination of vapor-liquid-solid and vapor-solid growth mechanisms were proposed to interpret the formation of CdS nanostructures. Photoluminescence measurement indicated that the nanobelts and nanosaws have a prominent green emission at about 512 nm, which is the band-to-band emission of CdS. The waveguide characteristics of both types of CdS nanostructures were observed and discussed.

The structures of the crystalline phase and columnar mesophase of rhodium (II) heptanoate and of its binary mixture with copper (II) heptanoate probed by EXAFS

NASA Astrophysics Data System (ADS)

Inb-Elhaj, M.; Guillon, D.; Skoulios, A.; Maldivi, P.; Giroud-Godquin, A. M.; Marchon, J.-C.

1992-12-01

EXAFS was used to investigate the local structure of the polar spines of rhodium (II) soaps in the columnar liquid crystalline state. It was also used to ascertain the degree of blending of the cores in binary mixtures of rhodium (II) and copper (II) soaps. For the pure rhodium soaps, the columns are shown to result from the stacking of binuclear metal-metal bonded dirhodium tetracarboxylate units bonded to one another by apical ligation of the metal atom of each complex with one of the oxygen atoms of the adjacent molecule. Mixtures of rhodium (II) and copper (II) soaps give a hexagonal columnar mesophase in which pure rhodium and pure copper columns are randomly distributed.

Long stroke jar bumper sub with safety sleeve

DOE Office of Scientific and Technical Information (OSTI.GOV)

Downen, J.L.; Sutliff, W.N.

1981-04-14

A hydraulic jar apparatus to be disposed in a drilling string embodying inner and outer telescopically arranged elements. Overlapping portions of the elements provide an annual chamber confining an operating liquid by an annular seal fixed to the outer element at the lower end of the chamber and an annular polly pack seal fixed to the outer element at the upper end of the chamber. A piston is extended radially from the inner element into the chamber and the chamber is divided by a cylinder on the outer element into low and high pressure sections. Impact shoulders are provided onmore » the elements in axially opposed relation to produce a jarring blow and the elements are telescopically coupled by a hexagonal spline sub assembly.« less

Multiphase Equation of State and Strength Properties of Beryllium from AB INITIO and Quantum Molecular Dynamics Calculations.

NASA Astrophysics Data System (ADS)

Robert, G.; Sollier, A.; Legrand, Ph.

2007-12-01

In the framework of density functional theory, static properties and phonon spectra of beryllium have been calculated under high compression (for pressures up to 4 Mbar) for two solid phases: hexagonal compact (hcp) and body-centered cubic (bcc). The melting curve and some isotherms in the liquid phase have been calculated using quantum molecular dynamics. The coupling of these theoretical data to a quasi-harmonic approach (phonon moments) allows us to suggest a new theoretical phase diagram and to build a multiphase equation of state (EOS) valid in a large range of pressure and temperature. The resulting Hugoniot curves as well as the evolution of the longitudinal sound speed with both pressure and temperature are in good agreement with available experimental data.

High-temperature fcc phase of Pr:  Negative thermal expansion and intermediate valence state

NASA Astrophysics Data System (ADS)

Kuznetsov, A. Yu.; Dmitriev, V. P.; Bandilet, O. I.; Weber, H.-P.

2003-08-01

A high-temperature angle-dispersive synchrotron radiation diffraction study has revealed the double hexagonal-close-packed-to-face-centered-cubic (dhcp-to-fcc) transformation in the Pr metal occurring martensitically between 575 and 1035 K. The high-temperature fcc phase shows a negative thermal expansion in the range 600 800 K, attributed to the 4f-electron delocalization. A phenomenological theory is developed, which explains consistently the observed effect in terms of the mean valence variation of the metal as a function of temperature; it also predicts the existence of an isostructural phase transition and of a critical end point of a gas-liquid type in compressed Pr. The analysis of published data on P-T variation of conductivity of Pr supports this prediction.

Discovery of a hexagonal ultradense hydrous phase in (Fe,Al)OOH

NASA Astrophysics Data System (ADS)

Zhang, Li; Yuan, Hongsheng; Meng, Yue; Mao, Ho-kwang

2018-03-01

A deep lower-mantle (DLM) water reservoir depends on availability of hydrous minerals which can store and transport water into the DLM without dehydration. Recent discoveries found hydrous phases AlOOH (Z = 2) with a CaCl2-type structure and FeOOH (Z = 4) with a cubic pyrite-type structure stable under the high-pressure–temperature (P-T) conditions of the DLM. Our experiments at 107–136 GPa and 2,400 K have further demonstrated that (Fe,Al)OOH is stabilized in a hexagonal lattice. By combining powder X-ray-diffraction techniques with multigrain indexation, we are able to determine this hexagonal hydrous phase with a = 10.5803(6) Å and c = 2.5897(3) Å at 110 GPa. Hexagonal (Fe,Al)OOH can transform to the cubic pyrite structure at low T with the same density. The hexagonal phase can be formed when δ-AlOOH incorporates FeOOH produced by reaction between water and Fe, which may store a substantial quantity of water in the DLM.

Bi2Te3 thin hexagonal nanoplatelets: Synthesis and its characterization studies

NASA Astrophysics Data System (ADS)

Vinoth, S.; Balaganapathi, T.; KaniAmuthan, B.; Arun, T.; Muthuselvam, I. Panneer; Chou, Fang-Cheng; Thilakan, P.

2017-08-01

Solvothermal synthesis and optimization of pure Bismuth telluride (Bi2Te3) hexagonal nanoplatelets was carried out from Bismuth Oxide (Bi2O3) and Tellurium dioxide (TeO2). XRD measurements revealed a sensitive change in crystallization behaviour in correlation with variation in Te/Bi stoichiometry identified through the exchange in intensities between (10 10 ̅) and (110) peaks. Further, Energy Dispersive X-ray (EDAX) analysis revealed the variation in Te/Bi ratio with respect to autoclave temperature. Field emission scanning electron Microscope (FESEM) and the high resolution transmission electron Microscope (HRTEM) studies show the complete growth of hexagonal nanoplatelets at 200 °C. Confocal Micro-Raman measurements revealed the occurrence of symmetry breaking in the synthesized hexagonal nanoplatelets. The electrical conductivity and the activation energy were recorded as 6.01×10-3 S/m and 0.042 eV respectively. Highest maximum absolute value of Seebeck coefficient of -355 μV/K was obtained for the hexagonal nanoplatelets.

Design considerations for quasi-phase-matching in doubly resonant lithium niobate hexagonal micro-resonators

NASA Astrophysics Data System (ADS)

Sono, Tleyane J.; Riziotis, Christos; Mailis, Sakellaris; Eason, Robert W.

2017-09-01

Fabrication capabilities of high optical quality hexagonal superstructures by chemical etching of inverted ferroelectric domains in lithium niobate platform suggests a route for efficient implementation of compact hexagonal microcavities. Such nonlinear optical hexagonal micro-resonators are proposed as a platform for second harmonic generation (SHG) by the combined mechanisms of total internal reflection (TIR) and quasi-phase-matching (QPM). The proposed scheme for SHG via TIR-QPM in a hexagonal microcavity can improve the efficiency and also the compactness of SHG devices compared to traditional linear-type based devices. A simple theoretical model based on six-bounce trajectory and phase matching conditions was capable for obtaining the optimal cavity size. Furthermore numerical simulation results based on finite difference time domain beam propagation method analysis confirmed the solutions obtained by demonstrating resonant operation of the microcavity for the second harmonic wave produced by TIR-QPM. Design aspects, optimization issues and characteristics of the proposed nonlinear device are presented.

Surfactant-assisted growth and optical properties of ZnO hexagonal bilayer disk-like microstructures

NASA Astrophysics Data System (ADS)

Zhu, Q. P.; Shen, X. Y.; Wang, L. L.; Zhu, L. P.; Wang, L. J.; Liao, G. H.

2018-01-01

ZnO hexagonal bilayer disk-like microstructures are successfully fabricated using a simple solvothermal method assisted with surfactant. The structure and morphology were investigated by XRD, SEM, and EDS. XRD result indicated that the as-obtained samples were well-crystallized wurtzite hexagonal ZnO structure. SEM images showed that the ZnO hexagonal bilayer disk-like assembles consist of two uniform and smooth disks with an average edge length of 6 μm and thickness of ˜4 μm. UV-vis spectrum reveals that ZnO sampls show an appreciable red shift and the band gap energy of the obtained ZnO samples were about 3.15 eV. A very strong UV emission at the ultraviolet (UV) region was observed in the photoluminescence (PL) spectrum of the as-prepared ZnO samples tested at room-temperature. A possible growth process of the ZnO hexagonal bilayer disk-like microstructures was schematically illustrated.

Is hexagonal boron nitride always good as a substrate for carbon nanotube-based devices?

PubMed

Kang, Seoung-Hun; Kim, Gunn; Kwon, Young-Kyun

2015-02-21

Hexagonal boron nitride sheets have been noted especially for their enhanced properties as substrates for sp(2) carbon-based nanodevices. To evaluate whether such enhanced properties would be retained under various realistic conditions, we investigate the structural and electronic properties of semiconducting carbon nanotubes on perfect and defective hexagonal boron nitride sheets under an external electric field as well as with a metal impurity, using density functional theory. We verify that the use of a perfect hexagonal boron nitride sheet as a substrate indeed improves the device performances of carbon nanotubes, compared with the use of conventional substrates such as SiO2. We further show that even the hexagonal boron nitride with some defects can show better performance as a substrate. Our calculations, on the other hand, also suggest that some defective boron nitride layers with a monovacancy and a nickel impurity could bring about poor device behavior since the imperfections impair electrical conductivity due to residual scattering under an applied electric field.

Intrinsic ferromagnetism in hexagonal boron nitride nanosheets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Si, M. S.; Gao, Daqiang, E-mail: gaodq@lzu.edu.cn, E-mail: xueds@lzu.edu.cn; Yang, Dezheng

2014-05-28

Understanding the mechanism of ferromagnetism in hexagonal boron nitride nanosheets, which possess only s and p electrons in comparison with normal ferromagnets based on localized d or f electrons, is a current challenge. In this work, we report an experimental finding that the ferromagnetic coupling is an intrinsic property of hexagonal boron nitride nanosheets, which has never been reported before. Moreover, we further confirm it from ab initio calculations. We show that the measured ferromagnetism should be attributed to the localized π states at edges, where the electron-electron interaction plays the role in this ferromagnetic ordering. More importantly, we demonstratemore » such edge-induced ferromagnetism causes a high Curie temperature well above room temperature. Our systematical work, including experimental measurements and theoretical confirmation, proves that such unusual room temperature ferromagnetism in hexagonal boron nitride nanosheets is edge-dependent, similar to widely reported graphene-based materials. It is believed that this work will open new perspectives for hexagonal boron nitride spintronic devices.« less

Algebraic signal processing theory: 2-D spatial hexagonal lattice.

PubMed

Pünschel, Markus; Rötteler, Martin

2007-06-01

We develop the framework for signal processing on a spatial, or undirected, 2-D hexagonal lattice for both an infinite and a finite array of signal samples. This framework includes the proper notions of z-transform, boundary conditions, filtering or convolution, spectrum, frequency response, and Fourier transform. In the finite case, the Fourier transform is called discrete triangle transform. Like the hexagonal lattice, this transform is nonseparable. The derivation of the framework makes it a natural extension of the algebraic signal processing theory that we recently introduced. Namely, we construct the proper signal models, given by polynomial algebras, bottom-up from a suitable definition of hexagonal space shifts using a procedure provided by the algebraic theory. These signal models, in turn, then provide all the basic signal processing concepts. The framework developed in this paper is related to Mersereau's early work on hexagonal lattices in the same way as the discrete cosine and sine transforms are related to the discrete Fourier transform-a fact that will be made rigorous in this paper.

Interlayer orientation-dependent light absorption and emission in monolayer semiconductor stacks

PubMed Central

Heo, Hoseok; Sung, Ji Ho; Cha, Soonyoung; Jang, Bo-Gyu; Kim, Joo-Youn; Jin, Gangtae; Lee, Donghun; Ahn, Ji-Hoon; Lee, Myoung-Jae; Shim, Ji Hoon; Choi, Hyunyong; Jo, Moon-Ho

2015-01-01

Two-dimensional stacks of dissimilar hexagonal monolayers exhibit unusual electronic, photonic and photovoltaic responses that arise from substantial interlayer excitations. Interband excitation phenomena in individual hexagonal monolayer occur in states at band edges (valleys) in the hexagonal momentum space; therefore, low-energy interlayer excitation in the hexagonal monolayer stacks can be directed by the two-dimensional rotational degree of each monolayer crystal. However, this rotation-dependent excitation is largely unknown, due to lack in control over the relative monolayer rotations, thereby leading to momentum-mismatched interlayer excitations. Here, we report that light absorption and emission in MoS2/WS2 monolayer stacks can be tunable from indirect- to direct-gap transitions in both spectral and dynamic characteristics, when the constituent monolayer crystals are coherently stacked without in-plane rotation misfit. Our study suggests that the interlayer rotational attributes determine tunable interlayer excitation as a new set of basis for investigating optical phenomena in a two-dimensional hexagonal monolayer system. PMID:26099952

IMPROVED TYPE OF FUEL ELEMENT

DOEpatents

Monson, H.O.

1961-01-24

A radiator-type fuel block assembly is described. It has a hexagonal body of neutron fissionable material having a plurality of longitudinal equal- spaced coolant channels therein aligned in rows parallel to each face of the hexagonal body. Each of these coolant channels is hexagonally shaped with the corners rounded and enlarged and the assembly has a maximum temperature isothermal line around each channel which is approximately straight and equidistant between adjacent channels.

Adiabatic demagnetization of the antiferromagnetic spin-1/2 Heisenberg hexagonal cluster

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deb, Moumita, E-mail: moumitadeb44@gmail.com; Ghosh, Asim Kumar, E-mail: asimkumar96@yahoo.com

2016-05-23

Exact analytic expressions of eigenvalues of the antiferromagnetic spin-1/2 Heisenberg hexagon in the presence of uniform magnetic field have been obtained. Magnetization process, nature of isentrops and properties of magneto caloric effect in terms of adiabatic demagnetization have been investigated. Theoretical results have been used to study the magneto caloric effect of the spin-1/2 Heisenberg hexagonal compound Cu{sub 3}WO{sub 6}.

Selective MBE growth of hexagonal networks of trapezoidal and triangular GaAs nanowires on patterned (1 1 1)B substrates

NASA Astrophysics Data System (ADS)

Tamai, Isao; Hasegawa, Hideki

2007-04-01

As a combination of novel hardware architecture and novel system architecture for future ultrahigh-density III-V nanodevice LSIs, the authors' group has recently proposed a hexagonal binary decision diagram (BDD) quantum circuit approach where gate-controlled path switching BDD node devices for a single or few electrons are laid out on a hexagonal nanowire network to realize a logic function. In this paper, attempts are made to establish a method to grow highly dense hexagonal nanowire networks for future BDD circuits by selective molecular beam epitaxy (MBE) on (1 1 1)B substrates. The (1 1 1)B orientation is suitable for BDD architecture because of the basic three-fold symmetry of the BDD node device. The growth experiments showed complex evolution of the cross-sectional structures, and it was explained in terms of kinetics determining facet boundaries. Straight arrays of triangular nanowires with 60 nm base width as well as hexagonal arrays of trapezoidal nanowires with a node density of 7.5×10 6 cm -2 were successfully grown with the aid of computer simulation. The result shows feasibility of growing high-density hexagonal networks of GaAs nanowires with precise control of the shape and size.

Effect of reductant and PVP on morphology and magnetic property of ultrafine Ni powders prepared via hydrothermal route

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Jun, E-mail: j-zhang@126.com; Wang, Xiucai; Li, Lili

2013-10-15

Graphical abstract: The ultrafine Ni powders with the shapes including sphere, pearl-string, leaf, fish-bone, hexagonal sheet and silknet were prepared through one-step hydrothermal reduction using different reductants. Their saturation magnetization, remanent magnetization and coercivity sequentially increase, and the coercivity of hexagonal sheet-like Ni powders increases by 25% compared with the Ni bulk counterpart. - Highlights: • The ultrafine Ni powders with various shapes of sphere, fish-bone, hexagonal sheet, etc. • Facile and one-step hydrothermal reduction using three reductants and PVP additive was developed. • Magnetic properties of the ultrafine Ni powders with different shapes were measured. • Compared with bulkmore » Ni material, coercivity of hexagonal sheet Ni increases by 25%. • The formation mechanism of the shapes was suggested. - Abstract: The ultrafine nickel particles with different shapes including sphere, pearl-string, leaf, fish-bone, hexagonal sheet and silknet were prepared through one-step hydrothermal reduction using hydrazine hydrate, sodium hypophosphite and ethylene glycol as reductants, polyvinylpyrrolidone as structure-directing agent. It has been verified with the characterization of X-ray powder diffraction and transmission/scanning electronic microscopy that as-prepared products belong to face-centered cubic structure of nickel microcrystals with high purity and fine dispersity. The magnetic hysteresis loops measured at room temperature reveal that the values of saturation magnetization, remanent magnetization and coercivity rise sequentially from silknet, sphere to hexagonal sheet. In comparison with nickel bulk counterpart, the coercivity of the hexagonal sheet nickel powders increases by 25%.« less

Electrochemical ion transfer across liquid/liquid interfaces confined within solid-state micropore arrays--simulations and experiments.

PubMed

Strutwolf, Jörg; Scanlon, Micheál D; Arrigan, Damien W M

2009-01-01

Miniaturised liquid/liquid interfaces provide benefits for bioanalytical detection with electrochemical methods. In this work, microporous silicon membranes which can be used for interface miniaturisation were characterized by simulations and experiments. The microporous membranes possessed hexagonal arrays of pores with radii between 10 and 25 microm, a pore depth of 100 microm and pore centre-to-centre separations between 99 and 986 microm. Cyclic voltammetry was used to monitor ion transfer across arrays of micro-interfaces between two immiscible electrolyte solutions (microITIES) formed at these membranes, with the organic phase present as an organogel. The results were compared to computational simulations taking into account mass transport by diffusion and encompassing diffusion to recessed interfaces and overlapped diffusion zones. The simulation and experimental data were both consistent with the situation where the location of the liquid/liquid (l/l) interface was on the aqueous side of the silicon membrane and the pores were filled with the organic phase. While the current for the forward potential scan (transfer of the ion from the aqueous phase to the organic phase) was strongly dependent on the location of the l/l interface, the current peak during the reverse scan (transfer of the ion from the organic phase to the aqueous phase) was influenced by the ratio of the transferring ion's diffusion coefficients in both phases. The diffusion coefficient of the transferring ion in the gelified organic phase was ca. nine times smaller than in the aqueous phase. Asymmetric cyclic voltammogram shapes were caused by the combined effect of non-symmetrical diffusion (spherical and linear) and by the inequality of the diffusion coefficient in both phases. Overlapping diffusion zones were responsible for the observation of current peaks instead of steady-state currents during the forward scan. The characterisation of the diffusion behaviour is an important requirement for application of these silicon membranes in electroanalytical chemistry.

Pressure-induced transformations in computer simulations of glassy water.

PubMed

Chiu, Janet; Starr, Francis W; Giovambattista, Nicolas

2013-11-14

Glassy water occurs in at least two broad categories: low-density amorphous (LDA) and high-density amorphous (HDA) solid water. We perform out-of-equilibrium molecular dynamics simulations to study the transformations of glassy water using the ST2 model. Specifically, we study the known (i) compression-induced LDA-to-HDA, (ii) decompression-induced HDA-to-LDA, and (iii) compression-induced hexagonal ice-to-HDA transformations. We study each transformation for a broad range of compression/decompression temperatures, enabling us to construct a "P-T phase diagram" for glassy water. The resulting phase diagram shows the same qualitative features reported from experiments. While many simulations have probed the liquid-state phase behavior, comparatively little work has examined the transitions of glassy water. We examine how the glass transformations relate to the (first-order) liquid-liquid phase transition previously reported for this model. Specifically, our results support the hypothesis that the liquid-liquid spinodal lines, between a low-density and high-density liquid, are extensions of the LDA-HDA transformation lines in the limit of slow compression. Extending decompression runs to negative pressures, we locate the sublimation lines for both LDA and hyperquenched glassy water (HGW), and find that HGW is relatively more stable to the vapor. Additionally, we observe spontaneous crystallization of HDA at high pressure to ice VII. Experiments have also seen crystallization of HDA, but to ice XII. Finally, we contrast the structure of LDA and HDA for the ST2 model with experiments. We find that while the radial distribution functions (RDFs) of LDA are similar to those observed in experiments, considerable differences exist between the HDA RDFs of ST2 water and experiment. The differences in HDA structure, as well as the formation of ice VII (a tetrahedral crystal), are a consequence of ST2 overemphasizing the tetrahedral character of water.

Pressure-induced transformations in computer simulations of glassy water

NASA Astrophysics Data System (ADS)

Chiu, Janet; Starr, Francis W.; Giovambattista, Nicolas

2013-11-01

Glassy water occurs in at least two broad categories: low-density amorphous (LDA) and high-density amorphous (HDA) solid water. We perform out-of-equilibrium molecular dynamics simulations to study the transformations of glassy water using the ST2 model. Specifically, we study the known (i) compression-induced LDA-to-HDA, (ii) decompression-induced HDA-to-LDA, and (iii) compression-induced hexagonal ice-to-HDA transformations. We study each transformation for a broad range of compression/decompression temperatures, enabling us to construct a "P-T phase diagram" for glassy water. The resulting phase diagram shows the same qualitative features reported from experiments. While many simulations have probed the liquid-state phase behavior, comparatively little work has examined the transitions of glassy water. We examine how the glass transformations relate to the (first-order) liquid-liquid phase transition previously reported for this model. Specifically, our results support the hypothesis that the liquid-liquid spinodal lines, between a low-density and high-density liquid, are extensions of the LDA-HDA transformation lines in the limit of slow compression. Extending decompression runs to negative pressures, we locate the sublimation lines for both LDA and hyperquenched glassy water (HGW), and find that HGW is relatively more stable to the vapor. Additionally, we observe spontaneous crystallization of HDA at high pressure to ice VII. Experiments have also seen crystallization of HDA, but to ice XII. Finally, we contrast the structure of LDA and HDA for the ST2 model with experiments. We find that while the radial distribution functions (RDFs) of LDA are similar to those observed in experiments, considerable differences exist between the HDA RDFs of ST2 water and experiment. The differences in HDA structure, as well as the formation of ice VII (a tetrahedral crystal), are a consequence of ST2 overemphasizing the tetrahedral character of water.

Extent and relevance of stacking disorder in “ice Ic”

PubMed Central

Kuhs, Werner F.; Sippel, Christian; Falenty, Andrzej; Hansen, Thomas C.

2012-01-01

A solid water phase commonly known as “cubic ice” or “ice Ic” is frequently encountered in various transitions between the solid, liquid, and gaseous phases of the water substance. It may form, e.g., by water freezing or vapor deposition in the Earth’s atmosphere or in extraterrestrial environments, and plays a central role in various cryopreservation techniques; its formation is observed over a wide temperature range from about 120 K up to the melting point of ice. There was multiple and compelling evidence in the past that this phase is not truly cubic but composed of disordered cubic and hexagonal stacking sequences. The complexity of the stacking disorder, however, appears to have been largely overlooked in most of the literature. By analyzing neutron diffraction data with our stacking-disorder model, we show that correlations between next-nearest layers are clearly developed, leading to marked deviations from a simple random stacking in almost all investigated cases. We follow the evolution of the stacking disorder as a function of time and temperature at conditions relevant to atmospheric processes; a continuous transformation toward normal hexagonal ice is observed. We establish a quantitative link between the crystallite size established by diffraction and electron microscopic images of the material; the crystallite size evolves from several nanometers into the micrometer range with progressive annealing. The crystallites are isometric with markedly rough surfaces parallel to the stacking direction, which has implications for atmospheric sciences. PMID:23236184

Direct detection of metal-insulator phase transitions using the modified Backus-Gilbert method

NASA Astrophysics Data System (ADS)

Ulybyshev, Maksim; Winterowd, Christopher; Zafeiropoulos, Savvas

2018-03-01

The detection of the (semi)metal-insulator phase transition can be extremely difficult if the local order parameter which characterizes the ordered phase is unknown. In some cases, it is even impossible to define a local order parameter: the most prominent example of such system is the spin liquid state. This state was proposed to exist in the Hubbard model on the hexagonal lattice in a region between the semimetal phase and the antiferromagnetic insulator phase. The existence of this phase has been the subject of a long debate. In order to detect these exotic phases we must use alternative methods to those used for more familiar examples of spontaneous symmetry breaking. We have modified the Backus-Gilbert method of analytic continuation which was previously used in the calculation of the pion quasiparticle mass in lattice QCD. The modification of the method consists of the introduction of the Tikhonov regularization scheme which was used to treat the ill-conditioned kernel. This modified Backus-Gilbert method is applied to the Euclidean propagators in momentum space calculated using the hybrid Monte Carlo algorithm. In this way, it is possible to reconstruct the full dispersion relation and to estimate the mass gap, which is a direct signal of the transition to the insulating state. We demonstrate the utility of this method in our calculations for the Hubbard model on the hexagonal lattice. We also apply the method to the metal-insulator phase transition in the Hubbard-Coulomb model on the square lattice.

Growth of High-Density Zinc Oxide Nanorods on Porous Silicon by Thermal Evaporation

PubMed Central

Rusli, Nurul Izni; Tanikawa, Masahiro; Mahmood, Mohamad Rusop; Yasui, Kanji; Hashim, Abdul Manaf

2012-01-01

The formation of high-density zinc oxide (ZnO) nanorods on porous silicon (PS) substrates at growth temperatures of 600–1000 °C by a simple thermal evaporation of zinc (Zn) powder in the presence of oxygen (O2) gas was systematically investigated. The high-density growth of ZnO nanorods with (0002) orientation over a large area was attributed to the rough surface of PS, which provides appropriate planes to promote deposition of Zn or ZnOx seeds as nucleation sites for the subsequent growth of ZnO nanorods. The geometrical morphologies of ZnO nanorods are determined by the ZnOx seed structures, i.e., cluster or layer structures. The flower-like hexagonal-faceted ZnO nanorods grown at 600 °C seem to be generated from the sparsely distributed ZnOx nanoclusters. Vertically aligned hexagonal-faceted ZnO nanorods grown at 800 °C may be inferred from the formation of dense arrays of ZnOx clusters. The formation of disordered ZnO nanorods formed at 1000 °C may due to the formation of a ZnOx seed layer. The growth mechanism involved has been described by a combination of self-catalyzed vapor-liquid-solid (VLS) and vapor-solid (VS) mechanism. The results suggest that for a more precise study on the growth of ZnO nanostructures involving the introduction of seeds, the initial seed structures must be taken into account given their significant effects.

Cromolyn as surface active drug (surfadrug): Effect of the self-association on diffusion and percutaneous permeation.

PubMed

Tavano, Lorena; Nicoletta, Fiore Pasquale; Picci, Nevio; Muzzalupo, Rita

2016-03-01

Cromolyn sodium, or disodium cromoglycate (CS), is a surface active drug: a pharmacologically active compound with an amphiphilic nature. At certain conditions it is able to self-associate in several kind of supramolecular aggregates. Since CS could play the role of both carrier and drug, bypassing the use of additional excipients and increasing the system biocompatibility, the effects of cromolyn self-aggregates on diffusion and percutaneous permeation across rabbit ear skin were investigated. Niosomes (vesicular systems, 0.5wt% of CS), monomeric and isotropic solutions (0.5 and 5wt% of CS), nematic (15wt% of CS) and hexagonal phases (30wt% of CS) were selected as supramolecular systems and tested as transdermal delivery systems. Results demonstrated that CS was able to form vesicular structures of about 500nm of diameter and this formulation gave the higher percutaneous permeation profile (systemic action), while isotropic solution and liquid crystals mesophases acted as slower release reservoir of drug on the skin surface (local action), as confirmed by diffusion coefficients. Diffusion rates through a synthetic membrane were dependent both on CS concentration present into the formulations and on its structural organization: maximum diffusion was noticed with isotropic solution, a lower amount of diffused cromolyn sodium was achieved by hexagonal phase. Consequently, CS appears as a versatile surfadrug as, depending on the disease degree, it is possible to modulate its permeation profile by choosing the most appropriate formulation. Copyright © 2015 Elsevier B.V. All rights reserved.

Shear-induced structural transitions in Newtonian non-Newtonian two-phase flow

NASA Astrophysics Data System (ADS)

Cristobal, G.; Rouch, J.; Colin, A.; Panizza, P.

2000-09-01

We show the existence under shear flow of steady states in a two-phase region of a brine-surfactant system in which lyotropic dilute lamellar (non-Newtonian) and sponge (Newtonian) phases are coexisting. At high shear rates and low sponge phase-volume fractions, we report on the existence of a dynamic transition corresponding to the formation of a colloidal crystal of multilamellar vesicles (or ``onions'') immersed in the sponge matrix. As the sponge phase-volume fraction increases, this transition exhibits a hysteresis loop leading to a structural bistability of the two-phase flow. Contrary to single phase lamellar systems where it is always 100%, the onion volume fraction can be monitored continuously from 0 to 100 %.

Quasi-random array imaging collimator

DOEpatents

Fenimore, E.E.

1980-08-20

A hexagonally shaped quasi-random no-two-holes-touching imaging collimator. The quasi-random array imaging collimator eliminates contamination from small angle off-axis rays by using a no-two-holes-touching pattern which simultaneously provides for a self-supporting array increasing throughput by elimination of a substrate. The present invention also provides maximum throughput using hexagonally shaped holes in a hexagonal lattice pattern for diffraction limited applications. Mosaicking is also disclosed for reducing fabrication effort.

Random array grid collimator

DOEpatents

Fenimore, E.E.

1980-08-22

A hexagonally shaped quasi-random no-two-holes touching grid collimator. The quasi-random array grid collimator eliminates contamination from small angle off-axis rays by using a no-two-holes-touching pattern which simultaneously provides for a self-supporting array increasng throughput by elimination of a substrate. The presentation invention also provides maximum throughput using hexagonally shaped holes in a hexagonal lattice pattern for diffraction limited applications. Mosaicking is also disclosed for reducing fabrication effort.

Surface charge conductivity of a topological insulator in a magnetic field: The effect of hexagonal warping

NASA Astrophysics Data System (ADS)

Akzyanov, R. S.; Rakhmanov, A. L.

2018-02-01

We investigate the influence of hexagonal warping on the transport properties of topological insulators. We study the charge conductivity within Kubo formalism in the first Born approximation using low-energy expansion of the Hamiltonian near the Dirac point. The effects of disorder, magnetic field, and chemical-potential value are analyzed in detail. We find that the presence of hexagonal warping significantly affects the conductivity of the topological insulator. In particular, it gives rise to the growth of the longitudinal conductivity with the increase of the disorder and anisotropic anomalous in-plane magnetoresistance. Hexagonal warping also affects the quantum anomalous Hall effect and anomalous out-of-plane magnetoresistance. The obtained results are consistent with the experimental data.

Multilayer DNA origami packed on hexagonal and hybrid lattices.

PubMed

Ke, Yonggang; Voigt, Niels V; Gothelf, Kurt V; Shih, William M

2012-01-25

"Scaffolded DNA origami" has been proven to be a powerful and efficient approach to construct two-dimensional or three-dimensional objects with great complexity. Multilayer DNA origami has been demonstrated with helices packing along either honeycomb-lattice geometry or square-lattice geometry. Here we report successful folding of multilayer DNA origami with helices arranged on a close-packed hexagonal lattice. This arrangement yields a higher density of helical packing and therefore higher resolution of spatial addressing than has been shown previously. We also demonstrate hybrid multilayer DNA origami with honeycomb-lattice, square-lattice, and hexagonal-lattice packing of helices all in one design. The availability of hexagonal close-packing of helices extends our ability to build complex structures using DNA nanotechnology. © 2011 American Chemical Society

Self-assembled multicompartment liquid crystalline lipid carriers for protein, peptide, and nucleic acid drug delivery.

PubMed

Angelova, Angelina; Angelov, Borislav; Mutafchieva, Rada; Lesieur, Sylviane; Couvreur, Patrick

2011-02-15

Lipids and lipopolymers self-assembled into biocompatible nano- and mesostructured functional materials offer many potential applications in medicine and diagnostics. In this Account, we demonstrate how high-resolution structural investigations of bicontinuous cubic templates made from lyotropic thermosensitive liquid-crystalline (LC) materials have initiated the development of innovative lipidopolymeric self-assembled nanocarriers. Such structures have tunable nanochannel sizes, morphologies, and hierarchical inner organizations and provide potential vehicles for the predictable loading and release of therapeutic proteins, peptides, or nucleic acids. This Account shows that structural studies of swelling of bicontinuous cubic lipid/water phases are essential for overcoming the nanoscale constraints for encapsulation of large therapeutic molecules in multicompartment lipid carriers. For the systems described here, we have employed time-resolved small-angle X-ray scattering (SAXS) and high-resolution freeze-fracture electronic microscopy (FF-EM) to study the morphology and the dynamic topological transitions of these nanostructured multicomponent amphiphilic assemblies. Quasi-elastic light scattering and circular dichroism spectroscopy can provide additional information at the nanoscale about the behavior of lipid/protein self-assemblies under conditions that approximate physiological hydration. We wanted to generalize these findings to control the stability and the hydration of the water nanochannels in liquid-crystalline lipid nanovehicles and confine therapeutic biomolecules within these structures. Therefore we analyzed the influence of amphiphilic and soluble additives (e.g. poly(ethylene glycol)monooleate (MO-PEG), octyl glucoside (OG), proteins) on the nanochannels' size in a diamond (D)-type bicontinuous cubic phase of the lipid glycerol monooleate (MO). At body temperature, we can stabilize long-living swollen states, corresponding to a diamond cubic phase with large water channels. Time-resolved X-ray diffraction (XRD) scans allowed us to detect metastable intermediate and coexisting structures and monitor the temperature-induced phase sequences of mixed systems containing glycerol monooleate, a soluble protein macromolecule, and an interfacial curvature modulating agent. These observed states correspond to the stages of the growth of the nanofluidic channel network. With the application of a thermal stimulus, the system becomes progressively more ordered into a double-diamond cubic lattice formed by a bicontinuous lipid membrane. High-resolution freeze-fracture electronic microscopy indicates that nanodomains are induced by the inclusion of proteins into nanopockets of the supramolecular cubosomic assemblies. These results contribute to the understanding of the structure and dynamics of functionalized self-assembled lipid nanosystems during stimuli-triggered LC phase transformations.

[Plasma temperature of white-eye hexagonal pattern in dielectric barrier discharge].

PubMed

Zhao, Yang; Dong, Li-fang; Fu, Hong-yan

2015-01-01

By using the water-electrode discharge experimental setup, the white-eye hexagonal pattern is firstly observed and investigated in the dielectric barrier discharge with the mixture of argon and air whose content can be varied whenever necessary, and the study shows that the white-eye cell is an interleaving of three different hexagonal sub-structures: the spot, the ring, and the halo. The white-eye hexagonal pattern has the excellent discharge stability and sustainability during the experiment. Pictures recorded by ordinary camera with long exposure time in the same argon content condition show that the spot, the ring, and the halo of the white-eye hexagonal pattern have different brightness, which may prove that their plasma states are different. And, it is worth noting that there are obvious differences not only on the brightness but also on the color of the white-eye cell in conditions of different argon content, which shows that its plasma state also changed with the variation of the argon content. The white-eye hexagonal pattern is observed at a lower applied voltage so that the temperature of the water electrodes almost keeps unchanged during the whole experiment, which is advantageous for the long term stable measurement. The plasma state will not be affected by the temperature of the electrodes during the continuous discharge. Based on the above phenomena, plasma temperatures of the spot, the ring, and the halo in white-eye hexagonal pattern including molecule vibrational temperature and variations of electron density at different argon content are investigated by means of optical emission spectroscopy (OES). The emission spectra of the N2 second positive band(C3Πu-->B3Πg)are measured, and the molecule vibrational temperature of the spot, the ring, and the halo of the white-eye hexagonal pattern are calculated by the emission intensities. Furthermore, emission spectra of Ar I (2P2-->1S5)is collected and the changes of its width with different argon content are used to estimate the variations of electron density of the spot, the ring, and the halo of the white-eye hexagonal pattern. In the same argon content condition, the molecule vibrational temperatures of halo, ring, and spot in the white-eye hexagonal pattern are in descending order, while the electron densities of halo, ring, and spot are in ascending order. With argon content increasing from 70% to 90%, both the molecule vibrational temperature and the electron density of the spot increase, while both of them of the halo decrease. And the molecule vibrational temperature of the ring keeps constant, while its electron density decreases. The experimental results indicate that the plasma state of the spot, the halo and the ring in a white-eye cell of the white-eye hexagonal pattern is different. These results are of great importance to the investigation of the multilayer structure of the patterns in dielectric barrier discharge and applications in industry.

DESIGN CHARACTERISTICS OF THE IDAHO NATIONAL LABORATORY HIGH-[TEMPERATURE GAS-COOLED TEST REACTOR

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sterbentz, James; Bayless, Paul; Strydom, Gerhard

A point design for a graphite-moderated, high-temperature, gas-cooled test reactor (HTG TR) has been developed by Idaho National Laboratory (INL) as part of a United States (U.S.) Department of Energy (DOE) initiative to explore and potentially expand the existing U.S. test reactor capabilities. This paper provides a summary of the design and its main attributes. The 200 MW HTG TR is a thermal-neutron spectrum reactor composed of hexagonal prismatic fuel and graphite reflector blocks. Twelve fuel columns (96 fuel blocks total and 6.34 m active core height) are arranged in two hexagonal rings to form a relatively compact, high-power density,more » annular core sandwiched between inner, outer, top, and bottom graphite reflectors. The HTG-TR is designed to operate at 7 MPa with a coolant inlet/outlet temperature of 325°C/650°C, and utilizes TRISO particle fuel from the DOE AGR Program with 425 ?m uranium oxycarbide (UCO) kernels and an enrichment of 15.5 wt% 235U. The primary mission of the HTG TR is material irradiation and therefore the core has been specifically designed and optimized to provide the highest possible thermal and fast neutron fluxes. The highest thermal neutron flux (3.90E+14 n/cm2s) occurs in the outer reflector, and the maximum fast flux levels (1.17E+14 n/cm2s) are produced in the central reflector column where most of the graphite has been removed. Due to high core temperatures under accident conditions, all the irradiation test facilities have been located in the inner and outer reflectors where fast flux levels decline. The core features a large number of irradiation positions with large test volumes and long test lengths, ideal for thermal neutron irradiation of large test articles. The total available test volume is more than 1100 liters. Up to four test loop facilities can be accommodated with pressure tube boundaries to isolate test articles and test fluids (e.g., liquid metal, liquid salt, light water) from the helium primary coolant system.« less

Molecular Design for Preparation of Hexagonal-Ordered Porous Films Based on Side-chain Type Liquid-Crystalline Star Polymer.

PubMed

Naka, Yumiko; Takayama, Hiromu; Koyama, Teruhisa; Le, Khoa V; Sasaki, Takeo

2018-05-02

Fabrication of regularly porous films by the breath-figure method has attracted much attention. The simple, low-cost technique uses the condensation of water droplets to produce these structures, but the phenomenon itself is complex, requiring control over many interacting parameters that change throughout the process. Developing a unified understanding for the molecular design of polymers to prepare ordered porous films is challenging, but required for further advancements. In this article, the effects of the chemical structure of polymers in the breath-figure technique were systematically explored using side-chain type liquid-crystalline (LC) star polymers. The formation of porous films was affected by the structure of the polymers. Although the entire film surface of poly(11-[4-(4-cyanobiphenyl)oxy]undecyl methacrylate) (P11CB) had a hexagonal ordered porous structure over a certain Mn value, regularly arranged holes did not easily form in poly(methyl methacrylate) (PMMA), even though the main chain of PMMA is similar to that of P11CB. Comparing P11CB and poly(11-[(1,1'-biphenyl)-4-yloxy]undecyl methacrylate) (P11B) (P11CB without cyano groups) showed that the local polar groups in hydrophobic polymers promoted the formation of ordered porous films. No holes formed in poly(4-cyanobiphenyl methacrylate) (P0CB) (P11CB without alkyl spacers) films due to its hydrophilicity. The introduction of alkyl chains in P0CB allowed the preparation of honeycomb-structured films by increasing the internal tension. However, alkyl chains in the side chain alone did not result in a porous structure, as in the case of poly(11-[(1,1'-biphenyl)-4-yloxy]undecyl methacrylate) (P11). Aromatic rings are also required to increase the Tg and improve film formability. In the present study, suitable molecular designs of polymers were found, specifically hydrophobic polymers with local polar groups, to form a regularly porous structure. Development of clear guidelines for the molecular design of polymers is the subject of our current research, which will enable the fabrication of porous films using various functional polymers.

Hexagonal Pixels and Indexing Scheme for Binary Images

NASA Technical Reports Server (NTRS)

Johnson, Gordon G.

2004-01-01

A scheme for resampling binaryimage data from a rectangular grid to a regular hexagonal grid and an associated tree-structured pixel-indexing scheme keyed to the level of resolution have been devised. This scheme could be utilized in conjunction with appropriate image-data-processing algorithms to enable automated retrieval and/or recognition of images. For some purposes, this scheme is superior to a prior scheme that relies on rectangular pixels: one example of such a purpose is recognition of fingerprints, which can be approximated more closely by use of line segments along hexagonal axes than by line segments along rectangular axes. This scheme could also be combined with algorithms for query-image-based retrieval of images via the Internet. A binary image on a rectangular grid is generated by raster scanning or by sampling on a stationary grid of rectangular pixels. In either case, each pixel (each cell in the rectangular grid) is denoted as either bright or dark, depending on whether the light level in the pixel is above or below a prescribed threshold. The binary data on such an image are stored in a matrix form that lends itself readily to searches of line segments aligned with either or both of the perpendicular coordinate axes. The first step in resampling onto a regular hexagonal grid is to make the resolution of the hexagonal grid fine enough to capture all the binaryimage detail from the rectangular grid. In practice, this amounts to choosing a hexagonal-cell width equal to or less than a third of the rectangular- cell width. Once the data have been resampled onto the hexagonal grid, the image can readily be checked for line segments aligned with the hexagonal coordinate axes, which typically lie at angles of 30deg, 90deg, and 150deg with respect to say, the horizontal rectangular coordinate axis. Optionally, one can then rotate the rectangular image by 90deg, then again sample onto the hexagonal grid and check for line segments at angles of 0deg, 60deg, and 120deg to the original horizontal coordinate axis. The net result is that one has checked for line segments at angular intervals of 30deg. For even finer angular resolution, one could, for example, then rotate the rectangular-grid image +/-45deg before sampling to perform checking for line segments at angular intervals of 15deg.

Three-dimensional visualization of coated vesicle formation in fibroblasts

PubMed Central

1980-01-01

Fibroblasts apparently ingest low density lipoproteins (LDL) by a selective mechanism of receptor-mediated endocytosis involving the formation of coated vesicles from the plasma membrane. However, it is not known exactly how coated vesicles collect LDL receptors and pinch off from the plasma membrane. In this report, the quick-freeze, deep- etch, rotary-replication method has been applied to fibroblasts; it displays with unusual clarity the coats that appear under the plasma membrane at the start of receptor-mediated endocytosis. These coats appear to be polygonal networks of 7-nm strands or struts arranged into 30-nm polygons, most of which are hexagons but some of which are 5- and 7-sided rings. The proportion of pentagons in each network increases as the coated area of the plasma membrane puckers up from its planar configuration (where the network is mostly hexagons) to its most sharply curved condition as a pinched-off coated vesicle. Coats around the smallest vesicles (which are icosahedrons of hexagons and pentagons) appear only slightly different from "empty coats" purified from homogenized brain, which are less symmetrical baskets containing more pentagons than hexagons. A search for structural intermediates in this coat transformation allows a test of T. Kanaseki and K. Kadota's (1969. J. Cell Biol. 42:202--220.) original idea that an internal rearrangement in this basketwork from hexagons to pentagons could "power" coated vesicle formation. The most noteworthy variations in the typical hexagonal honeycomb are focal juxtapositions of 5- and 7-sided polygons at points of partial contraction and curvature in the basketwork. These appear to precede complete contraction into individual pentagons completely surrounded by hexagons, which is the pattern that characterizes the final spherical baskets around coated vesicles. PMID:6987244

Studies of Water V. Five Phonons in Protonic Semiconductor Lattice Model of Pure Liquid Water

NASA Astrophysics Data System (ADS)

Jie, Binbin; Sah, Chihtang

2017-07-01

We report physics based confirmation (~1% RMS deviation), by existing experimental data, of proton-prohol (proton-hole) ion product (pH) and mobilities in pure liquid water (0-100{}{{o}}C, 1-atm pressure) anticipated from our melted-ice Hexagonal-Close-Packed (H{}2O){}4 Lattice Model. Five phonons are identified. (1) A propagating protonic phonon (520.9 meV from lone-pair-blue-shifted stretching mode of isolated water molecule) absorbed to generate a proton-prohol pair or detrap a tightly-bound proton. (2) Two (173.4 and 196.6 meV) bending-breathing protonic-proholic or protonic phonons absorbed during de-trapping-limited proton or proton-prohol mobilities. (3) Two propagating oxygenic-wateric Debye-Dispersive phonons (30.3 and 27.5 meV) absorbed during scattering-limited proton or proton-prohol mobilities. Summer School in Theoretical Physics funded by the National Natural Science Foundation of China, on Soft Materials Physics, hosted by the Physics Department of Xiamen University, China, during August 1 to 14, 2016. This was also just presented at the 2017 March Meeting (March 14 to 16) of the American Physical Society in New Orleans, USA.

Hybrid photoluminescent materials containing a benzobisthiazole core for liquid crystal and gel applications.

PubMed

Díaz, E; Elgueta, E; Sanchez, S A; Barberá, J; Vergara, J; Parra, M; Dahrouch, M

2017-03-01

Tetra- and hexacatenar amide compounds containing a linear centrosymmetric benzobisthiazole core were synthesized with good yields. These compounds were characterized and their structures confirmed by elemental analysis, and FT-IR, Maldi mass and NMR spectroscopy. All compounds exhibited excellent thermal stability up to 330 °C. The tetracatenar series containing a double substitution in the meta positions did not show mesomorphic behaviour, whereas the hexacatenar and tetracatenar series having a double substitution in the meta and para positions showed liquid crystal properties with optical textures typical of columnar mesophases corroborated by POM analysis. The mesomorphic properties were dependent on the length, number and position of alkoxy chains attached at the end of the rigid core. XRD studies of the hexacatenar series showed the hexagonal columnar structure of the mesophases. Photoluminescence properties in solution were observed in the visible region, with good quantum yields. In the solid state, these compounds behave as blue emitters and they are able to change colour with acid or base addition. The hexacatenar benzobisthiazole compound with an alkoxy chain of 14 carbons presented properties of a supergelator in chloroform, leading to the formation of a fluorescent organogel material with fluorescence emission in the blue region.

The surface energy of water: functional implications of hexagonal/cuboidal transformations in the surface arrays.

PubMed

Widdas, W F

2006-10-30

Hyde's scientific book The Language of Shape has emphasized the importance of minimum surfaces in the structure of biological membranes. Minimum surfaces can be visualized as the property which brings many droplets of liquids to spherical bubbles, since a sphere has the minimum surface to volume ratio. Thus, a sphere with a surface of 4pir2 and volume of 4/3pir3 has a surface to volume ratio of 3/r, that is, the ratio is dependent upon the reciprocal of the radius. The chemistry of water as dihydrides of the electronegative element oxygen is fundamentally dependent upon its polar properties and particularly the delta positive charges on the hydrogen atoms and the double delta negative charge on the larger oxygen atom, which from its mass (16 Da) is regarded as the centre of the water molecules. The cohesion of water as a liquid or as semi-crystal like structures in the surface depends upon electrostatic forces that are comparable in strength to covalent bonds. This review discusses the functional implications of some unexpected properties which have been evinced by model building and illustrated as a Poster in the 4th World Congress of Cellular and Molecular Biology.

Controllable Synthesis of Formaldehyde Modified Manganese Oxide Based on Gas-Liquid Interfacial Reaction and Its Application of Electrochemical Sensing.

PubMed

Bai, Wushuang; Sheng, Qinglin; Nie, Fei; Zheng, Jianbin

2015-12-30

Controllable synthesis of manganese oxides was performed via a simple one-step synthetic method. Then obtained manganese oxides which exhibit flower-like, cloud-like, hexagon-like, and rod-like morphologies were modified by formaldehyde based on a simple self-made gas-liquid reaction device respectively and the modified manganese oxides with coral-like, scallop-like and rod-like morphology were synthesized accordingly. The obtained materials were characterized and the formation mechanism was also researched. Then the modified manganese oxides were used to fabricate electrochemical sensors to detect H2O2. Comparison of electrochemical properties between three kinds of modified manganese oxides was investigated and the best one has been successfully employed as H2O2 sensor which shows a low detection limit of 0.01 μM, high sensitivity of 162.69 μA mM(-1) cm(-2), and wide linear range of 0.05 μM-12.78 mM. The study provides a new method for controllable synthesis of metal oxides, and electrochemical application of formaldehyde modified manganese oxides will provides a new strategy for electrochemical sensing with high performance, low cost, and simple fabrication.

Polarized Raman spectroscopic study of relaxed high density amorphous ices under pressure.

PubMed

Suzuki, Yoshiharu; Tominaga, Yasunori

2010-10-28

We have made high density amorphous ice (HDA) by the pressure-induced amorphization of hexagonal ice at 77 K and measured the volume change on isobaric heating in a pressure range between 0.1 and 1.5 GPa. The volume of HDA on heating below ∼0.35 GPa increases, while the volume of HDA on heating above ∼0.35 GPa decreases. The polarized OH-stretching Raman spectra of the relaxed HDAs are compared with that of the unannealed HDA. The relaxed HDAs are prepared at 0.2 GPa at 130 K and 1.5 GPa at 160 K. It is found that the relatively strong totally symmetric OH-stretching vibration mode around 3100 cm(-1) exists in the depolarized reduced Raman spectrum χ(VH)(") of the unannealed HDA and that its intensity rapidly decreases by relaxation. The χ(VH)(") profiles of the relaxed HDA are similar to those of liquid water. These results indicate that the HDA reaches a nearly equilibrium state by annealing and the intrinsic state of HDA relates to a liquid state. The pressure-volume curve of the relaxed HDA at 140 K seems to be smooth in the pressure range below 1.5 GPa.

Nitric oxide-sensing actuators for modulating structure in lipid-based liquid crystalline drug delivery systems.

PubMed

Liu, Qingtao; Hu, Jinming; Whittaker, Michael R; Davis, Thomas P; Boyd, Ben J

2017-12-15

Herein we report on the development of a nitric oxide-sensing lipid-based liquid crystalline (LLC) system specifically designed to release encapsulated drugs on exposure to NO through a stimulated phase change. A series of nitric oxide (NO)-sensing lipids compatible with phytantriol and GMO cubic phases were designed and synthesized, and utilized in enabling nitric oxide-sensing LLC systems. The nitric oxide (NO)-sensing lipids react with nitric oxide, resulting in hydrolysis of these lipids and phase transition of the LLC system. Specifically, the N-3-aminopyridinyl myristylamine (NAPyM)+phytantriol mixture formed a lamellar phase in excess aqueous environment. The NAPyM+phytantriol LLC responded to the nitric oxide gas as a chemical stimulus which triggers a phase transition from lamellar phase to inverse cubic and hexagonal phase. The nitric oxide-triggered phase transition of the LLC accelerated the release of encapsulated model drug from the LLC bulk phase, resulting in a 15-fold increase in the diffusion coefficient compared to the starting lamellar structure. The nitric oxide-sensing LLC system has potential application in the development of smart medicines to treat nitric oxide implicated diseases. Copyright © 2017 Elsevier Inc. All rights reserved.

Interlocking egg-crate type grid assembly

DOEpatents

Kast, Steven J.

1987-01-01

Disclosed is an interlocking egg-crate hexagonal grid for supporting a nuclear fuel pin in a hexagonal array. The grid is formed from strips bent at an angle of about 120.degree. at each vertex. Over some faces of each hexagonal cell the strips are coplanar but are arranged, by stacking and interlocking, to avoid any double thickness of metal in that plane. Springs and dimples are formed in the faces of each cell to hold the fuel pin substantially centered.

Interlocking egg-crate type grid assembly

DOEpatents

Kast, S.J.

1985-03-15

Disclosed is an interlocking egg-crate hexagonal grid for supporting a nuclear fuel pin in a hexagonal array. The grid is formed from strips bent at an angle of about 120/sup 0/ at each vertex. Over some faces of each hexagonal cell the strips are coplanar but are arranged, by stacking interlocking, to avoid any double thickness of metal in that plane. Springs and dimples are formed in the faces of each cell to hold the fuel pin substantially centered.

Manifestations of Kitaev physics in thermodynamic properties of hexagonal iridates and α-RuCl3

NASA Astrophysics Data System (ADS)

Tsirlin, Alexander

Kitaev model is hard to achieve in real materials. Best candidates available so far are hexagonal iridates M2IrO3 (M = Li and Na) and the recently discovered α-RuCl3 featuring hexagonal layers coupled by weak van der Waals bonding. I will review recent progress in crystal growth of these materials and compare their thermodynamic properties. Both hexagonal iridates and α-RuCl3 feature highly anisotropic Curie-Weiss temperatures that not only differ in magnitude but also change sign depending on the direction of the applied magnetic field. Néel temperatures are largely suppressed compared to the energy scale of the Curie-Weiss temperatures. These experimental observations will be linked to features of the electronic structure and to structural peculiarities associated with deviations from the ideal hexagonal symmetry. I will also discuss how the different nature of ligand atoms affects electronic structure and magnetic superexchange. This work has been done in collaboration with M. Majumder, M. Schmidt, M. Baenitz, F. Freund, and P. Gegenwart.

Hexagonal Hollow Tube Based Energy Absorbing Crash Buffers for Roadside Fixed Objects

NASA Astrophysics Data System (ADS)

Uddin, M. S.; Amirah Shafie, Nurul; Zivkovic, Grad

2017-03-01

The purpose of this study was to investigate the deformation of the energy absorbing hexagonal hollow tubes in a lateral compression. The aim is to design cost effective and high energy-absorbing buffer systems, which are capable of controlling out-of-control vehicles in high-speed zones. A nonlinear quasi-static finite element analysis was applied to determine the deformation and energy absorption capacity. The main parameters in the design were diameter and wall thickness of the tubes. Experimental test simulating the lateral compressive loading on a single tube was performed. Results show that as the diameter and the thickness increase, the deformation strength increases. Hexagonal tube with diameter of 219 mm and thickness of 4 mm is shown to have the highest energy absorption capability. Compared to existing cylindrical and octagonal shapes, the hexagonal tubes show the highest energy absorption capacity. Hexagonal tubes therefore can be regarded as a potential candidate for buffer designs in high speed zones. In addition, they would be compact, cost effective and facilitate ease of installation.

Preparation of novel layer-stack hexagonal CdO micro-rods by a pre-oxidation and subsequent evaporation process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peng, Kun, E-mail: kpeng@hnu.edu.cn; Hunan Province Key Laboratory for Spray Deposition Technology and Application, Hunan University, Changsha 410082; Jiang, Pan

2014-12-15

Graphical abstract: Layer-stack hexagonal cadmium oxide (CdO) micro-rods were prepared. - Highlights: • Novel hexagonal layer-stack structure CdO micro-rods were synthesized by a thermal evaporation method. • The pre-oxidation, vapor pressure and substrate nature play a key role on the formation of CdO rods. • The formation mechanism of CdO micro-rods was explained. - Abstract: Novel layer-stack hexagonal cadmium oxide (CdO) micro-rods were prepared by pre-oxidizing Cd granules and subsequent thermal oxidation under normal atmospheric pressure. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were performed to characterize the phase structure and microstructure. The pre-oxidation process, vapor pressure and substratemore » nature were the key factors for the formation of CdO micro-rods. The diameter of micro-rod and surface rough increased with increasing of thermal evaporation temperature, the length of micro-rod increased with the increasing of evaporation time. The formation of hexagonal layer-stack structure was explained by a vapor–solid mechanism.« less

Epitaxial hexagonal materials on IBAD-textured substrates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matias, Vladimir; Yung, Christopher

2017-08-15

A multilayer structure including a hexagonal epitaxial layer, such as GaN or other group III-nitride (III-N) semiconductors, a <111> oriented textured layer, and a non-single crystal substrate, and methods for making the same. The textured layer has a crystalline alignment preferably formed by the ion-beam assisted deposition (IBAD) texturing process and can be biaxially aligned. The in-plane crystalline texture of the textured layer is sufficiently low to allow growth of high quality hexagonal material, but can still be significantly greater than the required in-plane crystalline texture of the hexagonal material. The IBAD process enables low-cost, large-area, flexible metal foil substratesmore » to be used as potential alternatives to single-crystal sapphire and silicon for manufacture of electronic devices, enabling scaled-up roll-to-roll, sheet-to-sheet, or similar fabrication processes to be used. The user is able to choose a substrate for its mechanical and thermal properties, such as how well its coefficient of thermal expansion matches that of the hexagonal epitaxial layer, while choosing a textured layer that more closely lattice matches that layer.« less

Loss of preload in screwed implant joints as a function of time and tightening/untightening sequences.

PubMed

Bernardes, Sérgio Rocha; da Gloria Chiarello de Mattos, Maria; Hobkirk, John; Ribeiro, Ricardo Faria

2014-01-01

The purpose of this study was to determine whether abutment screw tightening and untightening influenced loss of preload in three different implant/abutment interfaces, or on the implant body. Five custom-fabricated machined titanium implants were used, each with its respective abutment, with different connection types, retention screws, and torque values (external hexagon with titanium screw/32 Ncm, external hexagon with coated screw/32 Ncm, internal hexagon/20 Ncm and internal conical/20 and 32 Ncm). Each implant tested had two strain gauges attached and was submitted to five tightening/untightening sequences. External hexagons resulted in the lowest preload values generated in the implant cervical third (mean of 27.75 N), while the internal hexagon had the highest values (mean of 219.61 N). There was no immediate significant loss of preload after screw tightening. Tightening/untightening sequences, regardless of the implant/abutment interface design or type of screw used in the study, did not result in any significant loss of initial preload. Conical implant connections demonstrated greater structural reinforcement within the internal connections.

First-principles study of the structural properties of Ge

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chang, K.J.; Cohen, M.L.

1986-12-15

With the use of an ab initio pseudopotential method, the structural properties of Ge are investigated at normal and high pressures. The pressure-induced structural phase transitions from cubic diamond to ..beta..-Sn, to simple hexagonal (sh), and to double hexagonal close packed (dhcp) are examined. With the possible exception of the dhcp structure, the calculated transition pressures, transition volumes, and axial ratios are in good agreement with experimental results. We find that sh Ge has characteristics similar to those of sh Si; the bonds between hexagonal layers are stronger than intralayer bonds and the transverse phonon modes become soft near themore » transitions from the sh to ..beta..-Sn and the sh to hcp structures. At normal pressures, we compare the crystal energies for the cubic diamond, hexagonal 2H, and hexagonal 4H structures. Because of the similar sp/sup 3/ bonds in these structures, the structural energy differences are less than about 14 meV, and the 2H and 4H phases are metastable with respect to the cubic diamond structure. The equation of state is also presented and compared with experiment.« less

Tropomodulin1 is required for membrane skeleton organization and hexagonal geometry of fiber cells in the mouse lens

PubMed Central

Nowak, Roberta B.; Fischer, Robert S.; Zoltoski, Rebecca K.; Kuszak, Jerome R.

2009-01-01

Hexagonal packing geometry is a hallmark of close-packed epithelial cells in metazoans. Here, we used fiber cells of the vertebrate eye lens as a model system to determine how the membrane skeleton controls hexagonal packing of post-mitotic cells. The membrane skeleton consists of spectrin tetramers linked to actin filaments (F-actin), which are capped by tropomodulin1 (Tmod1) and stabilized by tropomyosin (TM). In mouse lenses lacking Tmod1, initial fiber cell morphogenesis is normal, but fiber cell hexagonal shapes and packing geometry are not maintained as fiber cells mature. Absence of Tmod1 leads to decreased γTM levels, loss of F-actin from membranes, and disrupted distribution of β2-spectrin along fiber cell membranes. Regular interlocking membrane protrusions on fiber cells are replaced by irregularly spaced and misshapen protrusions. We conclude that Tmod1 and γTM regulation of F-actin stability on fiber cell membranes is critical for the long-range connectivity of the spectrin–actin network, which functions to maintain regular fiber cell hexagonal morphology and packing geometry. PMID:19752024

An orthogonal oriented quadrature hexagonal image pyramid

NASA Technical Reports Server (NTRS)

Watson, Andrew B.; Ahumada, Albert J., Jr.

1987-01-01

An image pyramid has been developed with basis functions that are orthogonal, self-similar, and localized in space, spatial frequency, orientation, and phase. The pyramid operates on a hexagonal sample lattice. The set of seven basis functions consist of three even high-pass kernels, three odd high-pass kernels, and one low-pass kernel. The three even kernels are identified when rotated by 60 or 120 deg, and likewise for the odd. The seven basis functions occupy a point and a hexagon of six nearest neighbors on a hexagonal sample lattice. At the lowest level of the pyramid, the input lattice is the image sample lattice. At each higher level, the input lattice is provided by the low-pass coefficients computed at the previous level. At each level, the output is subsampled in such a way as to yield a new hexagonal lattice with a spacing sq rt 7 larger than the previous level, so that the number of coefficients is reduced by a factor of 7 at each level. The relationship between this image code and the processing architecture of the primate visual cortex is discussed.

Method of manufacture of atomically thin boron nitride

DOEpatents

Zettl, Alexander K

2013-08-06

The present invention provides a method of fabricating at least one single layer hexagonal boron nitride (h-BN). In an exemplary embodiment, the method includes (1) suspending at least one multilayer boron nitride across a gap of a support structure and (2) performing a reactive ion etch upon the multilayer boron nitride to produce the single layer hexagonal boron nitride suspended across the gap of the support structure. The present invention also provides a method of fabricating single layer hexagonal boron nitride. In an exemplary embodiment, the method includes (1) providing multilayer boron nitride suspended across a gap of a support structure and (2) performing a reactive ion etch upon the multilayer boron nitride to produce the single layer hexagonal boron nitride suspended across the gap of the support structure.

Biophysics and protein corona analysis of Janus cyclodextrin-DNA nanocomplexes. Efficient cellular transfection on cancer cells.

PubMed

Martínez-Negro, M; Caracciolo, G; Palchetti, S; Pozzi, D; Capriotti, A L; Cavaliere, C; Laganà, A; Ortiz Mellet, C; Benito, J M; García Fernández, J M; Aicart, E; Junquera, E

2017-07-01

The self-assembling processes underlining the capabilities of facially differentiated ("Janus") polycationic amphiphilic cyclodextrins (paCDs) as non-viral gene nanocarriers have been investigated by a pluridisciplinary approach. Three representative Janus paCDs bearing a common tetradecahexanoyl multitail domain at the secondary face and differing in the topology of the cluster of amino groups at the primary side were selected for this study. All of them compact pEGFP-C3 plasmid DNA and promote transfection in HeLa and MCF-7 cells, both in absence and in presence of human serum. The electrochemical and structural characteristics of the paCD-pDNA complexes (CDplexes) have been studied by using zeta potential, DLS, SAXS, and cryo-TEM. paCDs and pDNA, when assembled in CDplexes, render effective charges that are lower than the nominal ones. The CDplexes show a self-assembling pattern corresponding to multilamellar lyotropic liquid crystal phases, characterized by a lamellar stacking of bilayers of the CD-based vectors with anionic pDNA sandwiched among them. When exposed to human serum, either in the absence or in the presence of pDNA, the surface of the cationic CD-based vector becomes coated by a protein corona (PC) whose composition has been analyzed by nanoLC-MS/MS. Some of the CDplexes herein studied showed moderate-to-high transfection levels in HeLa and MCF-7 cancer cells combined with moderate-to-high cell viabilities, as determined by FACS and MTT reduction assays. The ensemble of data provides a detail picture of the paCD-pDNA-PC association processes and a rational base to exploit the protein corona for targeted gene delivery on future in vivo applications. Copyright © 2017 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Shuang; Tovkach, Oleh; Golovaty, Dmitry

Flagellated bacteria such as Escherichia coli and Bacillus subtilis exhibit effective mechanisms for swimming in fluids and exploring the surrounding environment. In isotropic fluids such as water, the bacteria change swimming direction through the run-and-tumble process. Lyotropic chromonic liquid crystals (LCLCs) have been introduced recently as an anisotropic environment in which the direction of preferred orientation, the director, guides the bacterial trajectories. In this work, we describe the behavior of bacteria B. subtilis in a homeotropic LCLC geometry, in which the director is perpendicular to the bounding plates of a shallow cell. We demonstrate that the bacteria are capable ofmore » overcoming the stabilizing elastic forces of the LCLC and swim perpendicularly to the imposed director (and parallel to the bounding plates). The effect is explained by a finite surface anchoring of the director at the bacterial body; the role of surface anchoring is analyzed by numerical simulations of a rod realigning in an otherwise uniform director field. Shear flows produced by a swimming bacterium cause director distortions around its body, as evidenced both by experiments and numerical simulations. These distortions contribute to a repulsive force that keeps the swimming bacterium at a distance of a few micrometers away from the bounding plates. The homeotropic alignment of the director imposes two different scenarios of bacterial tumbling: one with an 180° reversal of the horizontal velocity and the other with the realignment of the bacterium by two consecutive 90° turns. Finally, in the second case, the angle between the bacterial body and the imposed director changes from 90° to 0° and then back to 90°; the new direction of swimming does not correlate with the previous swimming direction.« less

Solution Conformations of Graphene Oxide Sheets, and Two-Dimensional Nanofluidics

NASA Astrophysics Data System (ADS)

Koltonow, Andrew R.

This work reports studies on the physical properties of collections of nanosheets. First, the configurations of graphene oxide sheets in solution are studied. Polarized optical microscopy reveals quickly and decisively that sheets remain flat and form lyotropic liquid crystals over a wide range of solvent conditions. When solvent conditions are inhospitable enough, sheets agglomerate into stacks rather crumpling upon themselves. Theory and simulation suggest that the crumpled state, which can be formed by compressing sheets, is metastable. This work might correct a persistent misunderstanding about the solution physics of graphene oxide. The other major area of study concerns the hydration layers in between lamellar stacks of exfoliated, restacked nanosheets. These layers comprise massive arrays of parallel two-dimensional nanofluidic channels, which exhibit enhanced unipolar ionic conductivity with counterions as the majority charge carriers. Based on the previously discovered graphene oxide nanofluidic platform, exfoliated vermiculite nanofluidic channels are constructed, which shuttle protons through the hydration channels by a Grotthuss mechanism, and which show superior thermal stability to graphene oxide. The 2D nanofluidics platform is also used to demonstrate "kirigami nanofluidics", where ion transport can be manipulated by cutting the film into specific shapes. This can give rise to ionic current rectification. The rectification effect is attributed to the size and shape mismatch of the concentration polarization zones developed at the inlets and outlets of the nanofluidic channels. The kirigami nanofluidic platform can be used to fabricate ionic diodes and other simple devices. This material platform is expected to be a useful tool for nanofluidics researchers, because it offers a way to carry out nanofluidic experiments quickly with minimal equipment and little expense.

Nanostructured self-assembly materials from neat and aqueous solutions of C18 lipid pro-drug analogues of Capecitabine—a chemotherapy agent. Focus on nanoparticulate cubosomes™ of the oleyl analogue

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gong, Xiaojuan; Moghaddam, Minoo J.; Sagnella, Sharon M.

2014-09-24

A series of prodrug analogues based on the established chemotherapy agent, 5-fluorouracil, have been prepared and characterized. C18 alkyl and alkenyl chains with increasing degree of unsaturation were attached to the N 4 position of the 5-fluorocytosine (5-FC) base via a carbamate bond. Physicochemical characterization of the prodrug analogues was carried out using a combination of differential scanning calorimetry, cross-polarized optical microscopy, X-ray diffraction and small-angle X-ray scattering. The presence of a monounsaturated oleyl chain was found to promote lyotropic liquid crystalline phase formation in excess water with a fluid lamellar phase observed at room temperature and one or moremore » bicontinuous cubic phases at 37 °C. The bulk phase was successfully dispersed into liposomes or cubosomes at room and physiological temperature respectively. In vitro toxicity of the nanoparticulate 5-FCOle dispersions was evaluated against several normal and cancer cell types over a 48 h period and exhibited an IC 50 of -100 μM against all cell types. The in vivo efficacy of 5-FCOle cubosomes was assessed against the highly aggressive mouse 4T1 breast cancer model and compared to Capecitabine (a water-soluble commercially available 5-FU prodrug) delivered at the same dosages. After 21 days of treatment, the 0.5 mmol 5-FCOle treatment group exhibited a significantly smaller average tumour volume than all other treatment groups including Capecitabine at similar dosage. These results exemplify the potential of self-assembled amphiphile prodrugs for delivery of bioactives in vivo.« less

Structural and electronic stability of a volleyball-shaped B80 fullerene

NASA Astrophysics Data System (ADS)

Wang, Xiao-Qian

2010-10-01

We have studied the structural and electronic characteristics of a volleyball-shaped B80 cage using first-principles density-functional calculations. In contrast to the popularly ratified “magic” B80 buckyball with 20 hexagonal pyramids and 12 hollow pentagons, the volleyball-shaped B80 constitutes 12 pentagonal pyramids, 8 hexagonal pyramids, and 12 hollow hexagons. The B80 volleyball is markedly more stable than the previously assumed magic B80 buckyball, which is attributed to the improved aromaticity associated with the distinct configuration.

Evidence for graphite-like hexagonal AlN nanosheets epitaxially grown on single crystal Ag(111)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsipas, P.; Kassavetis, S.; Tsoutsou, D.

Ultrathin (sub-monolayer to 12 monolayers) AlN nanosheets are grown epitaxially by plasma assisted molecular beam epitaxy on Ag(111) single crystals. Electron diffraction and scanning tunneling microscopy provide evidence that AlN on Ag adopts a graphite-like hexagonal structure with a larger lattice constant compared to bulk-like wurtzite AlN. This claim is further supported by ultraviolet photoelectron spectroscopy indicating a reduced energy bandgap as expected for hexagonal AlN.

Room-temperature synthesis and photoluminescence of hexagonal CePO4 nanorods

NASA Astrophysics Data System (ADS)

Zhu, J.; Zhang, K.; Zhao, H. Y.

2018-01-01

Hexagonal CePO4 nanorods were synthesized via a simple chemical precipitation route at room-temperature without the presence of surfactants and then characterized by powder X-ray diffraction (XRD), energy-dispersive X-ray (EDX) spectrometry, scanning electron microscopy (SEM), transmission electron microscopy (TEM), ultraviolet-visible (UV-vis) absorption and photoluminescence (PL) spectroscopy. Hexagonal CePO4 nanorods exhibit strong ultraviolet absorption and ultraviolet luminescence, which correspond to the electronic transitions between 4f and 5d state of Ce3+ ions.

Hexagonally packed DNA within bacteriophage T7 stabilized by curvature stress.

PubMed Central

Odijk, T

1998-01-01

A continuum computation is proposed for the bending stress stabilizing DNA that is hexagonally packed within bacteriophage T7. Because the inner radius of the DNA spool is rather small, the stress of the curved DNA genome is strong enough to balance its electrostatic self-repulsion so as to form a stable hexagonal phase. The theory is in accord with the microscopically determined structure of bacteriophage T7 filled with DNA within the experimental margin of error. PMID:9726924

Epitaxial Growth of Cubic Crystalline Semiconductor Alloys on Basal Plane of Trigonal or Hexagonal Crystal

NASA Technical Reports Server (NTRS)

Park, Yeonjoon (Inventor); Choi, Sang H. (Inventor); King, Glen C. (Inventor)

2011-01-01

Hetero-epitaxial semiconductor materials comprising cubic crystalline semiconductor alloys grown on the basal plane of trigonal and hexagonal substrates, in which misfit dislocations are reduced by approximate lattice matching of the cubic crystal structure to underlying trigonal or hexagonal substrate structure, enabling the development of alloyed semiconductor layers of greater thickness, resulting in a new class of semiconductor materials and corresponding devices, including improved hetero-bipolar and high-electron mobility transistors, and high-mobility thermoelectric devices.

Characterization of the secondary flow in hexagonal ducts

NASA Astrophysics Data System (ADS)

Marin, O.; Vinuesa, R.; Obabko, A. V.; Schlatter, P.

2016-12-01

In this work we report the results of DNSs and LESs of the turbulent flow through hexagonal ducts at friction Reynolds numbers based on centerplane wall shear and duct half-height Reτ,c ≃ 180, 360, and 550. The evolution of the Fanning friction factor f with Re is in very good agreement with experimental measurements. A significant disagreement between the DNS and previous RANS simulations was found in the prediction of the in-plane velocity, and is explained through the inability of the RANS model to properly reproduce the secondary flow present in the hexagon. The kinetic energy of the secondary flow integrated over the cross-sectional area yz decreases with Re in the hexagon, whereas it remains constant with Re in square ducts at comparable Reynolds numbers. Close connection between the values of Reynolds stress u w ¯ on the horizontal wall close to the corner and the interaction of bursting events between the horizontal and inclined walls is found. This interaction leads to the formation of the secondary flow, and is less frequent in the hexagon as Re increases due to the 120∘ aperture of its vertex, whereas in the square duct the 90∘ corner leads to the same level of interaction with increasing Re. Analysis of turbulence statistics at the centerplane and the azimuthal variance of the mean flow and the fluctuations shows a close connection between hexagonal ducts and pipe flows, since the hexagon exhibits near-axisymmetric conditions up to a distance of around 0.15DH measured from its center. Spanwise distributions of wall-shear stress show that in square ducts the 90∘ corner sets the location of a high-speed streak at a distance zv+≃50 from it, whereas in hexagons the 120∘ aperture leads to a shorter distance of zv+≃38 . At these locations the root mean square of the wall-shear stresses exhibits an inflection point, which further shows the connections between the near-wall structures and the large-scale motions in the outer flow.

Characterization of the secondary flow in hexagonal ducts

DOE PAGES

Marin, O.; Vinuesa, R.; Obabko, A. V.; ...

2016-12-06

In this work we report the results of DNSs and LESs of the turbulent flow through hexagonal ducts at friction Reynolds numbers based on centerplane wall shear and duct half-height Re τ,c ≃ 180, 360, and 550. The evolution of the Fanning friction factor f with Re is in very good agreement with experimental measurements. A significant disagreement between the DNS and previous RANS simulations was found in the prediction of the in-plane velocity, and is explained through the inability of the RANS model to properly reproduce the secondary flow present in the hexagon. The kinetic energy of the secondarymore » flow integrated over the cross-sectional area < K > yz decreases with Re in the hexagon, whereas it remains constant with Re in square ducts at comparable Reynolds numbers. Close connection between the values of Reynolds stress uw¯ on the horizontal wall close to the corner and the interaction of bursting events between the horizontal and inclined walls is found. This interaction leads to the formation of the secondary flow, and is less frequent in the hexagon as Re increases due to the 120° aperture of its vertex, whereas in the square duct the 90° corner leads to the same level of interaction with increasing Re. Analysis of turbulence statistics at the centerplane and the azimuthal variance of the mean flow and the fluctuations shows a close connection between hexagonal ducts and pipe flows, since the hexagon exhibits near-axisymmetric conditions up to a distance of around 0.15 DH measured from its center. Spanwise distributions of wall-shear stress show that in square ducts the 90° corner sets the location of a high-speed streak at a distance z + v≃50 from it, whereas in hexagons the 120° aperture leads to a shorter distance of z + v≃38. Finally, at these locations the root mean square of the wall-shear stresses exhibits an inflection point, which further shows the connections between the near-wall structures and the large-scale motions in the outer flow.« less

Ionic depletion at the crystalline Gibbs layer of PEG-capped gold nanoparticle brushes at aqueous surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Wenjie; Zhang, Honghu; Mallapragada, Surya

In situ surface-sensitive x-ray diffraction and grazing incidence x-ray fluorescence spectroscopy (GIXFS) methods are combined to determine the ionic distributions across the liquid/vapor interfaces of thiolated-polyethylene-glycol–capped gold nanoparticle (PEG-AuNP) solutions. Induced by the addition of salts (i.e., Cs 2SO 4) to PEG-AuNPs solutions, two-dimensional hexagonal lattices of PEG-AuNPs form spontaneously at the aqueous surfaces, as is demonstrated by x-ray reflectivity and grazing incidence small-angle x-ray scattering. In conclusion, by taking advantage of element specificity with the GIXFS method, we find that the cation Cs + concentration at the crystalline film is significantly reduced in parts of the PEG-AuNP film comparedmore » with that in the bulk.« less

Enhancing the mechanical properties of BN nanosheet-polymer composites by uniaxial drawing

NASA Astrophysics Data System (ADS)

Jan, Rahim; May, Peter; Bell, Alan P.; Habib, Amir; Khan, Umar; Coleman, Jonathan N.

2014-04-01

We have used liquid exfoliation of hexagonal Boron-Nitride (BN) to prepare composites of BN nanosheets of three different sizes in polyvinylchloride matrices. These composites show low levels of reinforcement, consistent with poor alignment of the nanosheets as-described by a modified version of Halpin-Tsai theory. However, drawing of the composites to 300% strain results in a considerable increase in mechanical properties with the maximum composite modulus and strength both ~×3 higher than that of the pristine polymer. In addition, the rate of increase of modulus with BN volume fraction was up to 3-fold larger than for the unstrained composites. This is higher than can be explained by drawing-induced alignment using Halpin-Tsai theory. However, the data was consistent with a combination of alignment and strain-induced de-aggregation of BN multilayers.

Enhancing the mechanical properties of BN nanosheet-polymer composites by uniaxial drawing.

PubMed

Jan, Rahim; May, Peter; Bell, Alan P; Habib, Amir; Khan, Umar; Coleman, Jonathan N

2014-05-07

We have used liquid exfoliation of hexagonal Boron-Nitride (BN) to prepare composites of BN nanosheets of three different sizes in polyvinylchloride matrices. These composites show low levels of reinforcement, consistent with poor alignment of the nanosheets as-described by a modified version of Halpin-Tsai theory. However, drawing of the composites to 300% strain results in a considerable increase in mechanical properties with the maximum composite modulus and strength both ∼×3 higher than that of the pristine polymer. In addition, the rate of increase of modulus with BN volume fraction was up to 3-fold larger than for the unstrained composites. This is higher than can be explained by drawing-induced alignment using Halpin-Tsai theory. However, the data was consistent with a combination of alignment and strain-induced de-aggregation of BN multilayers.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Travesset, Alex

An extensive characterization of the low temperature phase diagram of particles interacting with power law or Lennard-Jones potentials is provided from Lattice Dynamical Theory. For power law systems, only two lattice structures are stable for certain values of the exponent (or softness) (A15, body centered cube (bcc)) and two more (face centered cubic (fcc), hexagonal close packed (hcp)) are always stable. Among them, only the fcc and bcc are equilibrium states. For Lennard-Jones systems, the equilibrium states are either hcp or fcc, with a coexistence curve in pressure and temperature that shows reentrant behavior. The hcp solid never coexists withmore » the liquid. In all cases analyzed, for both power law and Lennard-Jones potentials, the fcc crystal has higher entropy than the hcp. The role of anharmonic terms is thoroughly analyzed and a general thermodynamic integration to account for them is proposed.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Checco, A.; Hofmann, T.; DiMasi, E.

The details of air nanobubble trapping at the interface between water and a nanostructured hydrophobic silicon surface are investigated using X-ray scattering and contact angle measurements. Large-area silicon surfaces containing hexagonally packed, 20 nm wide hydrophobic cavities provide ideal model surfaces for studying the morphology of air nanobubbles trapped inside cavities and its dependence on the cavity depth. Transmission small-angle X-ray scattering measurements show stable trapping of air inside the cavities with a partial water penetration of 5-10 nm into the pores, independent of their large depth variation. This behavior is explained by consideration of capillary effects and the cavitymore » geometry. For parabolic cavities, the liquid can reach a thermodynamically stable configuration - a nearly planar nanobubble meniscus - by partially penetrating into the pores. This microscopic information correlates very well with the macroscopic surface wetting behavior.« less

Accurate Monte Carlo simulations on FCC and HCP Lennard-Jones solids at very low temperatures and high reduced densities up to 1.30

NASA Astrophysics Data System (ADS)

Adidharma, Hertanto; Tan, Sugata P.

2016-07-01

Canonical Monte Carlo simulations on face-centered cubic (FCC) and hexagonal closed packed (HCP) Lennard-Jones (LJ) solids are conducted at very low temperatures (0.10 ≤ T∗ ≤ 1.20) and high densities (0.96 ≤ ρ∗ ≤ 1.30). A simple and robust method is introduced to determine whether or not the cutoff distance used in the simulation is large enough to provide accurate thermodynamic properties, which enables us to distinguish the properties of FCC from that of HCP LJ solids with confidence, despite their close similarities. Free-energy expressions derived from the simulation results are also proposed, not only to describe the properties of those individual structures but also the FCC-liquid, FCC-vapor, and FCC-HCP solid phase equilibria.

Ionic depletion at the crystalline Gibbs layer of PEG-capped gold nanoparticle brushes at aqueous surfaces

DOE PAGES

Wang, Wenjie; Zhang, Honghu; Mallapragada, Surya; ...

2017-12-14

In situ surface-sensitive x-ray diffraction and grazing incidence x-ray fluorescence spectroscopy (GIXFS) methods are combined to determine the ionic distributions across the liquid/vapor interfaces of thiolated-polyethylene-glycol–capped gold nanoparticle (PEG-AuNP) solutions. Induced by the addition of salts (i.e., Cs 2SO 4) to PEG-AuNPs solutions, two-dimensional hexagonal lattices of PEG-AuNPs form spontaneously at the aqueous surfaces, as is demonstrated by x-ray reflectivity and grazing incidence small-angle x-ray scattering. In conclusion, by taking advantage of element specificity with the GIXFS method, we find that the cation Cs + concentration at the crystalline film is significantly reduced in parts of the PEG-AuNP film comparedmore » with that in the bulk.« less

Multi-object detection and tracking technology based on hexagonal opto-electronic detector

NASA Astrophysics Data System (ADS)

Song, Yong; Hao, Qun; Li, Xiang

2008-02-01

A novel multi-object detection and tracking technology based on hexagonal opto-electronic detector is proposed, in which (1) a new hexagonal detector, which is composed of 6 linear CCDs, has been firstly developed to achieve the field of view of 360 degree, (2) to achieve the detection and tracking of multi-object with high speed, the object recognition criterions of Object Signal Width Criterion (OSWC) and Horizontal Scale Ratio Criterion (HSRC) are proposed. In this paper, Simulated Experiments have been carried out to verify the validity of the proposed technology, which show that the detection and tracking of multi-object can be achieved with high speed by using the proposed hexagonal detector and the criterions of OSWC and HSRC, indicating that the technology offers significant advantages in Photo-electric Detection, Computer Vision, Virtual Reality, Augment Reality, etc.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Engel, Edgar A., E-mail: eae32@cam.ac.uk; Needs, Richard J.; Monserrat, Bartomeu

Surface energies of hexagonal and cubic water ice are calculated using first-principles quantum mechanical methods, including an accurate description of anharmonic nuclear vibrations. We consider two proton-orderings of the hexagonal and cubic ice basal surfaces and three proton-orderings of hexagonal ice prism surfaces, finding that vibrations reduce the surface energies by more than 10%. We compare our vibrational densities of states to recent sum frequency generation absorption measurements and identify surface proton-orderings of experimental ice samples and the origins of characteristic absorption peaks. We also calculate zero point quantum vibrational corrections to the surface electronic band gaps, which range frommore » −1.2 eV for the cubic ice basal surface up to −1.4 eV for the hexagonal ice prism surface. The vibrational corrections to the surface band gaps are up to 12% smaller than for bulk ice.« less

7-Hexagon Multifocal Electroretinography for an Objective Functional Assessment of the Macula in 14 Seconds.

PubMed

Schönbach, Etienne M; Chaikitmongkol, Voraporn; Annam, Rachel; McDonnell, Emma C; Wolfson, Yulia; Fletcher, Emily; Scholl, Hendrik P N

2017-01-01

We present the multifocal electroretinogram (mfERG) with a 7-hexagon array as an objective test of macular function that can be recorded in 14 s. We provide normal values and investigate its reproducibility and validity. Healthy participants underwent mfERG testing according to International Society for Clinical Electrophysiology of Vision (ISCEV) standards using the Espion Profile/D310 multifocal ERG system (Diagnosys, LLC, Lowell, MA, USA). One standard recording of a 61-hexagon array and 2 repeated recordings of a custom 7-hexagon array were obtained. A total of 13 subjects (mean age 46.9 years) were included. The median response densities were 12.5 nV/deg2 in the center and 5.2 nV/deg2 in the periphery. Intereye correlations were strong in both the center (ρCenter = 0.821; p < 0.0001) and the periphery (ρPeriphery = 0.862; p < 0.0001). Intraeye correlations were even stronger: ρCenter = 0.904 with p < 0.0001 and ρPeriphery = 0.955 with p < 0.0001. Bland-Altman plots demonstrated an acceptable retest mean difference in both the center and periphery, and narrow limits of agreement. We found strong correlations of the center (ρCenter = 0.826; p < 0.0001) and periphery (ρPeriphery = 0.848; p < 0.0001), with recordings obtained by the 61-hexagon method. The 7-hexagon mfERG provides reproducible results in agreement with results obtained according to the ISCEV standard. © 2017 S. Karger AG, Basel.

Control over self-assembly of diblock copolymers on hexagonal and square templates for high area density circuit boards.

PubMed

Feng, Jie; Cavicchi, Kevin A; Heinz, Hendrik

2011-12-27

Self-assembled diblock copolymer melts on patterned substrates can induce a smaller characteristic domain spacing compared to predefined lithographic patterns and enable the manufacture of circuit boards with a high area density of computing and storage units. Monte Carlo simulation using coarse-grain models of polystyrene-b-polydimethylsiloxane shows that the generation of high-density hexagonal and square patterns is controlled by the ratio N(D) of the surface area per post and the surface area per spherical domain of neat block copolymer. N(D) represents the preferred number of block copolymer domains per post. Selected integer numbers support the formation of ordered structures on hexagonal (1, 3, 4, 7, 9) and square (1, 2, 5, 7) templates. On square templates, only smaller numbers of block copolymer domains per post support the formation of ordered arrays with significant stabilization energies relative to hexagonal morphology. Deviation from suitable integer numbers N(D) increases the likelihood of transitional morphologies between square and hexagonal. Upon increasing the spacing of posts on the substrate, square arrays, nested square arrays, and disordered hexagonal morphologies with multiple coordination numbers were identified, accompanied by a decrease in stabilization energy. Control over the main design parameter N(D) may allow an up to 7-fold increase in density of spherical block copolymer domains per surface area in comparison to the density of square posts and provide access to a wide range of high-density nanostructures to pattern electronic devices.

Investigation on structural, thermal, optical and sensing properties of meta-stable hexagonal MoO(3) nanocrystals of one dimensional structure.

PubMed

Chithambararaj, Angamuthuraj; Bose, Arumugam Chandra

2011-01-01

Hexagonal molybdenum oxide (h-MoO(3)) was synthesized by a solution based chemical precipitation technique. Analysis by X-ray diffraction (XRD) confirmed that the as-synthesized powder had a metastable hexagonal structure. The characteristic vibrational band of Mo-O was identified from Fourier transform infrared spectroscopy (FT-IR). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images clearly depicted the morphology and size of h-MoO(3.) The morphology study showed that the product comprises one-dimensional (1D) hexagonal rods. From the electron energy loss spectroscopy (EELS) measurement, the elemental composition was investigated and confirmed from the characteristic peaks of molybdenum and oxygen. Thermogravimetric (TG) analysis on metastable MoO(3) revealed that the hexagonal phase was stable up to 430 °C and above this temperature complete transformation into a highly stable orthorhombic phase was achieved. The optical band gap energy was estimated from the Kubelka-Munk (K-M) function and was found to be 2.99 eV. Finally, the ethanol vapor-sensing behavior was investigated and the sensing response was found to vary linearly as a function of ethanol concentration in the parts per million (ppm) range.

On the buckling of hexagonal boron nitride nanoribbons via structural mechanics

NASA Astrophysics Data System (ADS)

Giannopoulos, Georgios I.

2018-03-01

Monolayer hexagonal boron nitride nanoribbons have similar crystal structure as graphene nanoribbons, have excellent mechanical, thermal insulating and dielectric properties and additionally present chemical stability. These allotropes of boron nitride can be used in novel applications, in which graphene is not compatible, to achieve remarkable performance. The purpose of the present work is to provide theoretical estimations regarding the buckling response of hexagonal boron nitride monolayer under compressive axial loadings. For this reason, a structural mechanics method is formulated which employs the exact equilibrium atomistic structure of the specific two-dimensional nanomaterial. In order to represent the interatomic interactions appearing between boron and nitrogen atoms, the Dreiding potential model is adopted which is realized by the use of three-dimensional, two-noded, spring-like finite elements of appropriate stiffness matrices. The critical compressive loads that cause the buckling of hexagonal boron nitride nanoribbons are computed with respect to their size and chirality while some indicative buckled shapes of them are illustrated. Important conclusions arise regarding the effect of the size and chirality on the structural stability of the hexagonal boron nitride monolayers. An analytical buckling formula, which provides good fitting of the numerical outcome, is proposed.

Polarization-free integrated gallium-nitride photonics

PubMed Central

Bayram, C.; Liu, R.

2017-01-01

Gallium Nitride (GaN) materials are the backbone of emerging solid state lighting. To date, GaN research has been primarily focused on hexagonal phase devices due to the natural crystallization. This approach limits the output power and efficiency of LEDs, particularly in the green spectrum. However, GaN can also be engineered to be in cubic phase. Cubic GaN has a lower bandgap (~200 meV) than hexagonal GaN that enables green LEDs much easily. Besides, cubic GaN has more isotropic properties (smaller effective masses, higher carrier mobility, higher doping efficiency, and higher optical gain than hexagonal GaN), and cleavage planes. Due to phase instability, however, cubic phase materials and devices have remained mostly unexplored. Here we review a new method of cubic phase GaN generation: Hexagonal-to-cubic phase transition, based on novel nano-patterning. We report a new crystallographic modelling of this hexagonal-to-cubic phase transition and systematically study the effects of nano-patterning on the GaN phase transition via transmission electron microscopy and electron backscatter diffraction experiments. In summary, silicon-integrated cubic phase GaN light emitters offer a unique opportunity for exploration in next generation photonics. PMID:29307953

Synthesis of hexagonal ultrathin tungsten oxide nanowires with diameters below 5 nm for enhanced photocatalytic performance

NASA Astrophysics Data System (ADS)

Lu, Huidan; Zhu, Qin; Zhang, Mengying; Yan, Yi; Liu, Yongping; Li, Ming; Yang, Zhishu; Geng, Peng

2018-04-01

Semiconductor with one dimension (1D) ultrathin nanostructure has been proved to be a promising nanomaterial in photocatalytic field. Great efforts were made on preparation of monoclinic ultrathin tungsten oxide nanowires. However, non-monoclinic phase tungsten oxides with 1D ultrathin structure, especially less than 5 nm width, have not been reported. Herein, we report the synthesis of hexagonal ultrathin tungsten oxide nanowires (U-WOx NW) by modified hydrothermal method. Microstructure characterization showed that U-WOx NW have the diameters of 1-3 nm below 5 nm and are hexagonal phase sub-stoichiometric WOx. U-WOx NW show absorption tail in the visible and near infrared region due to oxygen vacancies. For improving further photocatalytic performance, Ag co-catalyst was grown directly onto U-WOx NW surface by in situ redox reaction. Photocatalytic measurements revealed hexagonal U-WOx NW have better photodegradation activity, compared with commercial WO3(C-WO3) and oxidized U-WOx NW, ascribe to larger surface area, short diffusion length of photo-generated charge carriers and visible absorption of oxygen-vacancy-rich hexagonal ultrathin nanostructures. Moreover, the photocatalytic activity and stability of U-WOx NW using Ag co-catalyst were further improved.

Circles and Hexagons

NASA Image and Video Library

2017-10-09

Saturn's cloud belts generally move around the planet in a circular path, but one feature is slightly different. The planet's wandering, hexagon-shaped polar jet stream breaks the mold -- a reminder that surprises lurk everywhere in the solar system. This atmospheric feature was first observed by the Voyager mission in the early 1980s, and was dubbed "the hexagon." Cassini's visual and infrared mapping spectrometer was first to spy the hexagon during the mission, since it could see the feature's outline while the pole was still immersed in wintry darkness. The hexagon became visible to Cassini's imaging cameras as sunlight returned to the northern hemisphere. This view looks toward the northern hemisphere of Saturn -- in summer when this view was acquired -- from above 65 degrees north latitude. The image was taken with the Cassini spacecraft wide-angle camera on June 28, 2017 using a spectral filter which preferentially admits wavelengths of near-infrared light centered at 752 nanometers. The view was acquired at a distance of approximately 536,000 miles (862,000 kilometers) from Saturn. Image scale is 32 miles (52 kilometers) per pixel. The Cassini spacecraft ended its mission on Sept. 15, 2017. https://photojournal.jpl.nasa.gov/catalog/PIA21348

Cubic ice and large humidity with respect to ice in cold cirrus clouds

NASA Astrophysics Data System (ADS)

Bogdan, A.; Loerting, T.

2009-04-01

Recently several studies have reported about the possible formation of cubic ice in upper-tropospheric cirrus ice clouds and its role in the observed elevated relative humidity with respect to hexagonal ice, RHi, within the clouds. Since cubic ice is metastable with respect to stable hexagonal ice, its vapour pressure is higher. A key issue in determining the ratio of vapour pressures of cubic ice Pc and hexagonal ice Ph is the enthalpy of transformation from cubic to hexagonal ice Hc→h. By dividing the two integrated forms of the Clausius-Clapeyron equation for cubic ice and hexagonal ice, one obtains the relationship (1): ln Pc-- ln P*c-=--(Hc→h--) Ph P*h R 1T-- 1T* (1) from which the importance of Hc→h is evident. In many literature studies the approximation (2) is used: ln Pc-= Hc-→h. Ph RT (2) Using this approximated form one can predict the ratio of vapour pressures by measuring Hc→h. Unfortunately, the measurement of Hc→h is difficult. First, the enthalpy difference is very small, and the transition takes place over a broad temperature range, e.g., between 230 K and 260 K in some of our calorimetry experiments. Second, cubic ice (by contrast to hexagonal ice) can not be produced as a pure crystal. It always contains hexagonal stacking faults, which are evidenced by the (111)-hexagonal Bragg peak in the powder diffractogram. If the number of hexagonal stacking faults in cubic ice is high, then one could even consider this material as hexagonal ice with cubic stacking faults. Using the largest literature value of the change of enthalpy of transformation from cubic to hexagonal ice, Hc→h ? 160 J/mol, Murphy and Koop (2005) calculated that Pc would be ~10% higher than that of hexagonal ice Phat 180 K - 190 K, which agrees with the measurements obtained later by Shilling et al. (2006). Based on this result Shilling et al. concluded that "the formation of cubic ice at T < 202 K may significantly contribute to the persistent in-cloud water supersaturations" in the upper-tropospheric cold cirrus clouds. Using instead the value of Hc→h ? 50 J/mol (Handa et al., 1986; Mayer and Hallbrucker, 1987) the calculation gives that Pc is only ~3% larger than that of Ph. Recently it has been reported that emulsified water droplets freeze to cubic ice when being cooled at a rate of 10 K/min (Murray and Bertram, 2006,). We prepared emulsified droplets using the same emulsification technique and studied them with a differential scanning calorimeter (DSC) between 278 and 180 K using a scanning rate of 10 K/min. During the warming of the samples we observed a very broad, tiny exothermal peak approximately between 230 and 260 K. Kohl et al. (2000) observed exothermal peak at ~230 K during the warming at 30 K/min of several samples of hyperquenched glassy water (HGW) prepared at temperature between 130 and 190 K. They attributed this peak to the cubic-to-hexagonal ice transition and estimated Hc→h to be between ~33 and 75 J/mol. Johari (2005) used the value of Hc→h ? 37 J/mol. Assuming that in our case the broad peak between 230 and 260 K is also due to the cubic-to-hexagonal ice transition we obtained approximately between 10 and 25 J/mol for Hc→h. This low enthalpy of transformation suggests that cubic ice in the atmosphere contains many hexagonal stacking faults. Using these values of Hc→h for cubic ice as produced at atmospheric cooling rates, the above mentioned formula gives that Pc is larger than that of Ph only by ~1%. We, therefore, suggest that the difference in the water vapor pressures between ice Ic and ice Ih is small and does not play a significant role in the elevation of RHi in cold cirrus clouds. Murphy, D. M., and T. Koop (2005), Q. J. R. Meteorol. Soc. 131, 1539-1565. Shilling, J. E. et al. (2006). Geophys. Res. Lett. 33, L17801, doi:1029/2006GL026671. Handa, P. Y., D. D. Klug, and E. Whalley (1986). J. Chem. Phys. 84, 7009-7010. Mayer, E., and A. Hallbrucker (1987), Nature, 325, 601-602. Murray, B. J. and A. K. Bertram (2006), Phys. Chem. Chem. Phys. 8, 186-192. Kohl, I., E. Mayer, and A. Hallbrucker (2000), Phys. Chem. Chem. Phys. 2, 1579-1586. G. P. Johari, (2005), J. Chem. Phys. 122, 194504.

Neutron scattering investigation of a macroscopic single crystal of a lyotropic Lα phase

NASA Astrophysics Data System (ADS)

Goecking, K. D.; Monkenbusch, M.

1998-07-01

Water-rich lamellar samples of the quaternary microemulsion SDS-pentanol-water-dodecane have been prepared in form of 1 mm×10 mm×20 mm macroscopic mono domains. The shape is given by the quartz cuvette containing the sample, the layer planes are parallel to the cuvette walls. Diffraction patterns and "rocking curves" have been obtained by neutron diffraction using a triple-axis spectrometer. Three "pseudo-Bragg peaks" have been observed, their (relative) intensities yield a new experimental access to estimate the product of the elastic constants η-2 propto Bκ resulting in a lower value than obtained from synchrotron investigation using peak shape fitting (Roux D. et al., Micelles, Membranes, Microemulsions and Monolayers (Springer, New York, Berlin) 1994).

Epitaxial growth and photoluminescence of hexagonal CdS 1- xSe x alloy films

NASA Astrophysics Data System (ADS)

Grün, M.; Gerlach, H.; Breitkopf, Th.; Hetterich, M.; Reznitsky, A.; Kalt, H.; Klingshirn, C.

1995-01-01

CdSSe ternary alloy films were grown on GaAs(111) by hot-wall beam epitaxy. The hexagonal crystal phase is obtained. The composition varies from 0 to 40% selenium. Luminescence spectroscopy at low temperatures shows a dominant effect by alloy disorder. Localization of carriers, for example, is still observed at a pulsed optical excitation density of 6 mJ/cm 2. The overall quality of the CdSSe films is sufficient to use them as buffer layers for the growth of hexagonal superlattices.

Copper vapor-assisted growth of hexagonal graphene domains on silica islands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Jun; Que, Yande; Jiang, Lili

2016-07-11

Silica (SiO{sub 2}) islands with a dendritic structure were prepared on polycrystalline copper foil, using silane (SiH{sub 4}) as a precursor, by annealing at high temperature. Assisted by copper vapor from bare sections of the foil, single-layer hexagonal graphene domains were grown directly on the SiO{sub 2} islands by chemical vapor deposition. Scanning electron microscopy, atomic force microscopy, Raman spectra, and X-ray photoelectron spectroscopy confirm that hexagonal graphene domains, each measuring several microns, were synthesized on the silica islands.

Phase stabilisation of hexagonal barium titanate doped with transition metals: A computational study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dawson, J.A., E-mail: mtp09jd@sheffield.ac.uk; Freeman, C.L.; Harding, J.H.

Interatomic potentials recently developed for the modelling of BaTiO{sub 3} have been used to explore the stabilisation of the hexagonal polymorph of BaTiO{sub 3} by doping with transition metals (namely Mn, Co, Fe and Ni) at the Ti-site. Classical simulations have been completed on both the cubic and hexagonal polymorphs to investigate the energetic consequences of transition metal doping on each polymorph. Ti-site charge compensation mechanisms have been used for the multi-valent transition metal ions and cluster binding energies have been considered. Simulations show a significant energetic gain when doping occurs at Ti sites in the face sharing dimers (Ti{submore » 2} sites) of the hexagonal polymorph compared with the doping of the cubic polymorph. This energetic difference between the two polymorphs is true for all transition metals tested and all charge states and in the case of tri- and tetra-valent dopants negative solution energies are found for the hexagonal polymorph suggesting actual polymorph stabilisation occurs with the incorporation of these ions as observed experimentally. Oxidation during incorporation of Ni{sup 2+} and Fe{sup 3+} ions has also been considered. - Graphical abstract: The representation of the strongest binding energy clusters for tri-valent dopants—(a) Ti{sub 2}/O{sub 1} cluster and (b) Ti{sub 2}/O{sub 2} cluster. Highlights: ► Classical simulations show a significant energetic gain when doping occurs at Ti sites in the face sharing dimers (Ti2 sites) of the hexagonal polymorph compared with the doping of the cubic polymorph. ► This energetic difference between the two polymorphs is true for all transition metals tested and all charge states. ► In the case of tri- and tetra- valent dopants negative solution energies are found for the hexagonal polymorph suggesting actual polymorph stabilisation occurs with the incorporation of these ions.« less

Presence and persistence of a highly ordered lipid phase state in the avian stratum corneum.

PubMed

Champagne, Alex M; Pigg, Victoria A; Allen, Heather C; Williams, Joseph B

2018-06-07

To survive high temperatures in a terrestrial environment, animals must effectively balance evaporative heat loss and water conservation. In passerine birds, cutaneous water loss (CWL) is the primary avenue of water loss at thermoneutral temperatures and increases slightly as ambient temperature increases, indicating a change in the permeability of the skin. In the stratum corneum (SC), the outermost layer of the skin, lipids arranged in layers called lamellae serve as the primary barrier to CWL in birds. The permeability of these lamellae depends in large part on the ability of lipid molecules to pack closely together in an ordered orthorhombic phase state. However, as temperature increases, lipids of the SC become more disordered, and may pack in more permeable hexagonal or liquid crystalline phase states. In this study, we used Fourier transform infrared spectroscopy to monitor the phase state of lipids in the SC of house sparrows ( Passer domesticus ) at skin temperatures ranging from 25 to 50°C. As temperature increased, lipids became slightly more disordered, but remained predominantly in the orthorhombic phase, consistent with the small increase in CWL observed in house sparrows as ambient temperature increases. These results differ considerably from studies on mammalian SC, which find a predominantly hexagonal arrangement of lipids at temperatures above 37°C, and the increased order in avian SC may be explained by longer lipid chain length, scarcity of cholesterol and the presence of cerebrosides. Our results lend further insight into the arrangement and packing of individual lipid molecules in avian SC. © 2018. Published by The Company of Biologists Ltd.

The formation of Colloidal 2D/3D MoS2 Nanostructures in Organic Liquid Environment

NASA Astrophysics Data System (ADS)

Durgun, Engin; Sen, H. Sener; Oztas, Tugba; Ortac, Bulend

2015-03-01

2D MoS2 nanosheets (2D MoS2 NS) and fullerene-like MoS2 nanostructures (3D MoS2 NS) with varying sizes are synthesized by nanosecond laser ablation of hexagonal crystalline 2H-MoS2 powder in methanol. Structural, chemical, and optical properties of MoS2 NS are characterized by optical microscopy, SEM, TEM, XRD, Raman and UV/VIS/NIR absorption spectroscopy techniques. Results of structural analysis show that the obtained MoS2 NS mainly present layered morphology from micron to nanometer surface area. Detailed analysis of the product also proves the existence of inorganic polyhedral fullerene-like 3D MoS2 NS generated by pulsed laser ablation in methanol. The possible factors which may lead to formation of both 2D and 3D MoS2 NS in methanol are examined by ab initio calculations and shown that it is correlated with vacancy formation. The hexagonal crystalline structure of MoS2 NS was determined by XRD analysis. The colloidal MoS2 NS solution presents broadband absorption edge tailoring from UV region to NIR region. Investigations of MoS2 NS show that the one step physical process of pulsed laser ablation-bulk MoS2 powder interaction in organic solution opens doors to the formation of ``two scales'' micron- and nanometer-sized layered and fullerene-like morphology MoS2 structures. This work was partially supported by TUBITAK under the Project No. 113T050 and Bilim Akademisi - The Science Academy, Turkey under the BAGEP program.

Order parameters from image analysis: a honeycomb example

NASA Astrophysics Data System (ADS)

Kaatz, Forrest H.; Bultheel, Adhemar; Egami, Takeshi

2008-11-01

Honeybee combs have aroused interest in the ability of honeybees to form regular hexagonal geometric constructs since ancient times. Here we use a real space technique based on the pair distribution function (PDF) and radial distribution function (RDF), and a reciprocal space method utilizing the Debye-Waller Factor (DWF) to quantify the order for a range of honeycombs made by Apis mellifera ligustica. The PDFs and RDFs are fit with a series of Gaussian curves. We characterize the order in the honeycomb using a real space order parameter, OP 3 , to describe the order in the combs and a two-dimensional Fourier transform from which a Debye-Waller order parameter, u, is derived. Both OP 3 and u take values from [0, 1] where the value one represents perfect order. The analyzed combs have values of OP 3 from 0.33 to 0.60 and values of u from 0.59 to 0.69. RDF fits of honeycomb histograms show that naturally made comb can be crystalline in a 2D ordered structural sense, yet is more ‘liquid-like’ than cells made on ‘foundation’ wax. We show that with the assistance of man-made foundation wax, honeybees can manufacture highly ordered arrays of hexagonal cells. This is the first description of honeycomb utilizing the Debye-Waller Factor, and provides a complete analysis of the order in comb from a real-space order parameter and a reciprocal space order parameter. It is noted that the techniques used are general in nature and could be applied to any digital photograph of an ordered array.

Instrument adjustment knob locks to prevent accidental maladjustment

NASA Technical Reports Server (NTRS)

1964-01-01

A device, incorporating a collar with a hexagonal opening which fits snugly over a hexagonal nut used to engage instrument panel components, keeps the adjustment knob locked. A quick release mechanism frees the knob for rotational adjustment.

Investigation of electronic and magnetic properties of FeS: First principle and Monte Carlo simulations

NASA Astrophysics Data System (ADS)

Bouachraoui, Rachid; El Hachimi, Abdel Ghafour; Ziat, Younes; Bahmad, Lahoucine; Tahiri, Najim

2018-06-01

Electronic and magnetic properties of hexagonal Iron (II) Sulfide (hexagonal FeS) have been investigated by combining the Density functional theory (DFT) and Monte Carlo simulations (MCS). This compound is constituted by magnetic hexagonal lattice occupied by Fe2+ with spin state (S = 2). Based on ab initio method, we calculated the exchange coupling JFe-Fe between two magnetic atoms Fe-Fe in different directions. Also phase transitions, magnetic stability and magnetizations have been investigated in the framework of Monte Carlo simulations. Within this method, a second phase transition is observed at the Néel temperature TN = 450 K. This finding in good agreement with the reported data in the literature. The effect of the applied different parameters showed how can these parameters affect the critical temperature of this system. Moreover, we studied the density of states and found that the hexagonal FeS will be a promoting material for spintronic applications.

Oxygen interaction with hexagonal OsB 2 at high temperature

DOE PAGES

Xie, Zhilin; Blair, Richard G.; Orlovskaya, Nina; ...

2016-08-10

The stability of ReB 2-type hexagonal OsB 2 powder at high temperature with oxygen presence has been studied by thermogravimetric analysis, differential scanning calorimetry, SEM, EDS, and high-temperature scanning transmission electron microscopy and XRD. Results of the study revealed that OsB 2 ceramics interact readily with oxygen present in reducing atmosphere, especially at high temperature and produces boric acid, which decomposes on the surface of the powder resulting in the formation of boron vacancies in the hexagonal OsB 2 lattice as well as changes in the stoichiometry of the compound. It was also found that under low oxygen partial pressure,more » sintering of OsB 2 powders occurred at a relatively low temperature (900°C). Finally, hexagonal OsB 2 ceramic is prone to oxidation and it is very sensitive to oxygen partial pressures, especially at high temperatures.« less

Formation mechanism of graphite hexagonal pyramids by argon plasma etching of graphite substrates

NASA Astrophysics Data System (ADS)

Glad, X.; de Poucques, L.; Bougdira, J.

2015-12-01

A new graphite crystal morphology has been recently reported, namely the graphite hexagonal pyramids (GHPs). They are hexagonally-shaped crystals with diameters ranging from 50 to 800 nm and a constant apex angle of 40°. These nanostructures are formed from graphite substrates (flexible graphite and highly ordered pyrolytic graphite) in low pressure helicon coupling radiofrequency argon plasma at 25 eV ion energy and, purportedly, due to a physical etching process. In this paper, the occurrence of peculiar crystals is shown, presenting two hexagonal orientations obtained on both types of samples, which confirms such a formation mechanism. Moreover, by applying a pretreatment step with different time durations of inductive coupling radiofrequency argon plasma, for which the incident ion energy decreases at 12 eV, uniform coverage of the surface can be achieved with an influence on the density and size of the GHPs.

Additive Manufacturing of Dense Hexagonal Boron Nitride Objects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marquez Rossy, Andres E.; Armstrong, Beth L.; Elliott, Amy M.

The feasibility of manufacturing hexagonal boron nitride objects via additive manufacturing techniques was investigated. It was demonstrated that it is possible to hot-extrude thermoplastic filaments containing uniformly distributed boron nitride particles with a volume concentration as high as 60% and that these thermoplastic filaments can be used as feedstock for 3D-printing objects using a fused deposition system. Objects 3D-printed by fused deposition were subsequently sintered at high temperature to obtain dense ceramic products. In a parallel study the behavior of hexagonal boron nitride in aqueous solutions was investigated. It was shown that the addition of a cationic dispersant to anmore » azeotrope enabled the formulation of slurries with a volume concentration of boron nitride as high as 33%. Although these slurries exhibited complex rheological behavior, the results from this study are encouraging and provide a pathway for manufacturing hexagonal boron nitride objects via robocasting.« less

Optical Temperature Sensor Based on Infrared Excited Green Upconversion Emission in Hexagonal Phase NaLuF4:Yb3+/Er3+ Nanorods.

PubMed

Li, Dongyu; Tian, Linlin; Huang, Zhen; Shao, Lexi; Quan, Jun; Wang, Yuxiao

2016-04-01

Hexagonal phase NaLuF4:Yb3+/Er3+ nanorods were synthesized hydrothermally. An analysis of the intense green upconversion emissions at 525 nm and 550 nm in hexagonal phase NaLuF4:Yb3/+Er3+ nanorods under excitation power density of 4.2 W/cm2 available from a diode laser emitting at 976 nm, have been undertaken. Fluorescence intensity ratio (FIR) variation of temperature-sensitive green upconversion emissions at 525 nm and 550 nm in this material was recorded in the physiological range from 295 to 343 K. The maximum sensitivity derived from the FIR technique of the green upconversion emissions is approximately 0.0044 K-1. Experimental results implied that hexagonal phase NaLuF4:Yb3/+Er3+ nanorods was a potential candidate for optical temperature sensor.

Oxygen interaction with hexagonal OsB 2 at high temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xie, Zhilin; Blair, Richard G.; Orlovskaya, Nina

The stability of ReB 2-type hexagonal OsB 2 powder at high temperature with oxygen presence has been studied by thermogravimetric analysis, differential scanning calorimetry, SEM, EDS, and high-temperature scanning transmission electron microscopy and XRD. Results of the study revealed that OsB 2 ceramics interact readily with oxygen present in reducing atmosphere, especially at high temperature and produces boric acid, which decomposes on the surface of the powder resulting in the formation of boron vacancies in the hexagonal OsB 2 lattice as well as changes in the stoichiometry of the compound. It was also found that under low oxygen partial pressure,more » sintering of OsB 2 powders occurred at a relatively low temperature (900°C). Finally, hexagonal OsB 2 ceramic is prone to oxidation and it is very sensitive to oxygen partial pressures, especially at high temperatures.« less

Kinematic dynamo action in square and hexagonal patterns.

PubMed

Favier, B; Proctor, M R E

2013-11-01

We consider kinematic dynamo action in rapidly rotating Boussinesq convection just above onset. The velocity is constrained to have either a square or a hexagonal pattern. For the square pattern, large-scale dynamo action is observed at onset, with most of the magnetic energy being contained in the horizontally averaged component. As the magnetic Reynolds number increases, small-scale dynamo action becomes possible, reducing the overall growth rate of the dynamo. For the hexagonal pattern, the breaking of symmetry between up and down flows results in an effective pumping velocity. For intermediate rotation rates, this additional effect can prevent the growth of any mean-field dynamo, so that only a small-scale dynamo is eventually possible at large enough magnetic Reynolds number. For very large rotation rates, this pumping term becomes negligible, and the dynamo properties of square and hexagonal patterns are qualitatively similar. These results hold for both perfectly conducting and infinite magnetic permeability boundary conditions.

Hexagonal gradient scheme with RF spoiling improves spoiling performance for high-flip-angle fast gradient echo imaging.

PubMed

Hess, Aaron T; Robson, Matthew D

2017-03-01

To present a framework in which time-varying gradients are applied with RF spoiling to reduce unwanted signal, particularly at high flip angles. A time-varying gradient spoiler scheme compatible with RF spoiling is defined, in which spoiler gradients cycle through the vertices of a hexagon, which we call hexagonal spoiling. The method is compared with a traditional constant spoiling gradient both in the transition to and in the steady state. Extended phase graph (EPG) simulations, phantom acquisitions, and in vivo images were used to assess the method. Simulations, phantom and in vivo experiments showed that unwanted signal was markedly reduced by employing hexagonal spoiling, both in the transition to and in the steady state. For adipose tissue at 1.5 Tesla, the unwanted signal in the steady state with a 60 ° flip angle was reduced from 22% with constant spoiling to 2% with hexagonal spoiling. A time-varying gradient spoiler scheme that works with RF spoiling, called "hexagonal spoiling," has been presented and found to offer improved spoiling over the traditional constant spoiling gradient. Magn Reson Med 77:1231-1237, 2017. © 2016 The Authors Magnetic Resonance in Medicine published by Wiley Periodicals, Inc. on behalf of International Society for Magnetic Resonance in Medicine. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. © The Authors Magnetic Resonance in Medicine published by Wiley Periodicals, Inc. on behalf of International Society for Magnetic Resonance in Medicine.

Resistance of three implant-abutment interfaces to fatigue testing

PubMed Central

RIBEIRO, Cleide Gisele; MAIA, Maria Luiza Cabral; SCHERRER, Susanne S.; CARDOSO, Antonio Carlos; WISKOTT, H. W. Anselm

2011-01-01

The design and retentive properties of implant-abutment connectors affect the mechanical resistance of implants. A number of studies have been carried out to compare the efficacy of connecting mechanisms between abutment and fixture. Objectives The aims of this study were: 1) to compare 3 implant-abutment interfaces (external hexagon, internal hexagon and cone-in-cone) regarding the fatigue resistance of the prosthetic screw, 2) to evaluate the corresponding mode of failure, and 3) to compare the results of this study with data obtained in previous studies on Nobel Biocare and Straumann connectors. Materials and Methods In order to duplicate the alternating and multivectorial intraoral loading pattern, the specimens were submitted to the rotating cantilever beam test. The implants, abutments and restoration analogs were spun around their longitudinal axes while a perpendicular force was applied to the external end. The objective was to determine the force level at which 50% of the specimens survived 106 load cycles. The mean force levels at which 50% failed and the corresponding 95% confidence intervals were determined using the staircase procedure. Results The external hexagon interface presented better than the cone-in-cone and internal hexagon interfaces. There was no significant difference between the cone-in-cone and internal hex interfaces. Conclusion Although internal connections present a more favorable design, this study did not show any advantage in terms of strength. The external hexagon connector used in this study yielded similar results to those obtained in a previous study with Nobel Biocare and Straumann systems. However, the internal connections (cone-in-cone and internal hexagon) were mechanically inferior compared to previous results. PMID:21710094

Comparative study of torque resistance and microgaps between a combined Octatorx-cone connection and an internal hexagon implant-abutment connection.

PubMed

Khongkhunthian, Pathawee; Khongkhunthian, Sakornratana; Weerawatprachya, Winai; Pongpat, Kanuengnit; Aunmeungtong, Weerapan

2015-05-01

Although the implant-abutment connection may prevent crestal bone loss around dental implants, its failure often leads to treatment failure. Microgap and micromovement of the implant-abutment connection could be causes of bone resorption around dental implant neck. The purpose of this study was to compare torque resistance and microgaps between a new cone and index connection (Octatorx) and an internal hexagon implant-abutment connection (Internal hex). Twenty Octatorx and 20 internal hexagon connections were attached with retaining screws at 30 Ncm. In a torsion resistance test, 10 of each type of connection were attached to a universal testing machine. Torque resistance with 90 degrees per minute rotation speed was recorded. For microgap measurement, each of 10 connections was embedded in clear acrylic resin. The blocks were cut longitudinally. Twenty specimens of each connection were evaluated. Twelve measurements of microgaps (6 on each side of specimen) were recorded under scanning electron microscopy. The average torsion resistance of Octatorx (203.6 ±17.4 Ncm) was significantly greater than that of the internal hexagon (146.4 ±16.1 Ncm, P<.05). For the microgap, there was a significant difference (P=.001) between the median values of Octatorx (1.19 μm) and the internal hexagon (3.80 μm). In this study, the new connection, Octatorx, had a smaller microgap and greater torque resistance than the internal hexagon connection. Copyright © 2015 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

An Easily Constructed Model of a Coordination Polyhedron that Represents the Hexagonal Closest-Packed Structure.

ERIC Educational Resources Information Center

Yamana, Shukichi

1987-01-01

Illustrates the 29 steps involved in the development of a model of a coordination polyhedron that represents the hexagonal closest packed structure. Points out it is useful in teaching stereochemistry. (TW)