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Sample records for smectic-c mesophases revealed

  1. Smectic C chevrons in nanocylinders

    SciTech Connect

    Lefort, R. Morineau, D.; Jean, F.; Noirez, L.; Ndao, M.; Cerclier, C. V.

    2014-11-17

    The structure of an achiral smectic-C liquid crystal confined in nanocylinders with a planar surface anchoring is studied by small angle neutron scattering. We observe an invariant alignment of the nematic director with the pore axis, that promotes an original chevron structure with revolution symmetry.

  2. Microscopic organization of the smectic C phase

    NASA Astrophysics Data System (ADS)

    Glaser, Matthew A.; Lansac, Yves; Weider, Titus; Clark, Noel A.

    1998-03-01

    We have investigated the microstructure of a non-chiral smectic C liquid crystal, 4,n-hexyloxyphenyl-4,n^'-decyloxybenzoate, via large-scale atomistic simulation, and have compared the results with those obtained from modular mean-field models of molecular organization in the smectic C phase. We find that simple mean-field models successfully capture the main features of molecular organization observed in many-molecule simulations. Our large-scale simulations support the ``zig-zag'' model of smectic C ordering(R. Bartolino, J. Doucet, and G. Durand, Ann. Phys. 3), 389 (1978)., an observation that has a direct bearing on the microscopic origins of ferroelectric polarization in chiral smectic C materials. The use of large-scale simulation for the development of improved predictive models of ferroelectric polarization in chiral smectic C liquid crystals is discussed.

  3. New insights into the thermal stability of the smectic C phase.

    PubMed

    Porzio, François; Levert, Etienne; Vadnais, Richard; Soldera, Armand

    2014-04-10

    Subtle differences in the molecular structure of mesogens can lead to very different experimental polymorphisms. The smectic C (SmC) phase can actually be exhibited by one isomer and not the other, or the range of temperature can be completely different. Unveiling the deep connection between atomic structure and the very existence of the SmC phase will lead to the design of new performing liquid crystalline materials for ferroelectric or nonlinear optical applications. Our approach is based on running molecular dynamics simulation from an initial SmC arrangement of molecules. When the temperature is increased, the molecules automatically adjust in a more favorable organization. Such modification in the imposed initial self-assembly is governed by values of the nonbonded energies. Thanks to the combined use of simulation and experimental phase diagrams, we have unveiled part of the deep connection between atomic structure and the very existence of the SmC phase. The actual display of the SmC mesophase stems from a subtle balance between short-range interactions, which reveal arrangement of molecules within a smectic layer, and long-range interactions, which disclose organization of layers.

  4. Cholesteric mesophases

    NASA Astrophysics Data System (ADS)

    Sixou, P.; Gilli, J. M.; ten Bosch, A.; Fried, F.; Maïssa, P.; Varichon, L.; Godinho, M. H.

    1991-01-01

    In the past few years, there have been important developments concerning the role and the use of chirality in liquid crystals. An example which is now relatively well known is the chiral smectic C* low molecular weight liquid crystal (LMWLC) which lowers the response time of displays by a factor between one hundred and one thousand [1-3]. In chiral liquid crystal polymers (cholesteric or twisted nematic and smectic C*), it is necessary to understand the relation between the chemical structure and the properties of mesophases in liquid and solid polymer. Furthermore, chirality is also found in abundance in biopolymers and may be important for life processes. Applications in industry (high modulus fibers, sensors, non linear optics...) have already been realised or are being pursued. The aim of this paper is to emphasize the polymer character of these liquid crystals. What is the influence of the molecular weight, the degree of substitution, the viscoelasticity and the existence of a glass transition? How to use the polymer character to obtain new informations on the liquid crystal state or to make new devices? This rapid overview roughly covers the following parts: Formation and general properties of cholesteric mesophases: we give a rapid discussion of thermotropics and lyotropics, of the influence of degree of polymerisation, degree of substitution, concentration, temperature..., on the cholesteric-isotropic transition and on the order observed by textures or as described more quantitatively by the order parameter. Optical properties: we give a brief presentation of a theoretical work concerning the pitch prediction taking into account the asymmetric term in the interaction potential and the comparison with experimental results. Textures and defects which are mainly observed in these mesophases. Flow properties and rheological behaviour which are fundamental for processing. Blue phases near the isotropic-cholesteric transition which are discussed with emphasis on

  5. Smectic-C* alpha-smectic-C* Phase Transition and Critical Point in Binary Mixtures

    SciTech Connect

    Liu,Z.; Wang, S.; McCoy, B.; Cady, A.; Pindak, R.; Caliebe, W.; Takekoshi, K.; Ema, K.; Nguyen, H.; Huang, C.

    2006-01-01

    We have investigated the smectic-C*{sub {alpha}}-smectic-C* (SmC*{sub {alpha}}-SmC*) transition in a series of binary mixtures with resonant x-ray diffraction, differential optical reflectivity, and heat capacity measurements. Results show that the phases are separated by a first-order transition that ends at a critical point. We report the observation of such a critical point. We have proposed the appropriate order parameter and obtained values of two critical exponents associated with this transition. The values of the critical exponents suggest that long-range intersections are present in the SmC*{sub {alpha}}-SmC* critical regions.

  6. What about the Backbone Conformation in Nematic and Smectic C Phases of a ``Side-on'' Fixed LCP? A SANS Study

    NASA Astrophysics Data System (ADS)

    Lecommandoux, S.; Noirez, L.; Achard, M. F.; Hardouin, F.

    1997-10-01

    A polymorphism nematic - smectic C has been revealed for the first time in “side-on” fixed liquid crystalline polymers. By means of neutron investigations, structural and conformational results have been reported in both mesophases. An inversion of the backbone conformation is observed from the nematic phase to the smectic C phase. This new feature is compared to the well known situation of the N SA transition for “side-end” fixed liquid crystal polymers. Un polymorphisme de type nématique - smectique C a été pour la première fois révélé dans les polymères cristaux liquides en “haltère”. Des résultats structuraux et conformationnels obtenus par diffusion cohérente de neutrons sont présentés pour les deux mésophases. Une inversion de la conformation de la chaîne polymère est observée de la phase nématique à la phase smectique C. Ce comportement original est comparé au cas de la transition N SA pour des polymères cristaux liquides en “peigne”.

  7. Unique Pitch Evolution in the Smectic -C-alpha* Phase

    SciTech Connect

    Liu,Z.; McCoy, B.; Wang, S.; Pindak, R.; Caliebe, W.; Barois, P.; Fernandes, P.; Nguyen, H.; Hsu, C.; Wang, .

    2007-01-01

    Employing resonant x-ray diffraction, we observed unique pitch evolutions in the smectic-C{alpha}* phase in mixtures of two antiferroelectric liquid crystals. Our results show that the pitch in this phase continuously evolves across 4 layers, contradicting a theoretical model that predicts that the smectic-C{sub FI2}* phase intervenes in the smectic-C{alpha}* phase. The phase sequences we found can be explained by another model that includes one type of long-range interaction among smectic layers.

  8. Monolayer to interdigitated partial bilayer smectic C transition in thiophene-based spacer mesogens: X-ray diffraction and (13)C nuclear magnetic resonance studies.

    PubMed

    Kesava Reddy, M; Varathan, E; Lobo, Nitin P; Roy, Arun; Narasimhaswamy, T; Ramanathan, K V

    2015-10-06

    Mesophase organization of molecules built with thiophene at the center and linked via flexible spacers to rigid side arm core units and terminal alkoxy chains has been investigated. Thirty homologues realized by varying the span of the spacers as well as the length of the terminal chains have been studied. In addition to the enantiotropic nematic phase observed for all the mesogens, the increase of the spacer as well as the terminal chain lengths resulted in the smectic C phase. The molecular organization in the smectic phase as investigated by temperature dependent X-ray diffraction measurements revealed an interesting behavior that depended on the length of the spacer vis-a-vis the length of the terminal chain. Thus, a tilted interdigitated partial bilayer organization was observed for molecules with a shorter spacer length, while a tilted monolayer arrangement was observed for those with a longer spacer length. High-resolution solid state (13)C NMR studies carried out for representative mesogens indicated a U-shape for all the molecules, indicating that intermolecular interactions and molecular dynamics rather than molecular shape are responsible for the observed behavior. Models for the mesophase organization have been considered and the results understood in terms of segregation of incompatible parts of the mesogens combined with steric frustration leading to the observed lamellar order.

  9. Effects of electrohydrodynamic instability in smectic C liquid crystals

    NASA Astrophysics Data System (ADS)

    Denisova, O. A.; Chuvyrov, A. N.

    2013-03-01

    The effects of electrohydrodynamic instability (EHDI) in smectic C liquid crystals in an electric field are studied. The objects of study are oriented layers of para-hydroxybenzoic acid possessing a smectic phase. The observed effects are divided into three groups according to the character of the motion of molecular centers of mass and the orientation of the director and the smectic C liquid crystal layers. The instabilities of the azimuthal and Kapustin-Williams domains are experimentally found. The experimental cell consists of two glass plates with tin dioxide electrodes separated by Mylar spacers of a specified thickness. Various schemes of domain rotation are considered. The EHDI is found to depend on the layer geometry.

  10. Travelling waves in two-dimensional smectic-C domains

    NASA Astrophysics Data System (ADS)

    Claret, J.; Crusats, J.; Albalat, R.; Ignés-Mullol, J.; Martınez-Seara, H.; Reigada, R.; Sagués, F.

    2006-10-01

    Continued irradiation of smectic-C-like domains of photosensitive Langmuir monolayers from azobenzene derivatives induces the nucleation and propagation of orientational travelling waves as observed with Brewster angle microscopy (BAM). BAM image analysis has allowed to identify different dynamical behaviors involving the generation and propagation of such waves. A model based on the coupling between an orientational and a composition field proposes a scenario for dynamic self-assembly that accounts for most of the observed phenomena, and allows to pinpoint the relevance of boundary defects in wave-emitting structures. Supplementary material in the form of video files available from the Journal web page at http://dx.doi.org/10.1140/epje/i2006-10049-5 and are accessible for authorised users.

  11. Synthesis, structural and electrochemical characterization of benzimidazole compounds exhibiting a smectic C liquid crystal phase

    NASA Astrophysics Data System (ADS)

    Wei, Bingzhuo; Tan, Shuai; Liang, Ting; Cao, Siyu; Wu, Yong

    2017-04-01

    Mesomorphic benzimidazole compounds were prepared from a biphenyl benzoate based precursor by substitution reaction of alkyl bromide with 2-mercaptobenzimidazole. Molecular structures of the benzimidazole compounds were characterized by nuclear magnetic resonance (NMR), Fourier transform infrared (FT-IR) spectroscopy and elemental analysis. Differential scanning calorimetry (DSC) measurements and polarizing optical microscopic (POM) observations revealed that the benzimidazole compounds exhibited a thermotropic smectic C (SC) phase. Temperature dependent X-ray diffraction (XRD) patterns suggested a tilted bilayer smectic structure in which intermolecular hydrogen bonds between benzimidazole moieties formed lamellar arrangement. Electrochemical impedance spectroscopy (EIS) characterization suggested that the SC phase favored anhydrous proton conduction of the benzimidazole compounds and the proton conductivities showed an Arrhenius temperature dependence.

  12. Liquid crystal mesophases beyond commensurate four-layer periodicity

    SciTech Connect

    Huang, C. C.; Wang, Shun; Pan, LiDong; Liu, Z. Q.; McCoy, B. K.; Sasaki, Yuji; Ema, Kenji; Barois, P.; Pindak, Ron

    2015-01-02

    For more than one decade, SMC*d4, SmC*d3, and SmC*A were the only three confirmed commensurate SmC* variant phases with periodicities less than or equal four layers. In 2006, employing ellipsometry and resonant X-ray diffraction (RXRD), our research team first discovered a new liquid crystal mesophase having a six-layer periodicity in one ternary mixture which includes one sulfur-containing compound. From our ellipsometric results, this phase showed antiferroelectric-like optical response. This novel discovery inspired renewed interest to search for liquid crystal mesophases with commensurate periodicities greater than four layers. Soon after, another mesophase having a six-layer structure and showing a ferrielectric-like dielectric response, instead, was uncovered by RXRD measurements on a different binary mixture which has one bromine-containing compound. Meanwhile mesophases having a 5-, 8-, 12- or 15-layer periodicity were reported. However, numerous questions remain to be addressed associated with these unusual reported phases. Theoretical models giving rise to mesophases with periodicities greater than four layers have been developed; but, to date, none of them have provided satisfactory explanations of all the physical phenomena related to the mesophases exhibiting a six-layer structure. Moreover, the question “what is the source of long-range interactions between liquid-like smectic layers, which are responsible for establishing mesophases with long periodicities and mean-field behavior of the smectic-A–smectic-C transition?” remains unanswered for more than three decades.

  13. Dormant mesophase pitch

    SciTech Connect

    Otani, S.

    1984-09-18

    A novel carbonaceous pitch which is optically isotropic in nature and which turns into optically anisotropic when shear forces are applied thereto. The carbonaceous pitch may be obtained by hydrogenating the mesophase of a mesophase pitch to the extent that the mesophase is rendered soluble in quinoline. The carbonaceous pitch is used as a binder and an impregnator and as a precursor material for a highly oriented, high-strength and high-modulus carbon fiber, needle coke or the like carbonaceous materials.

  14. Negative Poisson's ratio and semisoft elasticity of smectic-C liquid-crystal elastomers

    NASA Astrophysics Data System (ADS)

    Brown, A. W.; Adams, J. M.

    2012-01-01

    Models of smectic-C liquid-crystal elastomers predict that they can display soft elasticity, in which the shape of the elastomer changes at no energy cost. The amplitude of the soft mode and the accompanying shears are dependent on the orientation of the layer normal and the director with respect to the stretch axis. We demonstrate that in some geometries the director is forced to rotate perpendicular to the stretch axis, causing lateral expansion of the sample—a negative Poisson's ratio. Current models do not include the effect of imperfections that must be present in the physical sample. We investigate the effect of a simple model of these imperfections on the soft modes in monodomain smectic-C elastomers in a variety of geometries. When stretching parallel to the layer normal (with imposed strain) the elastomer has a negative stiffness once the director starts to rotate. We show that this is a result of the negative Poisson's ratio in this geometry through a simple scalar model.

  15. Process for producing mesophase pitch

    SciTech Connect

    Izumi, T.; Igarashi, S.; Naito, T.

    1985-08-06

    A substantially uniform mesophase pitch is prepared by treating a mesophase forming pitch material at elevated temperatures above about 380/sup 0/ C. to produce a mixture of mesophase and non-mesophase pitch containing about 20% to about 80% mesophase. The mixture is then maintained at a temperature below about 400/sup 0/ C. for a time sufficient to allow the mesophase to coalesce and settle as a lower separable layer. A mesophase pitch so produced may contain from 90 to 100% mesophase with a softening point of less than 320/sup 0/ C.

  16. Orientational relaxation in free-standing smectic C film driven by rotating circular frame.

    PubMed

    Zakharov, A V; Vakulenko, A A

    2015-09-14

    The pecularities in the cˆ-director reorientation in free-standing smectic C film without of defects and stretched between two circular frames, the rest outer and rotating inner, have been investigated theoretically based on the hydrodynamic theory including the cˆ-director motion and with accounting for backflow. Since the orientation of the cˆ-director is fixed at the rims of the smectic film, the shear flow induced by rotating frame winds up of the cˆ-director field. It is found that the higher shearing flow produces the greater twisting rotation of the cˆ-director around the normal to the smectic film directed in the opposite sense with respect to the direction of the angular velocity. Calculations also show that the relaxation dynamics of the cˆ-director field depends crucially on the curvature of the inner rotating frame.

  17. Orientational relaxation in free-standing smectic C film driven by rotating circular frame

    NASA Astrophysics Data System (ADS)

    Zakharov, A. V.; Vakulenko, A. A.

    2015-09-01

    The pecularities in the c ˆ -director reorientation in free-standing smectic C film without of defects and stretched between two circular frames, the rest outer and rotating inner, have been investigated theoretically based on the hydrodynamic theory including the c ˆ -director motion and with accounting for backflow. Since the orientation of the c ˆ -director is fixed at the rims of the smectic film, the shear flow induced by rotating frame winds up of the c ˆ -director field. It is found that the higher shearing flow produces the greater twisting rotation of the c ˆ -director around the normal to the smectic film directed in the opposite sense with respect to the direction of the angular velocity. Calculations also show that the relaxation dynamics of the c ˆ -director field depends crucially on the curvature of the inner rotating frame.

  18. Discovery of a Novel Smectic-C Liquid Crystal Phase with Six Layer Periodicity

    SciTech Connect

    Wang, S.; Pindak, R.; Pan, L.D.; Liu, Z.Q; Nguyen, H.T.; Huang, C.C.

    2010-01-13

    We report the discovery of a new smectic-C* liquid-crystal phase with six-layer periodicity by resonant x-ray diffraction. Upon cooling, the new phase appears between the SmC{sub {alpha}}* phase having a helical structure and the SmC{sub d4}* phase with four-layer periodicity. This SmC{sub d6}* phase was identified in two mixtures which have an unusual reversed SmC{sub d4}*-SmC* phase sequence. The SmC{sub d6}* phase shows a distorted clock structure. Three theoretical models have predicted the existence of a six-layer phase. However, our experimental findings are not consistent with the theories.

  19. Pretransitional effects near the smectic-A-smectic-C* phase transition of hydrophilic and hydrophobic aerosil networks dispersed in ferroelectric liquid crystals

    SciTech Connect

    Cordoyiannis, George; Kralj, Samo; Nounesis, George; Kutnjak, Zdravko; Zumer, Slobodan

    2007-02-15

    A detailed x-ray scattering and high-resolution ac calorimetric study has been carried out near the smectic-A to chiral smectic-C phase transition of liquid-crystal compounds 4-(2-methyl butyl) phenyl 4-n-octylbiphenyl-4-carboxylate (CE8) and p-(n-decyloxy) benzylidene-p-amino-(2-methylbutyl) cinnamate (DOBAMBC) confined in hydrophilic and hydrophobic aerosil nanoparticle networks. The character of the transition, which is mean field near a tricritical point in bulk, is changed dramatically with an increase of aerosil-induced disorder. X-ray measurements revealed pretransitional behavior and compression of the smectic layers, phenomena that are strongly pronounced in high aerosil concentrations. A theoretical model that takes into account the interplay of relevant mechanisms is proposed to explain the observed phenomena. The effect of chirality on the interaction of liquid crystals with aerosils is discussed.

  20. Polymer stabilization of the smectic C-alpha* liquid crystal phase—Over tenfold thermal stabilization by confining networks of photo-polymerized reactive mesogens

    NASA Astrophysics Data System (ADS)

    Labeeb, A.; Gleeson, H. F.; Hegmann, T.

    2015-12-01

    The smectic C*-alpha (SmCα*) phase is one of the sub-phases of ferroelectric liquid crystals that has drawn much interest due to its electro-optical properties and ultrafast switching. Generally observed above the ferroelectric SmC* phase in temperature, the SmCα* commonly shows only very narrow phase temperature range of a few degree Celsius. To broaden the SmCα* phase, polymer stabilization was investigated for thermal phase stabilization. Two different reactive monomers were tested in three mixtures, and all three broadened the temperature range of the SmCα* phase from 3 °C to 39 °C. The current reversal method was used to determine the phase existence versus temperature. Moreover, the texture and network structure was studied by polarized optical microscopy and scanning electron microscopy, with the latter revealing the confinement of the smectic layer structure within the porous polymer network.

  1. Birefringence in the vicinity of the smectic-A to smectic-C phase transition: Crossover from X Y critical to tricritical behavior

    NASA Astrophysics Data System (ADS)

    Das, Malay Kumar; Chakraborty, Susanta; Dabrowski, Roman; Czerwiński, Michał

    2017-01-01

    High-resolution birefringence (Δ n ) measurements are carried out to probe the critical behavior at the smectic-A -smectic-C (Sm-A -Sm-C ) phase transition in a binary system. The critical behavior of this transition is explored with the aid of a differential quotient extracted from the Δ n values. The results obtained reveal that the Sm-A -Sm-C and nematic-smectic-A (N -Sm-A ) transitions exhibit nonuniversal behaviors with effective exponents lying between the tricritical and three-dimensional X Y values and follow two distinctly different curves with decreasing width of the Sm-A and N phases, respectively. The origin of such critical behavior is a unique feature for the respective phase transitions.

  2. Pressure settling of mesophase

    SciTech Connect

    Romine, H.E.

    1989-05-23

    This patent describes a process for producing mesophase pitch wherein a heavy aromatic hydrocarbon feedstock is heat soaked at a first pressure until a substantial portion of the feedstock has been converted to optically anisotropic material, and in which mesophase pitch is recovered from the heat soaked material by gravity settling, the improvement comprises: subjecting and maintaining for a time of up to about 15 minutes the heat soaked material, prior to recovery of mesophase pitch therefrom, to a second pressure which is at least 30 kPa higher than the first pressure for a time of up to about 15 minutes, whereby boiling of the heat soaked material is reduced and settling of mesophase pitch is enhanced.

  3. Process for producing mesophase pitch

    SciTech Connect

    Isumi, T.; Naito, T.; Igarashi, S.

    1988-11-29

    This patient describes process for producing a mesophase pitch having a mesophase content of above 90% and a softening point of below 320/sup 0/ C. comprising the steps of: heat-treating a pitch forming material at elevated temperatures above about 380/sup 0/C for a time sufficient to provide a mixture of mesophase and non-mesophase pitch containing about 20% to about 80% (by weight) of mesophase and a softening point of no greater than 250/sup 0/C; aging and settling the mesophase portion of the mixture of mesophase and non-mesophase pitch obtained in step by maintaining the mixture in a substantially quiescent condition and at a temperature below the temperature in the heat-treating step, at which temperature the mixture is sufficiently liquid so that the separation of the mesophase and non-mesophase portions of the mixture can be substantially accomplished, (and above about 350/sup 0/C) for a time sufficient for the mesophase portion of the mixture to coalesce and accumulate into a substantially lower homogeneous mesophase pitch layer containing at least 90% mesophase and an upper layer comprising the non-mesophase portion of the mixture; and separating the lower mesophase layer from the upper non-mesophase layer whereby a mesophase pitch which has a mesopphase content of above 90% and a softening point below 320/sup 0/C is obtained. heat-treated at a temperature in the range of about 380/sup 0/C to about 460/sup 0/C whereby thermal cracking and polycondensation reaction occur.

  4. Smectic C liquid crystal growth through surface orientation by ZnxCd1-xSe thin films

    NASA Astrophysics Data System (ADS)

    Katranchev, B.; Petrov, M.; Bineva, I.; Levi, Z.; Mineva, M.

    2012-12-01

    A smectic C liquid crystal (LC) texture, consisting of distinct local single crystals (DLSCs) was grown using predefined orientation of ternary nanocrystalline thin films of ZnxCd1-xSe. The surface morphology and orientation features of the ZnxCd1-xSe films were investigated by AFM measurements and micro-texture polarization analysis. The ZnxCd1-xSe surface causes a substantial enlargement of the smectic C DLSCs and induction of a surface bistable state. The specific character of the morphology of this coating leads to the decrease of the corresponding anchoring energy. Two new chiral states, not typical for this LC were indicated. The physical mechanism providing these new effects is presented.

  5. Polarity sensitive electric responses in a twisted smectic-C liquid crystal

    NASA Astrophysics Data System (ADS)

    Krishnamurthy, K. S.

    2013-12-01

    The observation of two polarity-sensitive electrical responses found in the low-frequency (<1 Hz) regime of a square wave field is reported for an achiral rodlike smectic-C liquid crystal with negative dielectric and conductivity anisotropies and in the 90°-twisted configuration. The first involves a transient director modulation appearing at each polarity reversal and vanishing under steady field conditions. The instability is polarity sensitive, with the maximum distortion localized near the negative electrode instead of the sample midplane. This is inferred from the wave-vector orientation alternating in the two halves of the driving cycle between the alignment directions at the two substrates. Various electro-optic characteristics of this temporal phenomenon are also described. Following a similar observation in nematic liquid crystals, we associate the transient periodic order with the Carr-Helfrich mechanism assisted by quadrupolar flexoelectric polarization obtaining under electric field gradients. The second polarity-sensitive effect manifests in the relative shift of the periodic Fréedericksz pattern upon field reversal. The shift, which is linear in field for low fields, tends to saturate for large fields. It is interpreted as due to flexoelectric polarization associated primarily with the c director twist about the layer normal. A model involving a periodic wedgelike band, which has the twist localized within it and is flanked by two uniformly and transversely aligned regions, accounts for the flexoelectric shift of the optical pattern.

  6. Method for producing mesophase continuously

    SciTech Connect

    Watanabe, M.

    1985-04-23

    A method for producing continuously 100% mesophase composed only of Q.I. component and Q.S. component in which a raw material of petroleum origin pitch is subjected continuously to a heat-treatment step in an amount necessary to produce a 100% mesophase taken out from a mesophase-growing and coalescing step, transferring the heat-formed pitch formed in the heat treatment step to a mesophase growing and coalescing step, taking out a definite amount of a non-mesophase pitch from the mesophase growing and coalescing step after stirring and heating treatment to return it to the heat-treatment step to repeat the stirring and heating treatment, and at the same time to take out 100% mesophase having constant properties from the mesophase growing and coalescing step.

  7. Process for producing mesophase pitch

    SciTech Connect

    Shibatani, H.; Kameda, T.; Takahashi, K.

    1985-07-09

    Mesophase pitch containing quinoline soluble mesophase is produced from a pitch having a specific aromatic hydrogen content with a short heat treatment time without conducting any special treatment such as extraction.

  8. Process for isolating mesophase pitch

    SciTech Connect

    Romine, H.E.; McConaghy, J.R. Jr.

    1991-07-16

    This patent describes a process for the preparation of mesophase pitch. It comprises combining an isotropic pitch containing mesogens with a solvent, effecting phase separation of the mesogens from the isotropic pitch under solvent supercritical conditions of temperature and pressure, wherein the mesogens associate together under solvent supercritical conditions of temperature and pressure to form mesophase pitch; and recovering mesophase pitch.

  9. Low melting mesophase pitches

    SciTech Connect

    Diefendorf, R.J.; Chen, S.H.

    1984-04-17

    A low melting point, low molecular weight, heptane insoluble, 1,2,4-trichlorobenzene soluble mesophase pitch useful in carbon fiber spinning as such or as a plasticizer in a carbon fiber spinning composition is obtained by heating chrysene, triphenylene or paraterphenyl as well as mixtures thereof and hydrocarbon fractions containing the same, dissolving the resulting heat treated material with 1,2,4-trichlorobenzene, and separating the insolubles, and then contacting the 1,2,4-trichlorobenzene soluble fraction with a sufficient amount of heptane to precipitate the low melting point, low molecular weight mesophase pitch.

  10. Method for producing mesophase pitch

    SciTech Connect

    Watarabe, M.

    1985-07-16

    A method for producing a 100% mesophase pitch composed only of Q.I. and Q.S. components is provided. This method comprises subjecting petroleum-origin pitch to heat treatment with stirring under a stream of a hydrocarbon gas of small carbon atom numbers at atmospheric or superatmospheric pressure, holding said heat-treated pitch in quiescent state to melt and coalesce only the mesophase therein and dividing and separating non-mesophase and mesophase layers. Resulting 100% mesophase enables us to produce high strength, high modulus carbon fibers.

  11. Method for producing mesophase pitch

    SciTech Connect

    Watanale, M.

    1985-07-16

    A method for producing a 100% mesophase composed only of Q.I. component and Q.S. component is provived. This method comprises forming mesophase by the heat treatment of petroleum-origin pitch, subjecting the heat-formed pitch to a condition of heating under quiescent state to cause only the mesophase in the heat-formed pitch to grow and coalesce, separating only the non-mesophase of the upper layer and repeating the operation of the heat treatment and maintenance of heating under a quiescent state by the separated non-mesophase, as a raw material.

  12. Polymer stabilization of the smectic C-alpha* liquid crystal phase—Over tenfold thermal stabilization by confining networks of photo-polymerized reactive mesogens

    SciTech Connect

    Labeeb, A.; Gleeson, H. F.; Hegmann, T.

    2015-12-07

    The smectic C*-alpha (SmC{sub α}*) phase is one of the sub-phases of ferroelectric liquid crystals that has drawn much interest due to its electro-optical properties and ultrafast switching. Generally observed above the ferroelectric SmC* phase in temperature, the SmC{sub α}* commonly shows only very narrow phase temperature range of a few degree Celsius. To broaden the SmC{sub α}* phase, polymer stabilization was investigated for thermal phase stabilization. Two different reactive monomers were tested in three mixtures, and all three broadened the temperature range of the SmC{sub α}* phase from 3 °C to 39 °C. The current reversal method was used to determine the phase existence versus temperature. Moreover, the texture and network structure was studied by polarized optical microscopy and scanning electron microscopy, with the latter revealing the confinement of the smectic layer structure within the porous polymer network.

  13. Critical behavior at the isotropic to nematic, nematic to smectic-A and smectic-A to smectic-C phase transitions in a pyrimidine liquid crystal compound

    NASA Astrophysics Data System (ADS)

    Chakraborty, Anish; Chakraborty, Susanta; Kumar Das, Malay

    2015-12-01

    High-resolution optical birefringence (∆n) measurement of a pyrimidine liquid crystal compound having nematic, smectic-A and smectic-C phases are reported. The high-resolution ∆n data are rather successful in assessing the critical anomaly at different phase transitions in the investigated compound with a reasonably good accuracy. The critical exponent β, describing the limiting behavior of the nematic order parameter close to the isotropic-nematic (I-N) phase transition, is found to be in good agreement with the tricritical hypothesis. The critical behavior at the nematic-smectic-A (N-Sm-A) and the smectic-A-smectic-C (Sm-A-Sm-C) phase transitions has been explored with the aid of a differential quotient extracted from the ∆n values. The yielded effective critical exponent α‧ is appeared to be nearly tricritical in nature for the N-Sm-A phase transition. For the Sm-A-Sm-C phase transition, α‧ exhibits a weak dependence on the fit range and assumes tricritical value for large temperature range considered, which again is found to be diminished slightly with reduction in the temperature range. Related critical amplitude quotient and corrections-to-scaling quotient are found to display deviations from the theoretical models. Such behavior signals the appearance of a non-Landau character for the orthogonal to tilted smectic phase transition in the investigated compound.

  14. Transitions induced by solubilized fat into reverse hexagonal mesophases.

    PubMed

    Amar-Yuli, Idit; Garti, Nissim

    2005-06-25

    . 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.

  15. Mesophase Behavior in Carbon Fiber Bundles.

    DTIC Science & Technology

    1982-06-01

    mesophase tends to occur preferentially t 00 PORN 1413 IFACOMILC 14UUNCLASSIFIED i SECURITY CLASSIFICATION OF THIS PAGE (When Datam UNCLASSIFIED...direct contact with relatively hard carbon fibers. A. IN-AUTOCLAVE QUENCHING A reasonable quenching rate must be achieved for specimens containing...thL iartially pyrolyzed specimens. Drastic fine-scale variations in hardness and toughness of pitch, mesophase, fiber, and epoxy can pose problems of

  16. Mesophase from anthracene oil-based pitches

    SciTech Connect

    P. Alvarez; J. Sutil; R. Santamaria; C. Blanco; R. Menendez; M. Granda

    2008-11-15

    This work deals with the preparation of the mesophase from two pitch-like materials obtained from anthracene oil by oxidative thermal condensation (AOP-1) and the subsequent thermal treatment and distillation of AOP-1 (AOP-2). The mesophase was obtained by the controlled pyrolysis (440-470{degree}C and different periods of residence times) and subsequent sedimentation of the samples. In the case of the pitch prepared by oxidative thermal condensation, a dynamic pressure of 5 bar was applied during the pyrolysis. The pressure was a critical parameter, and its influence was also investigated. The results show that AOP-1 requires higher temperatures and/or residence times to develop mesophase than AOP-2. After sedimentation, a sample consisting of mainly mesophase was produced in all of the cases. The characterization of the mesophases by means of techniques, such as elemental and thermogravimetric analysis and optical microscopy, showed that anthracene oil-based derivatives are appropriate precursors for producing QI-free mesophase with suitable properties for the fabrication of a wide range of carbon materials. 26 refs., 5 figs., 3 tabs.

  17. Crystalline mesophases: Structure, mobility, and pharmaceutical properties.

    PubMed

    Shalaev, Evgenyi; Wu, Ke; Shamblin, Sheri; Krzyzaniak, Joseph F; Descamps, Marc

    2016-05-01

    Crystalline mesophases, which are commonly classified according to their translational, orientational, and conformational order as liquid crystals, plastic crystals, and conformationally disordered crystals, represent a common state of condensed matter. As an intermediate state between crystalline and amorphous materials, crystalline mesophases resemble amorphous materials in relation to their molecular mobility, with the glass transition being their common property, and at the same time possessing a certain degree of translational periodicity (with the exception of nematic phase), with corresponding narrow peaks in X-ray diffraction patterns. For example, plastic crystals, which can be formed both by near-spherical molecules and molecules of lower symmetry, such as planar or chain molecules, can have both extremely sharp X-ray diffraction lines and exhibit glass transition. Fundamentals of structural arrangements in mesophases are compared with several types of disorder in crystalline materials, as well as with short-range ordering in amorphous solids. Main features of the molecular mobility in crystalline mesophases are found to be generally similar to amorphous materials, although some important differences do exist, depending on a particular type of mobility modes involved in relaxation processes. In several case studies reviewed, chemical stability appears to follow the extent of disorder, with the stability of crystalline mesophase found to be intermediate between amorphous (least stable) and crystalline (most stable) materials. Finally, detection of crystalline mesophases during manufacturing of two different types of dosage forms is discussed. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. Crystallizing Membrane Proteins Using Lipidic Mesophases

    PubMed Central

    Caffrey, Martin; Cherezov, Vadim

    2009-01-01

    A detailed protocol for crystallizing membrane proteins that makes use of lipidic mesophases is described. This has variously been referred to as the lipid cubic phase or in meso method. The method has been shown to be quite general in that it has been used to solve X-ray crystallographic structures of prokaryotic and eukaryotic proteins, proteins that are monomeric, homo- and hetero-multimeric, chromophore-containing and chromophore-free, and α-helical and β-barrel proteins. Its most recent successes are the human engineered β2-adrenergic and adenosine A2A G protein-coupled receptors. Protocols are provided for preparing and characterizing the lipidic mesophase, for reconstituting the protein into the monoolein-based mesophase, for functional assay of the protein in the mesophase, and for setting up crystallizations in manual mode. Methods for harvesting micro-crystals are also described. The time required to prepare the protein-loaded mesophase and to set up a crystallization plate manually is about one hour. PMID:19390528

  19. The steady and transient rheological behavior or mesophase pitches

    SciTech Connect

    Fleurot, O.; Edie, D.D.

    1996-12-31

    Carbonaceous mesophase, a discotic, nematic liquid crystal, is a common precursor for the production of high performance (high thermal conductivity) carbon fibers. During melt spinning of mesophase pitches into fiber form, the poly-domain structure is stretched and oriented. A highly-oriented as-spun structure can be readily graphitized, giving the final heat-treated fiber superior thermal properties. Obviously, understanding, predicting, and ultimately controlling the development of structure is critical, if the final properties of mesophase pitch carbon fibers are to be optimized. While the development of structure in mesophase has been qualitatively described, quantitative information is needed. Complicating factors are: (i) the physical properties of mesophase pitches depend on the nature of the precursor material used to produce the liquid crystalline fluid, (ii) the rheological properties of mesophase are highly temperature-dependent, and (iii) mesophase pitch is optically opaque. In this work, the development of structure during steady and transient flow was investigated for different mesophase pitches.

  20. Double epitaxy as a paradigm for templated growth of highly ordered three-dimensional mesophase crystals

    SciTech Connect

    Shin, Yongsoon; Tao, Jinhui; Arey, Bruce W.; Wang, Chongmin; Exarhos, Gregory J.; De Yoreo, James J.; Sushko, Maria L.; Liu, Jun

    2016-08-30

    Molecular templating and self-assembly are fundamental mechanisms for controlling the morphology of biominerals, while in synthetic two-dimensional layered materials similar levels of control over materials structure can be achieved through the epitaxial relationship with the substrate. In this study these two concepts are combined to provide an approach for the nucleation and growth of three-dimensional ordered mesophases on solid surfaces. A combined experimental and theoretical study revealed how atomic ordering of the substrate controls the structure of surfactant template and the orientation and morphology of the epitaxially grown inorganic material. Such dual epitaxial relationship between the substrate, surfactant template and inorganic mesophase gives rise to a highly ordered porous mesophase with a well-defined cubic lattice of pores. The level of control over material’s three-dimensional architecture achieved in this one-step synthesis is reminiscent to that in biomineralization.

  1. Formation and behavior of carbonaceous mesophase in petroleum pitch

    SciTech Connect

    Stevens, W.C.

    1985-01-01

    The phase behavior of conventional liquid crystals with nonmesomorphs was studied and compared to mixtures of mesophase pitches with aromatic molecules. Experimental phase diagrams of p-polyphenyls, p-azoxyanisol and various aromatic molecules were used to estimate the virtual mesophase-isotropic transition temperatures of the latter. The mesophase-isotropic transition in mesophase pitch, hidden by reactions, decreases the solubility of nonmesomorphs as would be predicted by the phase behavior of conventional liquid crystals. From vapor osmometry, gel permeation chromatography and elemental analysis, models of Ashland 240 and a solvent extracted Ashland 240 mesophase pitch were developed. The 3 to 5-ringed aromatic species contained within Ashland 240 are the polymerized subunits forming the branched molecules of the solvent extracted mesophase pitch. The effects of air blowing, sparging and heat soaking on the nature and constitution of mesophase formed from Ashland 240 pitch also were examined and compared to the solvent extracted pitch. The nature and consequently the behavior of the mesophase formed was found to be process dependent. The utility of mesophase pitches is derived largely from the local molecular orientation. Experimentally observed changes in local order as a function of temperature and time at temperature were attributed to the hidden mesophase-isotropic transition temperature and the reactions which mask this transition. The orientation, relaxation, and stabilization of locally ordered subunits into an overall preferred orientation was examined by melt spinning mesophase pitches into fibers.

  2. Molecular Dynamics in a Liquid Crystal with Reentrant Mesophases

    NASA Astrophysics Data System (ADS)

    Sebastião, P. J.; Ribeiro, A. C.; Nguyen, H. T.; Noack, F.

    1995-11-01

    It is well known that liquid crystalline compounds with a cyano terminal group can present peculiar polymorphisms in particular different types of smectic A mesophases and a reentrant behaviour for both nematic and smectic A mesophases. In this work we study by proton NMR relaxation the influence of these features on the molecular dynamics of the compound 4-cyanobenzoate-4'-octylbenzoyloxyphenyl (DB8CN Sym) in its nematic (N), partial bilayer smectic A (SAd), reentrant nematic (Nre) and reentrant smectic A (SA1) mesophases. Standard and fast field-cycling techniques were used for our spin-lattice relaxation's study over a broad frequency range of 6 decades (200 Hz up to 300 MHz). It was found that the molecular dynamics in the nematic mesophases is rather different from the molecular dynamics in the smectic A mesophases. However, the reentrant aspect present in both nematic and smectic A states is not associated to a major difference on the molecular dynamics of the nematic and reentrant nematic or smectic and reentrant smectic A mesophases. Order director fluctuations and rotations/reorientations are the most important relaxation mechanisms in the nematic mesophases in the lower and higher frequency limits, respectively, while self-diffusion has a very small contribution to the overall relaxation. As for the smectic A mesophases, self-diffusion and rotations/reorientations are the predominant relaxation mechanisms for frequencies above 20 kHz. The collective motions, which for these mesophases have to be associated with layer undulations with the frequency law T_1sim ν, are only important to the spin-lattice relaxation on the low part of the frequency spectrum (ν<10 kHz). The inclusion in the relaxation study of a contribution from the cross-relaxation between protons and nitrogen nuclei improves the quality of the 1/T_1 data fits in both kinds of mesophases. The combined study of the molecular dynamics in the N, SAd, Nre and SA1 mesophases of DB8CN Sym reveals

  3. Crystallizing Transmembrane Peptides in Lipidic Mesophases

    SciTech Connect

    Höfer, Nicole; Aragão, David; Caffrey, Martin

    2011-09-28

    Structure determination of membrane proteins by crystallographic means has been facilitated by crystallization in lipidic mesophases. It has been suggested, however, that this so-called in meso method, as originally implemented, would not apply to small protein targets having {le}4 transmembrane crossings. In our study, the hypothesis that the inherent flexibility of the mesophase would enable crystallogenesis of small proteins was tested using a transmembrane pentadecapeptide, linear gramicidin, which produced structure-grade crystals. This result suggests that the in meso method should be considered as a viable means for high-resolution structure determination of integral membrane peptides, many of which are predicted to be coded for in the human genome.

  4. Chiral organic compounds in induced cholesteric mesophases

    NASA Astrophysics Data System (ADS)

    Kutulya, Lidiya A.

    1998-09-01

    The results of original investigations being in touch with regularities of the chiral components molecular structure effect on the properties of induced cholesteric mesophases were generalized. It was shown that presence of an elongate (pi) -electron fragment in the chiral dopants molecules is general requirement of high helical twisting power ((beta) ). (beta) values and the character of temperature dependences of induced helical pitch are significantly effected by molecular shape of chiral dopants. Variation of the extent of (pi) -electron fragment anisometry, and also incorporation and variation of terminal alkyl or alkoxyl groups at chiral dopants molecules are useful approach to a regulation of temperature dependences of induced cholesteric helix pitch. Influence on thermal stability of mesophases of different types of chiral dopants was analyzed.

  5. Photonic mesophases from cut rod rotators

    SciTech Connect

    Stelson, Angela C.; Liddell Watson, Chekesha M.; Avendano, Carlos

    2016-01-14

    The photonic band properties of random rotator mesophases are calculated using supercell methods applied to cut rods on a hexagonal lattice. Inspired by the thermodynamic mesophase for anisotropic building blocks, we vary the shape factor of cut fraction for the randomly oriented basis. We find large, stable bandgaps with high gap isotropy in the inverted and direct structures as a function of cut fraction, dielectric contrast, and filling fraction. Bandgap sizes up to 34.5% are maximized at high dielectric contrast for rods separated in a matrix. The bandgaps open at dielectric contrasts as low as 2.0 for the transverse magnetic polarization and 2.25 for the transverse electric polarization. Additionally, the type of scattering that promotes the bandgap is correlated with the effect of disorder on bandgap size. Slow light properties are investigated in waveguide geometry and slowdown factors up to 5 × 10{sup 4} are found.

  6. Penetratin-induced transdermal delivery from H(II) mesophases of sodium diclofenac.

    PubMed

    Cohen-Avrahami, Marganit; Libster, Dima; Aserin, Abraham; Garti, Nissim

    2012-05-10

    Penetratin, a cell penetrating peptide is embedded within a reversed hexagonal (H(II)) mesophase for improved transdermal delivery of sodium diclofenac (Na-DFC). The H(II) mesophase serves as the solubilization reservoir and gel matrix whereas penetratin is the transdermal penetration enhancer for the drug. The systems were characterized and the interactions between the components were determined by SAXS, ATR-FTIR and SD-NMR. High affinity of Na-DFC to glycerol monooleate (GMO) was revealed, associated with increasing the order within the water channels. This affinity is enhanced upon heating and seems to be associated with GMO dehydration. Penetratin (PEN) is entrapped at the hydrophilic region of the H(II) mesophase, between the GMO headgroups, reducing the order of the system and decreasing the size of the hexagonal domains. The transdermal delivery rate of Na-DFC through porcine skin, from the H(II) mesophases, was enhanced by PEN and so also the cumulative transport crossing the skin. PEN induced accelerated drug diffusion through the stratum corneum, towards the different skin layers. The transdermal delivery enhancement is explained from the results of the ATR-FTIR analysis. It seems that PEN accelerates the structural transition of skin lipids from hexagonal to liquid. The disordering results in enhanced diffusion of Na-DFC through the stratum corneum, followed by enhanced overall penetration of the drug. Copyright © 2012 Elsevier B.V. All rights reserved.

  7. Process for the preparation of mesophase pitches

    SciTech Connect

    Tsuchitani, M.; Naito, S.; Nakajima, R.

    1989-05-11

    A process is described for preparing a mesophase pitch with a Mettler method softening point of lower than 320/sup 0/C, a mesophase content of higher than 90% when examined on a polarized microscope, a quinoline insoluble content of lower than 20% and a xylene soluble content of lower than 20% for manufacturing high performance carbon fibers comprising: (a) subjecting a heavy oil of petroleum or coal origin, or a heavy component obtainable from the heavy oil, the oil or component having substantially no xylene insoluble component, to a heat treatment in a tubular heater at a temperature of 400/sup 0/ to 600/sup 0/C under a pressure of 1 to 100 Kg/cm/sup 2/.G measured at the outlet of the tubular heater for 1 to 2000 sec so as to obtain a heat-treated material having 3 to 30 wt% of xylene insoluble component; (b) adding to the thus heat-treated material a monocyclic aromatic hydrocarbon solvent in an amount of 1 to 5 times on the heat-treated material, and recovering the newly formed insoluble component as an essentially isotropic high molecular weight bituminous material; (c) subjecting the high molecular weight bituminous material to a hydrogenation treatment at a temperature of 400/sup 0/ to 460/sup 0/C and a pressure of 20 to 200 Kg/cm/sup 2/.G with the addition of 1 to 5 times amount of a hydrogen-donating solvent based on the high molecular weight bituminous material thereby obtaining an essentially isotropic hydrogenated pitch; and (d) heat treating the hydrogenated pitch at 350/sup 0/ to 500/sup 0/C under a pressure up to atmospheric pressure to convert the hydrogenated pitch into the mesophase pitch.

  8. Optical and structural modeling of disclination lattices in carbonaceous mesophases.

    PubMed

    Gupta, Gaurav; Hwang, Dae Kun; Rey, Alejandro D

    2005-01-15

    An integrated microstructural and optical model for carbonaceous mesophases is developed and used to explain the principles that govern the formation and stability of experimentally observed disclination lattices. The model is able to capture the orientation features of disclination lattices, including the type and location of disclination lines, and the orientation field in the mesophase matrix. The optical model based on reflection polarized optical microscopy is able to replicate all the details observed in actual observations. The typical brush figures have the proper distribution, orientation, and intensity. The computational predictions offer science-based routes to create and control desirable material architectures based on carbonaceous mesophase-carbon fiber composites.

  9. Boronated mesophase pitch coke for lithium insertion

    NASA Astrophysics Data System (ADS)

    Frackowiak, E.; Machnikowski, J.; Kaczmarska, H.; Béguin, F.

    Boronated carbons from mesophase pitch have been used as materials for lithium storage in Li/carbon cells. Doping by boron has been realized by co-pyrolysis of coal tar pitch with the pyridine-borane complex. Amount of boron in mesocarbon microbeads (MCMB) varied from 1.4 to 1.8 wt.% affecting the texture of carbon. Optical microscopy and X-ray diffractograms have shown tendency to more disordered structure for boron-doped carbon. The values of specific reversible capacity ( x) varied from 0.7 to 1.1 depending significantly on the final temperature of pyrolysis (700-1150°C). The optimal charge/discharge performance was observed for boronated carbon heated at 1000°C.

  10. Stabilization and carbonization of mesophase pitch nanofiber

    NASA Astrophysics Data System (ADS)

    Fong, Hao; Reneker, Darrell H.

    2000-03-01

    Mesophase pitch nanofibers were made with diameters of several hundred nanometers to a few microns. Thermogravimetric analysis showed the stabilization reaction in air began at a temperature below 200^oC, and produced a 6% weight gain. Changes intensity of aliphatic C-H (2850-3000 and 1400-1450 cm-1) and carbonyl -CO- (1690-1750 cm-1) peaks in Fourier transform infrared spectra were observed as a result of stabilization. The intensities of aryl alkyl ether peaks at 1200-1275 cm-1 increased with stabilization in air. Solid state NMR results confirmed these changes. Carbonization in inert gas began when the temperature reached 300^oC. There was a 25% weight loss during the carbonization. Element analysis showed that the only carbon remained. The structures of pitch nanofibers, stabilized nanofibers and the resulting carbon nanofibers were investigated with scanning electron microscopy, transmission electron microscopy and X-ray diffraction.

  11. Tailoring the properties of polymers via formation of a mesophase

    SciTech Connect

    Di Girolamo, Rocco Auriemma, Finizia; De Rosa, Claudio; Malafronte, Anna

    2015-12-17

    The combination of the control of the concentration of stereodefects in isotactic polypropylene using metallocene catalysts and the crystallization via the mesophase is a strategy to tailor the mechanical properties. Stiff materials, flexible materials, and thermoplastic elastomers can be produced depending only on the concentration of rr stereodefects. We show that in the case of isotactic polypropylene (iPP) the material properties can be finely tuned at molecular level via formation of a solid mesophase, characterized by an intermediate degree of order between amorphous and crystalline state. The effect of different degree of stereoregularity on the mesophase formation, thermal stability, morphology, is analyzed at different length scales, using different technique including wide angle X-ray scattering, atomic and optical microscopy. Different morphologies are observed depending on the stereoregularity and conditions of crystallization. In contrast to the lamellar morphology of crystals normally obtained from the melt, the solid mesophase show a nodular morphology.

  12. Mesophase Separation and Probe Dynamics in Protein-Polyelectrolyte Coacervates

    NASA Astrophysics Data System (ADS)

    Kayitmazer, A. Basak; Bohidar, H. B.; Mattison, K. W.; Bose, A.; Russo, P. S.; Dubin, P. L.

    2007-03-01

    Protein-PE coacervates (PPC's) are self-assembling monophasic biomacromolecular fluids whose unique properties arise from transient heterogeneities. Among these properties are: high viscosity coupled with anomalously high protein diffusivity; rheological behavior intermediate between viscous solutions and gels; and little perturbation of protein native state. Despite their discovery 50 years ago, structure of coacervates is still poorly understood. Among the two models suggested for coacervate structure so far, we have verified the validity of one that proposes two states for protein in the coacervate. Cryo-TEM and static light scattering experiments on bovine serum albumin-poly(diallydimethylammonium chloride) coacervates have revealed heterogeneous scattering centers of several hundred nm, consistent with the presence of partially inter-connected dense domains surrounded by a large proportion of dilute domains, inferred from rheology. Fluorescence photobleaching recovery measurements of protein self-diffusion in coacervates have revealed temporal and spatial mesophasic heterogeneities over broad time and length scales; i.e. 50-700 nm and 0.5-30 sec.

  13. Chemical activation of carbon mesophase pitches.

    PubMed

    Mora, E; Blanco, C; Pajares, J A; Santamaría, R; Menéndez, R

    2006-06-01

    This paper studies the chemical activation of mesophase pitches of different origins in order to obtain activated carbons suitable for use as electrodes in supercapacitors. The effect that the activating agent (NaOH, LiOH, and KOH), the alkaline hydroxide/pitch ratio, and the activation temperature had on the characteristics of the resultant activated carbons was studied. LiOH was found to be a noneffective activating agent, while activation with NaOH and KOH yielded activated carbons with high apparent surface areas and pore volumes. The increase of the KOH/pitch ratio caused an increase of the chemical attack on the carbon, producing higher burnoffs and development of porosity. Extremely high apparent surface areas were obtained when the petroleum pitch was activated with 5:1 KOH/carbon ratio. The increase of the activation temperature caused an increase of the burnoff, although the differences were not as significant as those derived from the use of different proportions of activating agent.

  14. Solubilization of vitamin E into H(II) LLC mesophase in the presence and in the absence of vitamin C.

    PubMed

    Bitan-Cherbakovsky, Liron; Yuli-Amar, Idit; Aserin, Abraham; Garti, Nissim

    2010-03-02

    The synergistic solubilization of two major hydrophilic (vitamin C, ascorbic acid, AA) and lipophilic (vitamin E, D-alpha-tocopherol, VE) antioxidants within reverse hexagonal (H(II)) mesophases is reported. The H(II) mesophases are composed of monoolein (GMO)/VE/AA/water. A wide range of VE concentration was examined (on the expense of GMO concentrations) while the AA and water concentrations remained constant (4 and 12.5 wt %, respectively) in order to expand the H(II) mesophase. SAXS and DSC combined with ATR-FTIR techniques were utilized to study the interactions between each solubilizate and the H(II) component that enabled the synergistic accommodation of the hydrophilic and hydrophobic molecules. It was revealed that up to 27 wt % VE solubilized within the H(II) mesophase. This hydrophobic additive localized at the lipophilic GMO tail region solvating the surfactant tails, thereby enabling the formation of the H(II) structure. As a result, the lattice parameter and the melting point of the hydrophobic tails decreased. Above 27 wt % VE (up to 33 wt %), once the GMO lipophilic region was homogenously solvated, additional VE molecules located closer to the interface. At this range of concentrations, new hydrogen bonds between O-H groups of VE and O-H groups of GMO were formed. Once 35 wt % VE was introduced, the H(II) structure transformed to face-centered reverse micellar cubic phase (Fd3m, Q(227)).

  15. Food volatile compounds facilitating HII mesophase formation: solubilization and stability.

    PubMed

    Amar-Zrihen, Natali; Aserin, Abraham; Garti, Nissim

    2011-05-25

    Four lipophilic food volatile molecules of different chemical characteristics, phenylacetaldehyde, 2,6-dimethyl-5-heptenal, linalool, and trans-4-decenal, were solubilized into binary mixtures of monoolein/water, facilitating the formation of reverse hexagonal (H(II)) mesophases at room temperature without the need of solvents or triglycerides. Some of the flavor compounds are important building blocks of the hexagonal mesostructure, preventing phase transition with aging. The solubilization loads were relatively high: 12.6, 10.0, 12.6, and 10.0 wt % for phenylacetaldehyde, 2,6-dimethyl-5-heptenal, linalool, and trans-4-decenal, respectively. Phenylacetaldehyde formed mixtures of lamellar and cubic phases. Linalool, 2,6-dimethyl-5-heptenal, and trans-4-decenal induced structural shift from lamellar directly to H(II) mesophase, remaining stable at room temperature. Lattice parameters were found to increase with water content and to decrease with temperature and/or food volatile content. trans-4-Decenal produces more stable H(II) mesophase compared to linalool-loaded mesophase. At 40-60 °C, depending on the chemical structure and on the solubilization location of the food volatile compounds, the H(II) mesophase transforms to isotropic micellar phase, facilitating the release of the food volatile compounds. Molecular interactions suggest the existence of two consecutive stages in the solubilization process.

  16. Lipolysis and structure controlled drug release from reversed hexagonal mesophase.

    PubMed

    Garti, Nissim; Hoshen, Geut; Aserin, Abraham

    2012-06-01

    The present work investigates a system composed of a ternary reversed hexagonal mesophase (H(II)) loaded with a lipase for modulating drug delivery capabilities of the system. Thermomyces lanuginosa lipase was solubilized into H(II) mesophase for the benefits of continuing lipolysis of the lipids, consequently disordering and decomposing the hexagonal mesophase and thereby enhancing the diffusion of the encapsulated drug. A single transition from the H(II) structure to a random micellar phase was detected during the lipolysis. In the first lipolysis stage the hexagonal system (glycerol monooleate, tricaprylin, and water) preserved its symmetry within ca. 200 min. During this step about 40-60% molar of the lipids were hydrolyzed, and a gradual shrinking of the H(II) cylinders (decrease of 8 Å in lattice parameter) was detected. In the second lipolysis stage, the H(II) mesophase gradually disintegrated (faster rate) and the release of a model drug (sodium diclofenac) was significantly enhanced, which was assumed to be lipolysis rate-controlled. After about 15 h the H(II) mesophase was disintegrated into two dispersed immiscible phases. The release obeyed two-step Higuchi kinetics with two consecutive linear correlations of the drug release. Copyright © 2012 Elsevier B.V. All rights reserved.

  17. Mesophase pitches, carbon fiber precursors, and carbonized fibers

    SciTech Connect

    Sumner, M.B.; Hettinger, M.P.

    1993-08-24

    A process is described for the production of a stabilized carbon fiber which process comprises: forming a film having a thickness in the range of about 0.025 mm (0.001 in) to about 2.5 mm (0.1 in), of a catalytic pitch; maintaining said film at a temperature in the range of about 327 C to about 427 C and a pressure in the range of about 20 microns of mercury to about 1 atm for a time that is sufficient to produce a heavy isotropic pitch having a softening point in the range of about 127 C to about 288 C, a coking value in the range of about 55 wt % to about 95 wt %, and a maximum mesophase content of 5 vol %; agitating said heavy isotropic pitch while passing an inert gas through said heavy isotropic pitch at a rate of up to about 30 SCFH/1b at a temperature in the range of about 327 C to about 454 C for a time that is sufficient to provide a mesophase pitch having a vol. % of mesophase of at least 60; converting said mesophase pitch into green fibers; and stabilizing for a minimum time ranging from about 14 to about 288 minutes said green fibers with an oxidizing agent while heating said green fibers to a starting temperature of about 41 C to 221 C that is below the glass transition temperature of the mesophase pitch, and thereafter increasing the temperature of said green fiber at a rate of between about 1 C/min and 6 C/min to a final temperature in the range of about 282 C to 343 C to provide a stabilized carbon fiber.

  18. Columnar mesophases of hexabenzocoronene derivatives. II. Charge carrier mobility

    NASA Astrophysics Data System (ADS)

    Kirkpatrick, James; Marcon, Valentina; Kremer, Kurt; Nelson, Jenny; Andrienko, Denis

    2008-09-01

    Combining atomistic molecular dynamic simulations, Marcus-Hush theory description of charge transport rates, and master equation description of charge dynamics, we correlate the temperature-driven change of the mesophase structure with the change of charge carrier mobilities in columnar phases of hexabenzocoronene derivatives. The time dependence of fluctuations in transfer integrals shows that static disorder is predominant in determining charge transport characteristics. Both site energies and transfer integrals are distributed because of disorder in the molecular arrangement. It is shown that the contributions to the site energies from polarization and electrostatic effects are of opposite sign for positive charges. We look at three mesophases of hexabenzocoronene: herringbone, discotic, and columnar disordered. All results are compared to time resolved microwave conductivity data and show excellent agreement with no fitting parameters.

  19. Microfluidic Generation of Lipidic Mesophases for Membrane Protein Crystallization

    SciTech Connect

    Perry, S.; Roberts, G; Tice, J; Gennis, R; Kenis, P

    2009-01-01

    We report on a microfluidic method for the formation of aqueous/lipid mesophases to enable screening of suitable crystallization conditions of membrane proteins from a membrane-like phase in sub-20 nL volumes. This integrated microfluidic chip and the employed mixing strategy address the specific challenges associated with the mixing of fluids of highly different viscosities (here a factor of 30) as well as the non-Newtonian character of the resulting mesophases. The chip requires less than 20 nL of material per condition screened, whereas typically on the order of 10 {micro}L or more is needed for a batch preparation in the present screening methods. We validated our approach with the successful crystallization of the membrane protein bacteriorhodopsin.

  20. Frank elastic constants in LC mesophases of polymeric semiconductors

    NASA Astrophysics Data System (ADS)

    Gemuenden, Patrick; Kremer, Kurt; Daoulas, Kostas Ch.

    2014-03-01

    Liquid crystalline (LC) mesophases of polymeric semiconductors, e.g. poly(alkylthiophenes), can facilitate processing to obtain morphologies with improved properties. We develop a particle-based modeling approach to study nematic mesophases of such systems. The method uses soft, directional interactions and is inspired by field theoretical approaches to LCs. It enables us to generate large morphologies and calculate Frank elastic constants (FC). Besides interesting theoretical questions related to the behavior of FCs in polymer nematics, they are important when linking particle-based with continuum media descriptions of LCs. We calculate FC related to bend, splay and twist deformations from the fluctuation spectra of the local nematic director. The magnitudes of FC measured in the simulations agree with those reported in experiments on polymer nematics. We discuss their dependence on system parameters, e.g. chain length, and we compare with predictions by analytical field theory. This work was partially supported by BMBF grant MORPHEUS (FKZ 13N11704).

  1. Unusual structural evolution of poly(lactic acid) upon annealing in the presence of an initially oriented mesophase.

    PubMed

    Wang, Yaming; Li, Ming; Wang, Kaojin; Shao, Chunguang; Li, Qian; Shen, Changyu

    2014-03-14

    Uniaxial deformations of amorphous poly(lactic acid) (PLA) films were performed at two different temperatures, 70 and 80 °C, at various draw strains. The samples deformed at 70 °C showed a strain-induced mesophase, and the structural ordering and thermal stability increased as the draw strain increased. Further annealing was performed in situ at constant length at the drawing temperature of 70 °C for the films drawn to strains of 100% and 230%. Unusually, we found that after annealing, the crystal structure of the film at lower strain was more ordered than the one at higher strain. Further investigations revealed that upon annealing the structural evolution followed a distinct molecular mechanism for the samples stretched to the two draw strains. For the sample drawn to 100%, the mesophase melted very quickly upon annealing, resulting in chain randomization and the release of the constraints on the thermodynamic relaxation of the oriented amorphous chains. The chain relaxation motions had a beneficial effect on the occurrence of the conformational rearrangements that are necessary for crystalline ordering. By contrast, for the 230% sample, the melting of the mesophase was slow and most of the chain orientations were preserved upon annealing. As a result, a less ordered crystal structure was formed since the local relaxation motions that are necessary for promoting crystalline order via conformational rearrangements were hindered.

  2. Crystallizing Membrane Proteins for Structure Determination using Lipidic Mesophases

    PubMed Central

    Caffrey, Martin; Porter, Christopher

    2010-01-01

    A detailed protocol for crystallizing membrane proteins by using lipidic mesophases is described. This method has variously been referred to as the lipidic cubic phase or in meso method. The method has been shown to be quite versatile in that it has been used to solve X-ray crystallographic structures of prokaryotic and eukaryotic proteins, proteins that are monomeric, homo- and hetero-multimeric, chromophore-containing and chromophore-free, and alpha-helical and beta-barrel proteins. Recent successes using in meso crystallization are the human engineered beta2-adrenergic and adenosine A2a G protein-coupled receptors. Protocols are presented for reconstituting the membrane protein into the monoolein-based mesophase, and for setting up crystallizations in the manual mode. Additional steps in the overall process, such as crystal harvesting, are to be addressed in future video articles. The time required to prepare the protein-loaded mesophase and to set up a crystallization plate manually is about one hour. PMID:21113125

  3. Membrane protein crystallization in lipidic mesophases: detergent effects.

    PubMed Central

    Ai, X; Caffrey, M

    2000-01-01

    The "cubic phase method" for growing crystals of membrane proteins uses a complex mixture of water, lipid, protein, and other components. The current view is that the cubic phase is integral to the process. Thus additives from whatever source introduce the possibility of destabilizing the phase, thereby compromising the crystallization process. Detergents are used to solubilize membrane proteins and are likely to be ported into the cubic medium with the target protein. Depending on the identity and concentration of the detergent, the cubic phase, which itself is membranous, may be solubilized or destabilized in such a way as to render it unsuitable as a crystal growing system. The nonionic detergent n-dodecyl-beta-D-maltopyranoside is commonly used in membrane protein work. In this study, we evaluate its effect on the cubic mesophase of hydrated monoolein. X-ray diffraction was used for phase identification and mesophase microstructure characterization. The results show that while low levels of the detergent are tolerated, increasing concentrations trigger a cubic-to-lamellar phase transition in a temperature-dependent manner. This finding is rationalized in the context of complementary molecular shapes of the lipid and the detergent and has implications for the mechanism of crystallization in lipidic mesophases as discussed. PMID:10866965

  4. Crystallizing Membrane Proteins in Lipidic Mesophases. A Host Lipid Screen

    PubMed Central

    Li, Dianfan; Lee, Jean; Caffrey, Martin

    2011-01-01

    The default lipid for the bulk of the crystallogenesis studies performed to date using the cubic mesophase method is monoolein. There is no good reason however, why this 18-carbon, cis-monounsaturated monoacylglycerol should be the preferred lipid for all target membrane proteins. The latter come from an array of biomembrane types with varying properties that include hydrophobic thickness, intrinsic curvature, lateral pressure profile, lipid and protein makeup, and compositional asymmetry. Thus, it seems reasonable that screening for crystallizability based on the identity of the lipid creating the hosting mesophase would be worthwhile. For this, monoacylglycerols with differing acyl chain characteristics, such as length and olefinic bond position, must be available. A lipid synthesis and purification program is in place in the author's laboratory to serve this need. In the current study with the outer membrane sugar transporter, OprB, we demonstrate the utility of host lipid screening as a means for generating diffraction-quality crystals. Host lipid screening is likely to prove a generally useful strategy for mesophase-based crystallization of membrane proteins. PMID:21743796

  5. Crystallizing Membrane Proteins in Lipidic Mesophases. A Host Lipid Screen

    SciTech Connect

    Li, Dianfan; Lee, Jean; Caffrey, Martin

    2011-11-30

    The default lipid for the bulk of the crystallogenesis studies performed to date using the cubic mesophase method is monoolein. There is no good reason, however, why this 18-carbon, cis-monounsaturated monoacylglycerol should be the preferred lipid for all target membrane proteins. The latter come from an array of biomembrane types with varying properties that include hydrophobic thickness, intrinsic curvature, lateral pressure profile, lipid and protein makeup, and compositional asymmetry. Thus, it seems reasonable that screening for crystallizability based on the identity of the lipid creating the hosting mesophase would be worthwhile. For this, monoacylglycerols with differing acyl chain characteristics, such as length and olefinic bond position, must be available. A lipid synthesis and purification program is in place in the author's laboratory to serve this need. In the current study with the outer membrane sugar transporter, OprB, we demonstrate the utility of host lipid screening as a means for generating diffraction-quality crystals. Host lipid screening is likely to prove a generally useful strategy for mesophase-based crystallization of membrane proteins.

  6. Degree of disorder in cubic mesophases in thermotropics: thermodynamic study of a liquid crystal showing two cubic mesophases.

    PubMed

    Saito, Kazuya; Shinhara, Takashi; Nakamoto, Tadahiro; Kutsumizu, Shoichi; Yano, S; Sorai, Michio

    2002-03-01

    Heat capacity of a thermotropic mesogen ANBC(22) (4(')-alkoxy-3(')-nitrobiphenyl-4-carboxylic acid with 22 carbon atoms in alkyl chain) showing two cubic mesophases was measured by adiabatic calorimetry between 13 and 480 K. Excess enthalpies and entropies due to phase transitions were determined. A small thermal anomaly due to the cubic Im3m-->cubic Ia3d phase transition was successfully detected. Through an analysis of chain-length dependence of the entropy of transition, the sequence of two cubic mesophases (with space groups Ia3d and Im3m) is deduced for thermotropic mesogens ANBC(n). It is shown that the disorder of the core arrangement decreases in the order of Sm-C-->cubic (Im3m)-->cubic (Ia3d) while that of the chain in the reverse order cubic (Ia3d)-->cubic (Im3m)-->Sm C.

  7. A study on the effect of heat treatment temperature on mesophase development in coal tar pitch

    NASA Astrophysics Data System (ADS)

    Soni, Neha; Shah, Raviraj K.; Shrivastava, Rakesh; Datar, Manoj

    2013-06-01

    In the present study, a zero quinoline insoluble (QI) isotropic coal tar pitch was taken for the preparation of mesophase pitch. The pitch was heated in inert atmosphere at different heat treatment temperatures keeping same heating rate and soaking time to study the formation, growth and coalescence of mesophase spheres in the pitch. Such pitches were characterized for insoluble content (QI & TI), mesophase content, sulphur content, weight loss in inert atmosphere, softening point, coking value (CVC), C/H ratio etc. Results show that the insoluble content (QI & TI) and mesophase content of pitch increase with increase of heat treatment temperature.

  8. Identification of a potential conformationally disordered mesophase in a small molecule: experimental and computational approaches.

    PubMed

    Chakravarty, Paroma; Bates, Simon; Thomas, Leonard

    2013-08-05

    GNE068, a small organic molecule, was obtained as an amorphous form (GNE068-A) after isolation from ethanol and as a partially disordered form (GNE068-PC) from ethyl acetate. On subsequent characterization, GNE068-PC exhibited a number of properties that were anomalous for a two phase crystalline-amorphous system but consistent with the presence of a solid state phase having intermediate order (mesomorphous). Modulated DSC measurements of GNE068-PC revealed an overlapping endotherm and glass transition in the 135-145 °C range. ΔH of the endotherm showed strong heating rate dependence. Variable temperature XRPD (25-160 °C) revealed structure loss in GNE068-PC, suggesting the endotherm to be an "apparent melt". In addition, gentle grinding of GNE068-PC in a mortar led to a marked decrease in XRPD peak intensities, indicating a "soft" crystalline lattice. Computational analysis of XRPD data revealed the presence of two noncrystalline contributions, one of which was associated with GNE068-A. The second was a variable component that could be modeled as diffuse scattering from local disorder within the associated crystal structure, suggesting a mesomorphous system. Owing to the dominance of the noncrystalline diffuse scattering in GNE068-PC and the observed lattice deformation, the mesomorphous phase exhibited properties consistent with a conformationally disordered mesophase. Because of the intimate association of the residual solvent (ethyl acetate) with the lattice long-range order, loss of solvent on heating through the glass transition temperature of the local disorder caused irrecoverable loss of the long-range order. This precluded the observation of characteristic thermodynamic mesophase behavior above the glass transition temperature.

  9. Crowded Star Mesogens: Guest-Controlled Stability of Mesophases from Unconventional Liquid-Crystal Molecules.

    PubMed

    Lehmann, Matthias; Maier, Philipp; Grüne, Matthias; Hügel, Markus

    2017-01-23

    The molecular design of crowded hexasubstituted star mesogens based on a benzene core and alternating substitution with oligo(phenylenevinylene) arms and aryl units generates free space between the conjugated arm scaffolds. Various arylcarboxy building blocks, decorated with alkoxy chains, have been incorporated in the void by mixing, hydrogen bonding or covalent bonds to the aryl groups. The mesogens assemble in columnar stacks ranging from soft crystals to rectangular and hexagonal columnar liquid crystals, revealed by polarized optical microscopy, differential scanning calorimetry, X-ray scattering and modelling. The stability of the mesophases is crucially influenced by the binding mode of the arylcarboxy guest building blocks. The origin of the variation in clearing temperature is unravelled by modelling, cohesive energy density considerations and solid-state NMR spectroscopy. The control over the transition temperature is important for the formation of aligned thin films and thus for potential applications.

  10. Controlling enzymatic activity and kinetics in swollen mesophases by physical nano-confinement.

    PubMed

    Sun, Wenjie; Vallooran, Jijo J; Zabara, Alexandru; Mezzenga, Raffaele

    2014-06-21

    Bicontinuous lipid cubic mesophases are widely investigated as hosting matrices for functional enzymes to build biosensors and bio-devices due to their unique structural characteristics. However, the enzymatic activity within standard mesophases (in-meso) is severely hindered by the relatively small diameter of the mesophase aqueous channels, which provide only limited space for enzymes, and restrict them into a highly confined environment. We show that the enzymatic activity of a model enzyme, horseradish peroxidase (HRP), can be accurately controlled by relaxing its confinement within the cubic phases' water channels, when the aqueous channel diameters are systematically swollen with varying amount of hydration-enhancing sugar ester. The in-meso activity and kinetics of HRP are then systematically investigated by UV-vis spectroscopy, as a function of the size of the aqueous mesophase channels. The enzymatic activity of HRP increases with the swelling of the water channels. In swollen mesophases with water channel diameter larger than the HRP size, the enzymatic activity is more than double that measured in standard mesophases, approaching again the enzymatic activity of free HRP in bulk water. We also show that the physically-entrapped enzymes in the mesophases exhibit a restricted-diffusion-induced initial lag period and report the first observation of in-meso enzymatic kinetics significantly deviating from the normal Michaelis-Menten behaviour observed in free solutions, with deviations vanishing when enzyme confinement is released by swelling the mesophase.

  11. Nanoconfinement crystallization of frustrated alkyl groups: crossover of mesophase to crystalline structure.

    PubMed

    Shi, Haifeng; Wang, Haixia; Xin, John H; Zhang, Xingxiang; Wang, Dujin

    2011-04-07

    Crossover of mesophase to crystalline structure in the nanoconfinement crystallization process of frustrated side groups elucidates the critical crystal thickness d(c) or the length scale of side groups, which defines the transition process from mesophase (hexagonal and monoclinic phase) to crystalline phase (orthorhombic phase) of confined CH(2) sequences in a given crystal size restriction.

  12. Positional, reorientational, and bond orientational order in DNA mesophases.

    PubMed

    Lorman, V; Podgornik, R; Zeks, B

    2001-11-19

    We investigate the orientational order of transverse polarization vectors of long, stiff polymer molecules and their coupling to bond orientational and positional order in high density mesophases. Homogeneous ordering of transverse polarization vector promotes distortions in the hexatic phase, whereas inhomogeneous ordering precipitates crystallization of the 2D sections with different orientations of the transverse polarization vector on each molecule in the unit cell. We propose possible scenarios for going from the hexatic phase, through the distorted hexatic phase, to the crystalline phase with an orthorhombic unit cell observed experimentally for the case of DNA.

  13. Magnetic alignment of mesophase pitch-based carbon fibers

    NASA Astrophysics Data System (ADS)

    Matthews, M. J.; Dresselhaus, M. S.; Dresselhaus, G.; Endo, M.; Nishimura, Y.; Hiraoka, T.; Tamaki, N.

    1996-07-01

    Mesophase pitch-based carbon fibers (MPCFs) have recently been developed for use as high performance anode materials in Li ion secondary batteries, having a microscopic as well as macroscopic structure especially suitable for Li storage. Because of the highly anisotropic diamagnetic moment observed between 50 and 310 K in pristine milled MPCF segments, they can easily be oriented parallel to an applied magnetic field, as observed by scanning electron microscopy. A simple model is proposed to explain both the observed alignment of undoped fibers and the suppression of alignment in B-doped MPCFs for relatively small applied magnetic fields, because of their smaller diamagnetic moment.

  14. Influence of powder properties on the sintering of polyaromatic mesophases to high-strength isotropic graphite

    SciTech Connect

    Braun, M.; Gschwindt, A.; Hoffmann, W.R.

    1995-09-01

    The paper reviews the state of the art in sintering of polyaromatic mesophase powders to high-strength isotropic carbons and graphites. Synthesis of mesophase pitches from different precursor materials (petroleum- and coal tar pitch) using a net thermal or a catalyzed process, the preparation of mesophase powders from mesophase pitches and the influence of the powder properties on the sintering are discussed. Special attention is given to the role of thermoplasticity and the particle size of the mesophase powder as key properties for the production of high-strength carbons and graphites. After a graphitization treatment, isotropic graphites with a flexural strength of 160 MPa can be obtained, a value which probably represents an upper limit.

  15. Large-amplitude motion in polymer crystals and mesophases

    SciTech Connect

    Wunderlich, B. |

    1994-12-31

    Large-amplitude motion of macromolecules involves mainly rotation about bonds (conformational motion). In the liquid phases, the large- amplitude motion is coupled with disorder and accounts for the flow and viscoelastic behavior. Perfectly ordered crystals, in contrast, permit only little large-amplitude motion. The mesophases are intermediate in order and mobility. In crystals, large-amplitude motion leads initially to gauche defects and kinks (conformational defects), and ultimately may produce conformationally disordered crystals (conis crystals). Molecular dynamics simulations of crystals with up to 30,000 atoms have been carried out and show the mechanism of defect formation, permit the study of the distribution of defects, and the visualization of hexagonal crystals. Distinction between main-chain liquid-crystalline macromolecules and condis crystals, the two mesophases of polymers, can be done on basis of analysis of phase separation (partial crystallinity), present in condis crystals and not in liquid crystals. Solid state NMR is the tool of choice for detecting mobile and rigid phases. In highly drawn fibers one can find four different states of order and mobility. Besides the (defect) crystalline phase and the isotropic amorphous phase, an intermediate oriented phase and a rigid amorphous phase exists.

  16. Effect of sodium diclofenac loads on mesophase components and structure.

    PubMed

    Efrat, Rivka; Shalev, Deborah E; Hoffman, Roy E; Aserin, Abraham; Garti, Nissim

    2008-07-15

    We studied the effect of a model electrolytic drug on intermolecular interactions, conformational changes, and phase transitions in structured discontinuous cubic QL lyotropic liquid crystals. These changes were due to competition with hydration of the lipid headgroups. Structural changes of the phase induced by solubilization loads of sodium diclofenac (Na-DFC) were investigated by directly observing the water, ethanol, and Na-DFC components of the resulting phases using 2H and 23Na NMR. Na-DFC interacted with the surfactant glycerol monoolein (GMO) at the interface while interfering with the mesophase curvature and also competed with hydration of the surfactant headgroups. Increasing quantities of solubilized Na-DFC promoted phase transitions from cubic phase (discontinuous (QL) and bicontinuous (Q)) into lamellar structures and subsequently into a disordered lamellar phase. Quadrupolar coupling of deuterated ethanol by 2H NMR showed that it is located near the headgroups of the lipid and apparently is hydrogen bonded to the GMO headgroups. A phase transition between two lamellar phases (L alpha to L alpha*) was seen by 23Na NMR of Na-DFC at a concentration where the characteristics of the drug change from kosmotropic to chaotropic. These findings show that loads of solubilized drug may affect the structure of its vehicle and, as a result, its transport across skin-blood barriers. The structural changes of the mesophase may also aid controlled drug delivery.

  17. Mesophase separation in polyelectrolyte-mixed micelle coacervates.

    PubMed

    Dubin, Paul L; Li, Yajuan; Jaeger, Werner

    2008-05-06

    Mesophase separation has been identified in a polycation/anionic-nonionic mixed micelle system formed by the coacervation of poly(diallyldimethylammoniumchloride)/sodium dodecylsulfate-Triton X-100 in 0.40 M NaCl. The resultant dense, optically clear fluid was studied by turbidity, dynamic light scattering (DLS), and rheology. The presence of two diffusion modes in DLS points to microscopic heterogeneity: coexistence of micelle-rich (dense) domains with micelle-poor (dilute) domains. With an increase in temperature above 20 degrees C, the turbidity rises rapidly along with the intensity of the slow mode. The concomitant decrease in the diffusivity of the slow mode signals an increase in the effective viscosity of the dense domain. With further increase in temperature, dramatic shear thinning is observed, and finally, macroscopic phase separation can be identified by centrifugation. At a temperature near that for quiescent phase separation, we observe shear-induced phase separation. We propose a mechanism to explain the connection between temperature- and shear-induced mesophase separation.

  18. HIV-TAT enhances the transdermal delivery of NSAID drugs from liquid crystalline mesophases.

    PubMed

    Cohen-Avrahami, Marganit; Shames, Alexander I; Ottaviani, M Francesca; Aserin, Abraham; Garti, Nissim

    2014-06-12

    Sodium diclofenac (Na-DFC) and celecoxib (CLXB) are common nonsteroidal anti-inflammatory (NSAID) drugs which suffer from poor bioavailability and severe side effects when consumed orally, and their transdermal delivery might present important advantages. In this study, the drugs were solubilized in cubic and lamellar mesophases as transdermal delivery vehicles, and a cell-penetrating peptide, HIV-TAT (TAT), was examined as a skin penetration enhancer. SD-NMR, ATR-FTIR, and EPR measurements revealed that, in the cubic mesophase (which is rich in water content), TAT populates the aqueous cores and binds water, while in the dense lamellar system (with the lower water content) TAT is bound also to the glycerol monooleate (GMO) and increases the microviscosity and the order degree. TAT secondary structure in the cubic system was found to be a random coil while once it was embedded in the closely packed lamellar system it transforms to a more ordered compact state of β-turns arranged around the GMO headgroups. TAT remarkably increased the diffusion of Na-DFC and CLXB from the cubic systems by 6- and 9-fold enhancement, respectively. TAT effect on drug diffusion from the lamellar systems was limited to an increase of 1.3- and 1.7-fold, respectively. The dense packing and strong binding in the lamellar phase led to slow diffusion rates and slower drug release in controlled pattern. These effects of the chemical composition and vehicle geometry on drug diffusion are demonstrated with the impacts of TAT which can be specifically utilized for controlling skin delivery of drugs as required.

  19. Lysozyme entrapped within reverse hexagonal mesophases: physical properties and structural behavior.

    PubMed

    Mishraki, Tehila; Libster, Dima; Aserin, Abraham; Garti, Nissim

    2010-01-01

    A model protein (lysozyme) was incorporated into monoolein-based reverse hexagonal (H(II)) mesophase and its structure effects were characterized by small angle X-ray scattering, ATR-FTIR spectroscopy, and rheological measurements. Modifications in molecular organization of the H(II) mesophases as well as the conformational stability of lysozyme (LSZ) as a function of pH and denaturating agent (urea) were clarified. Up to 3 wt.% LSZ can be solubilized into the H(II). The vibration FTIR analysis revealed that LSZ interacted with OH groups of glycerol monooleate (GMO) in the outer interface region, resulting in strong hydrogen bonding between the surfactant and its environment. Simultaneously, the decrease in the hydrogen-bonded carbonyl population of GMO was monitored, indicating dehydration of the monoolein carbonyls. These molecular interactions yielded a minor decrease in the lattice parameter of the systems, as detected by small angle X-ray scattering. Furthermore, LSZ was crystallized within the medium of the hexagonal structures in a single crystal form. The alpha-helix conformation of lysozyme was stabilized at high pH conditions, demonstrating greater helical structure content, compared to D(2)O solution. Moreover, the hexagonal phase decreased the unfavorable alpha-->beta transition in lysozyme, thereby increasing the stability of the protein under chemical denaturation. The rheological behavior of the hexagonal structures varied with the incorporation of LSZ, reflected in stronger elastic properties and pronounced solid-like response of the systems. The hydrogen bonding enhancement in the interface region of the structures was most likely responsible for these phenomena. The results of this study provided valuable information on the use of hexagonal systems as a carrier for incorporation and stabilization of proteins for various applications.

  20. Controlling enzymatic activity and kinetics in swollen mesophases by physical nano-confinement

    NASA Astrophysics Data System (ADS)

    Sun, Wenjie; Vallooran, Jijo J.; Zabara, Alexandru; Mezzenga, Raffaele

    2014-05-01

    Bicontinuous lipid cubic mesophases are widely investigated as hosting matrices for functional enzymes to build biosensors and bio-devices due to their unique structural characteristics. However, the enzymatic activity within standard mesophases (in-meso) is severely hindered by the relatively small diameter of the mesophase aqueous channels, which provide only limited space for enzymes, and restrict them into a highly confined environment. We show that the enzymatic activity of a model enzyme, horseradish peroxidase (HRP), can be accurately controlled by relaxing its confinement within the cubic phases' water channels, when the aqueous channel diameters are systematically swollen with varying amount of hydration-enhancing sugar ester. The in-meso activity and kinetics of HRP are then systematically investigated by UV-vis spectroscopy, as a function of the size of the aqueous mesophase channels. The enzymatic activity of HRP increases with the swelling of the water channels. In swollen mesophases with water channel diameter larger than the HRP size, the enzymatic activity is more than double that measured in standard mesophases, approaching again the enzymatic activity of free HRP in bulk water. We also show that the physically-entrapped enzymes in the mesophases exhibit a restricted-diffusion-induced initial lag period and report the first observation of in-meso enzymatic kinetics significantly deviating from the normal Michaelis-Menten behaviour observed in free solutions, with deviations vanishing when enzyme confinement is released by swelling the mesophase.Bicontinuous lipid cubic mesophases are widely investigated as hosting matrices for functional enzymes to build biosensors and bio-devices due to their unique structural characteristics. However, the enzymatic activity within standard mesophases (in-meso) is severely hindered by the relatively small diameter of the mesophase aqueous channels, which provide only limited space for enzymes, and restrict them

  1. An investigation of the kinetics of the mesophase transformations in petroleum pitch by the ESR method

    SciTech Connect

    Samoilov, V.M.; Frolov, V.I.; Kotosonov, A.S.; Ostronov, B.G.; Rumyantsev, S.M.

    1983-01-01

    The amount of ..cap alpha../sub 1/ fraction, the concentration of paramagnetic centers, and the width of the line of the ESR signal have been determined for samples of mesophase pitches obtained by treating an initial petroleum pitch at 400-440/sup 0/C. The applicability of the ESR method for studying the kinetics and mechanism of the process of mesophase transformations has been shown. From the change in the parameters studied the rate constants and activation energies of the processes of the formation and growth of the aromatic regions of polyconjugation and of the accumulation of mesophase have been calculated.

  2. Method for producing mesophase-containing pitch by using carrier gas

    SciTech Connect

    Watanabe, M.

    1984-12-11

    A method for producing a mesophase-containing pitch from petroleum pitch or coal tar pitch is disclosed. According to this method volatile distillate fractions, which are harmful to mesophase formation and present originally in the raw material pitch or formed as by-product during heat treatment time are driven off by using a carrier gas at a temperature of 360/sup 0/ to 450/sup 0/ C. in order to shorten the overall heat treatment time and advance the mesophase formation smoothly by the increase of stirring effect.

  3. The Significant Structure Theory Applied to a Mesophase System

    PubMed Central

    Ma, Shao-mu; Eyring, H.

    1975-01-01

    The significant structure theory of liquids is extended to the mesophase system with p-azoxyanisole as an example. This compound has two different structures, a nematic phase and an isotropic phase, in its liquid state. In this study the nematic phase is treated as subject to a second volume and temperature-dependent degeneracy formally like that due to melting. The isotropic phase is treated as a normal liquid. The specific heat, thermal expansion coefficient, compressibility, volume, entropy of transitions, and heat of transitions are calculated and compared to the observed values. This analysis differs from previous ones in including the volume dependence as well as the temperature dependence in one explicit expression for the Helmholtz free energy. PMID:16592217

  4. Preparation of mesophase pitch by aromatics-rich distillate of naphthenic vacuum gas oil.

    PubMed

    Li, Ming; Liu, Dong; Du, Hui; Li, Qinyin; Hou, Xulian; Ye, Jiashun

    Two aromatics-rich distillates R1 and R2 with different properties from naphthenic base vacuum gas oil were used for preparing mesophase pitch through high-pressure thermal treatment. (1)H-NMR, FT-IR and VPO were employed to characterize the structural parameters of the raw materials. The products' optical texture and molecular structure were analyzed by polarized light optical microscopy, (1)H-NMR, FT-IR and XRD. The effect of raw materials' structure on the formation of mesophase pitch was discussed. The results showed that the structure of the raw material had an important effect on the formation of mesophase pitch. The raw material R2 with higher aromaticity, more naphthenic structure and less alkyl side chains was easy to form mesophase pitch with large-domains optical texture, lower softening point and more ordered crystal structure.

  5. An amorphous mesophase generated by thermal annealing for high-performance organic photovoltaic devices.

    PubMed

    Tanaka, Hideyuki; Abe, Yoko; Matsuo, Yutaka; Kawai, Junya; Soga, Iwao; Sato, Yoshiharu; Nakamura, Eiichi

    2012-07-10

    Thermal annealing of a p-i-n organic photovoltaic device containing a crystalline benzoporphyrin donor and solvated crystals of a silylmethylfullerene acceptor increases the device performance at a temperature where partial desolvation of the acceptor produces an amorphous mesophase. This suggests that the mesophase improves the hierarchical ordering of the materials, that is, the morphology of the n-layer and the interfacial contact and, hence, the carrier generation efficiency at the donor-acceptor interface.

  6. Enzyme Kinetics in Liquid Crystalline Mesophases: Size Matters, But Also Topology.

    PubMed

    Sun, Wenjie; Vallooran, Jijo J; Mezzenga, Raffaele

    2015-04-21

    Lyotropic liquid crystalline systems (LLCs) are excellent immobilizing carriers for enzymes, due to their biocompatibility and well-defined pore nanostructure. Here we show that the liquid crystalline mesophase topology can greatly influence the enzymatic activity in a typical peroxidase (Horseradish peroxidase, HRP) enzymatic reaction. Enzyme kinetics was investigated in different LLC mesophases based on monolinolein, with varying symmetries and dimensions such as the 1D cylindrical inverse hexagonal phase (HII), the 2D planar lamellar phase (Lα), and two 3D bicontinuous cubic phases of double diamond (Pn3m) and gyroid (Ia3d) space groups. As expected, the mesophase with largest water channel size shows highest activity, regardless of the topology. Interestingly, however, when mesophases with different topologies have the same water channel size, then the topology plays the dominant role, and the enzyme showed the highest activity in the 3D tetra-fold connected Pn3m, followed by the Ia3d with trifold connectivity, and finally the 1D HII phase. This study demonstrates that the enzymatic activity in LLC mesophases depends on both the water channel size and the topology of the mesophase.

  7. Effects of Detergent β-Octylglucoside and Phosphate Salt Solutions on Phase Behavior of Monoolein Mesophases

    PubMed Central

    Khvostichenko, Daria S.; Ng, Johnathan J.D.; Perry, Sarah L.; Menon, Monisha; Kenis, Paul J.A.

    2013-01-01

    Using small-angle x-ray scattering (SAXS), we investigated the phase behavior of mesophases of monoolein (MO) mixed with additives commonly used for the crystallization of membrane proteins from lipidic mesophases. In particular, we examined the effect of sodium and potassium phosphate salts and the detergent β-octylglucoside (βOG) over a wide range of compositions relevant for the crystallization of membrane proteins in lipidic mesophases. We studied two types of systems: 1), ternary mixtures of MO with salt solutions above the hydration boundary; and 2), quaternary mixtures of MO with βOG and salt solutions over a wide range of hydration conditions. All quaternary mixtures showed highly regular lyotropic phase behavior with the same sequence of phases (Lα, Ia3d, and Pn3m) as MO/water mixtures at similar temperatures. The effects of additives in quaternary systems agreed qualitatively with those found in ternary mixtures in which only one additive is present. However, quantitative differences in the effects of additives on the lattice parameters of fully hydrated mesophases were found between ternary and quaternary mixtures. We discuss the implications of these findings for mechanistic investigations of membrane protein crystallization in lipidic mesophases and for studies of the suitability of precipitants for mesophase-based crystallization methods. PMID:24138861

  8. Supercritical fluid extraction: Preparing a superior mesophase precursor for carbon fibers. Final report

    SciTech Connect

    Thies, M.C.

    1994-08-01

    Supercritical fluid (SCF) extraction is being investigated for the production of mesophase pitch, the liquid-crystalline precursor for the manufacture of high-performance carbon fibers. The mesophase pitch is produced by fractionation of an isotropic petroleum pitch with supercritical toluene in a region of liquid-liquid equilibrium that exists at pressures above 40 bar. Dramatic improvements in the reliability of the apparatus have recently been made, and mesophase pitch can now be produced on a routine basis. An experimental program was conducted to explore the effects of temperature, solvent-to-pitch (S/P) ratio, and solvent solubility parameter on the properties of the mesophase pitch produced. Temperatures of 320 and 360 deg C, solubility parameters of 3.7 and 5.0 (cal/cc)(1/2), and S/P ratios of 2.5 and 3.5 were chosen to conform to a two-level, augmented factorial experiment. A linear model correlated the data to a high degree of certainty. Results indicate that the authors can adjust SCF operating conditions and tailor-make a mesophase pitch for a given end use. They have discovered a semitheoretical method for predicting a priori the softening point and yield of mesophase pitch for a given set of SCF operating conditions. The SCF extraction process can be represented on a pseudoternary phase diagram, and good estimates of product yields and softening points can be made from a limited experimental data measured at other conditions.

  9. HII mesophase as a drug delivery system for topical application of methyl salicylate.

    PubMed

    Liang, Xin; Chen, Yu-Lin; Jiang, Xiao-Jing; Wang, Sheng-Mei; Zhang, Ji-Wen; Gui, Shuang-Ying

    2017-03-30

    The main objective of this study was to develop reversed hexagonal (HII) mesophase for transdermal delivery of methyl salicylate. The formulation was prepared, characterized and evaluated for its skin penetration in vitro and skin retention in vivo. Preliminary pharmacodynamics and skin irritation were also investigated. The formulation was identified as hexagonal structure. In vitro study exhibited that HII mesophase enhanced the skin permeation by delivering 2.61 times more methyl salicylate than the commercially available cream. Meanwhile, HII mesophase presented higher bioavailability as AUC(0-24) and AUC(0-∞) were 32.894μg·mL(-1) and 32.935μg·mL(-1) respectively, while the cream were 12.791μg·mL(-1) and 12.970μg·mL(-1). Preliminary pharmacodynamics studies demonstrated that HII mesophase possessed anti-inflammatory and analgesic effects for inhibiting paw edema, granuloma and pain. MeSa HII mesophase showed no skin irritation on the normal rat skin. Thus, HII mesophase was considered as an effective delivery system for MeSa.

  10. Influence of the counteranion on the ability of 1-dodecyl-3-methyltriazolium ionic liquids to form mesophases

    SciTech Connect

    Stappert, Kathrin; Unal, Derya; Spielberg, Eike T.; Mudring, Anja -Verena

    2014-11-25

    The influence of the counteranion on the ability of the mesogenic cation 1-methyl-3-dodecyl-triazolium to form mesophases is explored. To that avail, salts of the cation with anions of different size, shape, and hydrogen bonding capability such as Cl, Br, I, I3, PF6, and Tf2N [bis(trifluorosulfonyl)amide] were synthesized and characterized. The crystal structures of the bromide, the iodide, and the triiodide reveal that the cations form bilayers with cations oriented in opposite directions featuring interdigitated alkyl tails. Within the layers, the cations are separated by anions. The rod-shaped triiodide anion forces the triazolium cation to align with it in this crystal structure but due to its space requirement reduces the alkyl chain interdigitation which prevents the formation of a mesophase. Rather the compound transforms directly from a crystalline solid to an (ionic) liquid like the analogous bis(trifluorosulfonyl)amide. In contrast, the simple halides and the hexafluorophosphate form liquid crystalline phases. As a result, their clearing points shift with increasing anion radius to lower temperatures.

  11. Influence of the counteranion on the ability of 1-dodecyl-3-methyltriazolium ionic liquids to form mesophases

    DOE PAGES

    Stappert, Kathrin; Unal, Derya; Spielberg, Eike T.; ...

    2014-11-25

    The influence of the counteranion on the ability of the mesogenic cation 1-methyl-3-dodecyl-triazolium to form mesophases is explored. To that avail, salts of the cation with anions of different size, shape, and hydrogen bonding capability such as Cl–, Br–, I–, I3–, PF6–, and Tf2N– [bis(trifluorosulfonyl)amide] were synthesized and characterized. The crystal structures of the bromide, the iodide, and the triiodide reveal that the cations form bilayers with cations oriented in opposite directions featuring interdigitated alkyl tails. Within the layers, the cations are separated by anions. The rod-shaped triiodide anion forces the triazolium cation to align with it in this crystalmore » structure but due to its space requirement reduces the alkyl chain interdigitation which prevents the formation of a mesophase. Rather the compound transforms directly from a crystalline solid to an (ionic) liquid like the analogous bis(trifluorosulfonyl)amide. In contrast, the simple halides and the hexafluorophosphate form liquid crystalline phases. As a result, their clearing points shift with increasing anion radius to lower temperatures.« less

  12. Mesophases in polyethylene, polypropylene, and poly(1-butene)

    SciTech Connect

    Androsch, Rene J; Di Lorenzo, Maria; Schick, Christoph; Wunderlich, Bernhard {nmn}

    2010-01-01

    This paper contains new views about the amorphous and partially ordered phases of the three polymers listed in the title. The discussion is based on information on structure, thermodynamic stability, and large-amplitude molecular motion. Polyethylene is the basic backbone of all alkene polymers, and the other two are the first members of the vinyl polymers which have stereospecifically placed alkyl side chains. Their multiphase structures consist of metastable crystals, mesophases, and surrounding rigid and mobile amorphous fractions. All these phases have sizes ranging from micrometer dimensions down to nanometers. Besides the phase structures, information about the molecular coupling between the phases must be considered. Depending on temperature, the polymer phases can vary from solid (rigid) to liquid (mobile). New knowledge is also gained by cross-comparison of the title polymers. The experimental information was gained from (a) various forms of slow, fast, and temperature-modulated thermal analysis to identify equilibrium and non-equilibrium states, (b) measurement of structure and morphology at various length scales, and (c) tracing of the large-amplitude molecular motion, the kinetics of order/disorder changes, and the liquid/solid transitions (glass transitions). It is shown that much more needs to be known about the various phases and their coupling to characterize a given polymer and to fine-tune its properties for a given application.

  13. DNA mesophases induced by spermidine: structural properties and biological implications.

    PubMed Central

    Pelta, J; Durand, D; Doucet, J; Livolant, F

    1996-01-01

    Conditions of formation of DNA aggregates by the addition of spermidine were determined with 146 base pair DNA fragments as a function of spermidine and NaCl concentration. Two different phases of spermidine-DNA complexes are obtained: a cholesteric liquid crystalline phase with a large helical pitch, with interhelix distances ranging from 31.6 to 32.6 A, and a columnar hexagonal phase with a restricted fluidity in which DNA molecules are more closely packed (29.85 +/- 0.05 A). In both phases, the DNA molecule retains its B form. These phases are always observed in equilibrium with the dilute isotropic solution, and their phase diagram is defined for a DNA concentration of 1 mg/ml. DNA liquid crystalline phases induced by spermidine are compared with the DNA mesophases already described in concentrated solutions in the absence of spermidine. We propose that the liquid crystalline character of the spermidine DNA complexes is involved in the stimulation of the functional properties of the DNA reported in numerous experimental articles, and we discuss how the nature of the phase could regulate the degree of activity of the molecule. Images FIGURE 4 FIGURE 5 FIGURE 6 FIGURE 8 FIGURE 10 PMID:8804588

  14. Osmotically Induced Reversible Transitions in Lipid-DNA Mesophases

    PubMed Central

    Danino, Dganit; Kesselman, Ellina; Saper, Gadiel; Petrache, Horia I.; Harries, Daniel

    2009-01-01

    We follow the effect of osmotic pressure on isoelectric complexes that self-assemble from mixtures of DNA and mixed neutral and cationic lipids. Using small angle x-ray diffraction and freeze-fracture cryo-electron microscopy, we find that lamellar complexes known to form in aqueous solutions can reversibly transition to hexagonal mesophases under high enough osmotic stress exerted by adding a neutral polymer. Using molecular spacings derived from x-ray diffraction, we estimate the reversible osmotic pressure-volume (Π-V) work needed to induce this transition. We find that the transition free energy is comparable to the work required to elastically bend lipid layers around DNA. Consistent with this, the required work is significantly lowered by an addition of hexanol, which is known to soften lipid bilayers. Our findings not only help to resolve the free-energy contributions associated with lipid-DNA complex formation, but they also demonstrate the importance that osmotic stress can have to the macromolecular phase geometry in realistic biological environments. PMID:19348739

  15. Osmotically induced reversible transitions in lipid-DNA mesophases.

    PubMed

    Danino, Dganit; Kesselman, Ellina; Saper, Gadiel; Petrache, Horia I; Harries, Daniel

    2009-04-08

    We follow the effect of osmotic pressure on isoelectric complexes that self-assemble from mixtures of DNA and mixed neutral and cationic lipids. Using small angle x-ray diffraction and freeze-fracture cryo-electron microscopy, we find that lamellar complexes known to form in aqueous solutions can reversibly transition to hexagonal mesophases under high enough osmotic stress exerted by adding a neutral polymer. Using molecular spacings derived from x-ray diffraction, we estimate the reversible osmotic pressure-volume (Pi-V) work needed to induce this transition. We find that the transition free energy is comparable to the work required to elastically bend lipid layers around DNA. Consistent with this, the required work is significantly lowered by an addition of hexanol, which is known to soften lipid bilayers. Our findings not only help to resolve the free-energy contributions associated with lipid-DNA complex formation, but they also demonstrate the importance that osmotic stress can have to the macromolecular phase geometry in realistic biological environments.

  16. Mesophase stabilization in ionic liquid crystals through pairing equally shaped mesogenic cations and anions

    SciTech Connect

    Stappert, Kathrin; Lipinski, Gregor; Kopiec, Gabriel; Spielberg, Eike T.; Mudring, Anja -Verena

    2015-07-23

    The synthesis and properties of a set of novel ionic liquid crystals with congruently shaped cations and anions are reported to check whether pairing mesogenic cations with mesogenic anions leads to a stabilization of a liquid crystalline phase. To that avail 1-alkyl-3-methyl-triazolium cations with an alkyl chain length of 10, 12, and 14 carbon atoms have been combined with p-alkyloxy-benzenesulfonate anions with different alkyl chain lengths (n = 10, 12, and 14). The corresponding triazolium iodides have been synthesized as reference compounds where the cation and anion have strong size and shape mismatch. The mesomorphic behavior of all compounds is studied by differential scanning calorimetry and polarizing optical microscopy. All compounds except 1-methyl-3-decyltriazolium iodide, which qualifies as an ionic liquid, are thermotropic ionic liquid crystals. All other compounds adopt smectic A phases. As a result, a comparison of the thermal phase behavior of the 1-methyl-3-decyltriazolium bromides to the corresponding p-alkoxy-benzensulfonates reveals that definitely the mesophase is stabilized by pairing the rod-shaped 1-alkyl-3-methyltriazolium cation with a rod-like anion of similar size.

  17. Mesophase stabilization in ionic liquid crystals through pairing equally shaped mesogenic cations and anions

    DOE PAGES

    Stappert, Kathrin; Lipinski, Gregor; Kopiec, Gabriel; ...

    2015-07-23

    The synthesis and properties of a set of novel ionic liquid crystals with congruently shaped cations and anions are reported to check whether pairing mesogenic cations with mesogenic anions leads to a stabilization of a liquid crystalline phase. To that avail 1-alkyl-3-methyl-triazolium cations with an alkyl chain length of 10, 12, and 14 carbon atoms have been combined with p-alkyloxy-benzenesulfonate anions with different alkyl chain lengths (n = 10, 12, and 14). The corresponding triazolium iodides have been synthesized as reference compounds where the cation and anion have strong size and shape mismatch. The mesomorphic behavior of all compounds ismore » studied by differential scanning calorimetry and polarizing optical microscopy. All compounds except 1-methyl-3-decyltriazolium iodide, which qualifies as an ionic liquid, are thermotropic ionic liquid crystals. All other compounds adopt smectic A phases. As a result, a comparison of the thermal phase behavior of the 1-methyl-3-decyltriazolium bromides to the corresponding p-alkoxy-benzensulfonates reveals that definitely the mesophase is stabilized by pairing the rod-shaped 1-alkyl-3-methyltriazolium cation with a rod-like anion of similar size.« less

  18. 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

  19. An X-ray transparent microfluidic platform for screening of the phase behavior of lipidic mesophases.

    PubMed

    Khvostichenko, Daria S; Kondrashkina, Elena; Perry, Sarah L; Pawate, Ashtamurthy S; Brister, Keith; Kenis, Paul J A

    2013-09-21

    Lipidic mesophases are a class of highly ordered soft materials that form when certain lipids are mixed with water. Understanding the relationship between the composition and the microstructure of mesophases is necessary for fundamental studies of self-assembly in amphiphilic systems and for applications, such as the crystallization of membrane proteins. However, the laborious formulation protocol for highly viscous mesophases and the large amounts of material required for sample formulation are significant obstacles in such studies. Here we report a microfluidic platform that facilitates investigations of the phase behavior of mesophases by reducing sample consumption 300-fold, and automating and parallelizing sample formulation. The mesophases were formulated on-chip using less than 80 nL of material per sample and their microstructure was analyzed in situ using small-angle X-ray scattering (SAXS). The 220 μm-thick X-ray compatible platform was comprised of thin polydimethylsiloxane (PDMS) layers sandwiched between cyclic olefin copolymer (COC) sheets. Uniform mesophases were prepared using an active on-chip mixing strategy coupled with periodic cooling of the sample to reduce viscosity. We validated the platform by preparing and analyzing mesophases of the lipid monoolein (MO) mixed with aqueous solutions of different concentrations of β-octylglucoside (βOG), a detergent frequently used in membrane protein crystallization. Four samples were prepared in parallel on chip, by first metering and automatically diluting βOG to obtain detergent solutions of different concentration, then metering MO, and finally mixing by actuation of pneumatic valves. Integration of detergent dilution and subsequent mixing significantly reduced the number of manual steps needed for sample preparation. Three different types of mesophases typical for MO were successfully identified in SAXS data from on-chip samples. Microstructural parameters of identical samples formulated in

  20. Controlling molecular transport and sustained drug release in lipid-based liquid crystalline mesophases.

    PubMed

    Zabara, Alexandru; Mezzenga, Raffaele

    2014-08-28

    Lipid-based lyotropic liquid crystals, also referred to as reversed liquid crystalline mesophases, such as bicontinuous cubic, hexagonal or micellar cubic phases, have attracted deep interest in the last few decades due to the possibility of observing these systems at thermodynamic equilibrium in excess water conditions. This becomes of immediate significance for applications in the colloidal environment, such as in the food, cosmetic and pharmaceutical arenas. One possible application regarded as very promising is that of controlled delivery of functional ingredients. Different crystallographic structures of the lipid mesophase give access to different diffusion coefficients and distinct diffusion modes. It becomes thus crucial to engineer the space group of the mesophase in a controlled way, and ideally, in a stimuli-responsive manner. In this article we review the state of the art on diffusion and molecular transport in lipid-based mesophases and we discuss recent contributions to the controlled delivery of molecules and colloids through these systems. In particular we focus on the different available strategies relying on either endogenous or exogenous stimuli to induce changes in the symmetry and transport properties of lipid-based mesophases and we discuss the impact and implications this may have on controlled drug delivery.

  1. Dynamics of edge dislocations in a sheared lamellar mesophase.

    PubMed

    Kumaran, V

    2013-10-07

    The dynamics and interactions of edge dislocations in a nearly aligned sheared lamellar mesophase is analysed to provide insights into the relationship between disorder and rheology. First, the mesoscale permeation and momentum equations for the displacement field in the presence of external forces are derived from the model H equations for the concentration and momentum field. The secondary flow generated due to the mean shear around an isolated defect is calculated, and the excess viscosity due to the presence of the defect is determined from the excess energy dissipation due to the secondary flow. The excess viscosity for an isolated defect is found to increase with system size in the cross-stream direction as L(3/2) for an isolated defect, though this divergence is cut-off due to interactions in a defect suspension. As the defects are sheared past each other due to the mean flow, the Peach-Koehler force due to elastic interaction between pairs of defects is found to cause no net displacement relative to each other as they approach from large separation to the distance of closest approach. The equivalent force due to viscous interactions is found to increase the separation for defects of opposite sign, and decrease the separation for defects of same sign. During defect interactions, we find that there is no buckling instability due to dilation of layers for systems of realistic size. However, there is another mechanism, which is the velocity difference generated across a slightly deformed bilayer due to the mean shear, which could result in the creation of new defects.

  2. Dynamics of edge dislocations in a sheared lamellar mesophase

    NASA Astrophysics Data System (ADS)

    Kumaran, V.

    2013-10-01

    The dynamics and interactions of edge dislocations in a nearly aligned sheared lamellar mesophase is analysed to provide insights into the relationship between disorder and rheology. First, the mesoscale permeation and momentum equations for the displacement field in the presence of external forces are derived from the model H equations for the concentration and momentum field. The secondary flow generated due to the mean shear around an isolated defect is calculated, and the excess viscosity due to the presence of the defect is determined from the excess energy dissipation due to the secondary flow. The excess viscosity for an isolated defect is found to increase with system size in the cross-stream direction as L3/2 for an isolated defect, though this divergence is cut-off due to interactions in a defect suspension. As the defects are sheared past each other due to the mean flow, the Peach-Koehler force due to elastic interaction between pairs of defects is found to cause no net displacement relative to each other as they approach from large separation to the distance of closest approach. The equivalent force due to viscous interactions is found to increase the separation for defects of opposite sign, and decrease the separation for defects of same sign. During defect interactions, we find that there is no buckling instability due to dilation of layers for systems of realistic size. However, there is another mechanism, which is the velocity difference generated across a slightly deformed bilayer due to the mean shear, which could result in the creation of new defects.

  3. Broadening of mesophase temperature range induced by doping calamitic mesogen with banana-shaped mesogen

    NASA Astrophysics Data System (ADS)

    Cvetinov, Miroslav; Stojanović, Maja; Obadović, Dušanka; Vajda, Aniko; Fodor-Csorba, Katalin; Eber, Nandor

    2016-03-01

    We have investigated three binary mixtures composed of selected banana-shaped dopant in low concentrations and calamitic mesogen in high. Banana-shaped dopant forms a B7 phase, while the calamitic mesogen exhibit nematic and smectic SmA and SmC phases. The occurring mesophases have been identified by their optical textures. At dopant concentrations of 2.2 and 3.1 mol%, there is evident broadening of nematic and smectic SmA temperature ranges in respect to the pure calamitic compound. Yet, the mixture with dopant concentration of 7 mol% exhibits narrower temperature ranges of mesophases. Increasing dopant concentration caused lowering of all phase transitions temperatures (TI-N, TN-SmA, TSmA-SmC) in all investigated mixtures. Therefore, mixing classic calamitic compounds with novel banana-shaped compound in low concentrations is viable way to attain useful mesophase range for application in industry.

  4. H(II) mesophase and peptide cell-penetrating enhancers for improved transdermal delivery of sodium diclofenac.

    PubMed

    Cohen-Avrahami, Marganit; Aserin, Abraham; Garti, Nissim

    2010-06-01

    This study develops a novel transdermal delivery vehicle for the enhanced delivery of sodium diclofenac (Na-DFC). The system utilizes the advantages of reversed hexagonal lyotropic liquid crystals (H(II)LC), combined with a peptide cell penetration enhancer (CPE), creating together an adaptable system that provides versatile options in the field of transdermal delivery. This enhancer peptide is based on a family of amphipatic peptides that exhibit improved membrane permeability. Franz permeation cell experiments revealed that the peptide enhancer (RALA) improved Na-DFC skin penetration of the liquid crystal 2.2-fold. We studied the structural effects of RALA solubilization on the H(II) mesophase. RALA acts as a chaotropic agent, interfering in the structure of the water, and causes a measurable swelling of the aqueous cylinders by 5A. Small angle X-ray scattering (SAXS) and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) measurements reveal enhanced hydration of the glycerol monooleate (GMO) headgroups and a 6.5% increase in the fraction of non-freezable water resulting from RALA incorporation. RALA caused a gradual increase in the GMO effective headgroup area due to the hydration, leading eventually to a transform of the hexagonal structure towards a lamellar one. Circular dichroism and ATR-FTIR measurements showed a conservation of the peptide structure when incorporated into the H(II) mesophase. The combined H(II)LC-CPE systems can serve as high potential vehicles for a variety of drugs, as they can easily be modified by varying the composition and temperature, according to the required dose and delivery features.

  5. The effect of dendrimer generations on the structure of Q(G) LLC mesophase and drug release.

    PubMed

    Bitan-Cherbakovsky, Liron; Aserin, Abraham; Garti, Nissim

    2014-10-01

    In this paper the cosolubilization of 2nd, 3rd, and 4th generations of polypropyleneimine (PPI: PPI-G2, -G3, and -G4) dendrimers with sodium diclofenac (Na-DFC) into reverse gyroid cubic (Q(G)) liquid crystals is reported. Structural properties and interactions of PPI dendrimers with and without the drug were studied using small-angle X-ray scattering, attenuated total reflected Fourier transform infrared (ATR-FTIR) spectroscopy, and differential scanning calorimetry (DSC) measurements. Incorporation of PPI-G2 (without Na-DFC) into Q(G) mesophase led to a decrease of 78Å in the lattice parameter. Solubilization of higher PPI generations, G3 and G4, led to increases in the lattice parameter to 57Å and 64Å, respectively. At 25wt%, each of the dendrimers caused a phase transition Q(G)→reverse hexagonal (HII). According to ATR-FTIR and DSC, the large lattice parameter values of G3 and G4 (relative to G2) embedment were assigned to their interactions with the carboxyl groups of GMO at the interface in comparison to the strong interaction of PPI-G2 with the water. Cosolubilization of Na-DFC with PPI-G2 revealed enlargement of the lattice parameter (of the new HII mesophase), while in the case of G3 and G4 systems no significant influence was seen with Na-DFC. The release of Na-DFC from Q(G) and HII systems was followed by UV-vis spectroscopy and revealed generation-dependence on drug release. As dendrimer generation increased, the cumulative drug release decreased.

  6. The Dependency of Nematic and Twist-bend Mesophase Formation on Bend Angle

    PubMed Central

    Mandle, Richard J.; Archbold, Craig T.; Sarju, Julia P.; Andrews, Jessica L.; Goodby, John W.

    2016-01-01

    We have prepared and studied a family of cyanobiphenyl dimers with varying linking groups with a view to exploring how molecular structure dictates the stability of the nematic and twist-bend nematic mesophases. Using molecular modelling and 1D 1H NOESY NMR spectroscopy, we determine the angle between the two aromatic core units for each dimer and find a strong dependency of the stability of both the nematic and twist-bend mesophases upon this angle, thereby satisfying earlier theoretical models. PMID:27819300

  7. X-ray characterization of mesophases of human telomeric G-quadruplexes and other DNA analogues

    NASA Astrophysics Data System (ADS)

    Yasar, Selcuk; Schimelman, Jacob B.; Aksoyoglu, M. Alphan; Steinmetz, Nicole F.; French, Roger H.; Parsegian, V. Adrian; Podgornik, Rudolf

    2016-06-01

    Observed in the folds of guanine-rich oligonucleotides, non-canonical G-quadruplex structures are based on G-quartets formed by hydrogen bonding and cation-coordination of guanosines. In dilute 5‧-guanosine monophosphate (GMP) solutions, G-quartets form by the self-assembly of four GMP nucleotides. We use x-ray diffraction to characterize the columnar liquid-crystalline mesophases in concentrated solutions of various model G-quadruplexes. We then probe the transitions between mesophases by varying the PEG solution osmotic pressure, thus mimicking in vivo molecular crowding conditions. Using the GMP-quadruplex, built by the stacking of G-quartets with no covalent linking between them, as the baseline, we report the liquid-crystalline phase behaviors of two other related G-quadruplexes: (i) the intramolecular parallel-stranded G-quadruplex formed by the 22-mer four-repeat human telomeric sequence AG3(TTAG3)3 and (ii) the intermolecular parallel-stranded G-quadruplex formed by the TG4T oligonucleotides. Finally, we compare the mesophases of the G-quadruplexes, under PEG-induced crowding conditions, with the corresponding mesophases of the canonical duplex and triplex DNA analogues.

  8. X-ray characterization of mesophases of human telomeric G-quadruplexes and other DNA analogues

    SciTech Connect

    Yasar, Selcuk; Schimelman, Jacob B.; Aksoyoglu, M. Alphan; Steinmetz, Nicole F.; French, Roger H.; Parsegian, V. Adrian; Podgornik, Rudolf

    2016-06-02

    We report that observed in the folds of guanine-rich oligonucleotides, non-canonical G-quadruplex structures are based on G-quartets formed by hydrogen bonding and cation-coordination of guanosines. In dilute 5'-guanosine monophosphate (GMP) solutions, G-quartets form by the self-assembly of four GMP nucleotides. We use x-ray diffraction to characterize the columnar liquid-crystalline mesophases in concentrated solutions of various model G-quadruplexes. We then probe the transitions between mesophases by varying the PEG solution osmotic pressure, thus mimicking in vivo molecular crowding conditions. Using the GMP-quadruplex, built by the stacking of G-quartets with no covalent linking between them, as the baseline, we report the liquid-crystalline phase behaviors of two other related G-quadruplexes: (i) the intramolecular parallel-stranded G-quadruplex formed by the 22-mer four-repeat human telomeric sequence AG3 (TTAG3)3 and (ii) the intermolecular parallel-stranded G-quadruplex formed by the TG(4)T oligonucleotides. Finally, we compare the mesophases of the G-quadruplexes, under PEG-induced crowding conditions, with the corresponding mesophases of the canonical duplex and triplex DNA analogues.

  9. X-ray characterization of mesophases of human telomeric G-quadruplexes and other DNA analogues

    DOE PAGES

    Yasar, Selcuk; Schimelman, Jacob B.; Aksoyoglu, M. Alphan; ...

    2016-06-02

    We report that observed in the folds of guanine-rich oligonucleotides, non-canonical G-quadruplex structures are based on G-quartets formed by hydrogen bonding and cation-coordination of guanosines. In dilute 5'-guanosine monophosphate (GMP) solutions, G-quartets form by the self-assembly of four GMP nucleotides. We use x-ray diffraction to characterize the columnar liquid-crystalline mesophases in concentrated solutions of various model G-quadruplexes. We then probe the transitions between mesophases by varying the PEG solution osmotic pressure, thus mimicking in vivo molecular crowding conditions. Using the GMP-quadruplex, built by the stacking of G-quartets with no covalent linking between them, as the baseline, we report the liquid-crystallinemore » phase behaviors of two other related G-quadruplexes: (i) the intramolecular parallel-stranded G-quadruplex formed by the 22-mer four-repeat human telomeric sequence AG3 (TTAG3)3 and (ii) the intermolecular parallel-stranded G-quadruplex formed by the TG(4)T oligonucleotides. Finally, we compare the mesophases of the G-quadruplexes, under PEG-induced crowding conditions, with the corresponding mesophases of the canonical duplex and triplex DNA analogues.« less

  10. X-ray characterization of mesophases of human telomeric G-quadruplexes and other DNA analogues

    PubMed Central

    Yasar, Selcuk; Schimelman, Jacob B.; Aksoyoglu, M. Alphan; Steinmetz, Nicole F.; French, Roger H.; Parsegian, V. Adrian; Podgornik, Rudolf

    2016-01-01

    Observed in the folds of guanine-rich oligonucleotides, non-canonical G-quadruplex structures are based on G-quartets formed by hydrogen bonding and cation-coordination of guanosines. In dilute 5′-guanosine monophosphate (GMP) solutions, G-quartets form by the self-assembly of four GMP nucleotides. We use x-ray diffraction to characterize the columnar liquid-crystalline mesophases in concentrated solutions of various model G-quadruplexes. We then probe the transitions between mesophases by varying the PEG solution osmotic pressure, thus mimicking in vivo molecular crowding conditions. Using the GMP-quadruplex, built by the stacking of G-quartets with no covalent linking between them, as the baseline, we report the liquid-crystalline phase behaviors of two other related G-quadruplexes: (i) the intramolecular parallel-stranded G-quadruplex formed by the 22-mer four-repeat human telomeric sequence AG3(TTAG3)3 and (ii) the intermolecular parallel-stranded G-quadruplex formed by the TG4T oligonucleotides. Finally, we compare the mesophases of the G-quadruplexes, under PEG-induced crowding conditions, with the corresponding mesophases of the canonical duplex and triplex DNA analogues. PMID:27249961

  11. A narrow ESR signal and mesophase transformations in the heat treatment of coals and pitches

    SciTech Connect

    Farber, M.S.

    1982-01-01

    The author discusses changes in the EPR spectrum when coal, pitch and its fractions are heated directly in the spectrometer resonator. It is shown that the high temperature maximum of EPR signals is determined to a significant extent by the narrow signal. This suggests that the narrow signal spectrum is related to the mesophase structures during the synthesis process.

  12. Supramolecular structures and columnar mesophase induction in nondiscoid pyrazoles by complexation to rhodium(I).

    PubMed

    Giménez, Raquel; Elduque, Anabel; López, José Antonio; Barbera, Joaquín; Cavero, Emma; Lantero, Ignacio; Oro, Luis A; Serrano, José Luis

    2006-12-11

    Several new cis-[RhCl(CO)2(Ln)] complexes have been prepared using different polycatenar pyrazole ligands (Ln) in order to obtain columnar liquid crystalline arrangements. The topology of the ligand plays an essential role, and a mesophase is induced at room temperature from a nonmesogenic pyrazole only when it is symmetrically substituted with six decyloxy chains. The single-crystal structure of a methoxy-substituted analogue, 3,5-bis(3,4,5-trimethoxyphenyl)pyrazole, is formed by globular tetrameric structures held together by H-bonding. However, parallel dimers are present in the corresponding cis-chlorodicarbonylrhodium(I) complex, a situation that explains the induction of a columnar mesophase in the decyloxy-substituted complex. The XRD pattern of the mesophase is consistent with a hexagonal symmetry in which the columns are formed by molecules assembled in an antiparallel mode. The crystal-to-mesophase transition was also detected by spectroscopic techniques as a shift in the IR carbonyl stretching bands and the appearance of a charge-transfer band in the absorption spectrum with thermochromic behavior.

  13. Development of Direct and Optical Polarized Nuclear Magnetic Resonance (NMR) Methods for Characterization and Engineering of Mesophased Molecular Structures

    SciTech Connect

    Maxwell, R; Baumann, T; Taylor, B

    2002-01-29

    The development of NMR methods for the characterization of structure and dynamics in mesophase composite systems was originally proposed in this LDRD. Mesophase systems are organic/inorganic hybrid materials whose size and motional properties span the definition of liquids and solids, such as highly viscous gels or colloidal suspensions. They are often composite, ill defined, macromolecular structures that prove difficult to characterize. Mesophase materials are of broad scientific and programmatic interest and include composite load bearing foams, aerogels, optical coatings, silicate oligomers, porous heterogeneous catalysts, and nanostructured materials such as semiconductor quantum dot superlattices. Since mesophased materials and precursors generally lack long-range order they have proven to be difficult to characterize beyond local, shortrange order. NMR methods are optimal for such a task since NMR observables are sensitive to wide ranges of length (0-30{angstrom}) and time (10{sup -9}-10{sup 0}sec) scales. We have developed a suit of NMR methods to measure local, intermediate, and long range structure in a series of mesophase systems and have constructed correlations between NMR observables and molecular size, topology, and network structure. The goal of this research was the development of a strong LLNL capability in the characterization of mesophased materials by NMR spectroscopy that will lead to a capability in rational synthesis of such materials and a fundamental understanding of their structure-property relationships. We demonstrate our progress towards attaining this goal by presenting NMR results on four mesophased model systems.

  14. High performance carbon fibers from mesophases produced by supercritical fluid extraction

    NASA Astrophysics Data System (ADS)

    Dauche, Franck Michel

    The purpose of this research is to investigate the potential of supercritical fluid extraction for the production of an improved precursor for the manufacture of high thermal conductivity carbon fibers. Mesophase pitch fractions were produced by the continuous fractionation of an isotropic petroleum-based pitch with supercritical toluene in a region of liquid-liquid equilibrium. A statistical experimental design was used to investigate a region of extraction operating conditions from which the fractions were expected to exhibit superior spinnability. Chemical and physical characterizations were performed on the fractions, and the results were used to explore the effect of the extraction conditions on the mesophase properties. DRIFT data were shown to be particularly useful for characterizing the chemical composition of the mesophase fractions produced, and GPC was successfully used to determine their molecular weight distribution. Two thermodynamic models based on the SAFT equation together with (1) the concepts of continuous thermodynamics (2) molecular weight information on the oligomeric nature of the feed pitch were used to correlate the measured results. By using three adjustable parameters, solvent compositions and molecular weight distributions in each phase were calculated. Although the oligomeric model is able to qualitatively represent trends observed in the data, it cannot as yet be used to quantitatively predict phase compositions. Based on the characterizations of the supercritically extracted mesophases produced, selected fractions were melt-spun into round- and ribbon-shaped fibers using a laboratory-scale melt-spinning apparatus. It was found that a relatively narrow window of mesophase properties and compositions allowed fiber making without off-gassing. For a given spinnable mesophase, wide angle X-ray diffraction was used on as-spun fibers produced over a wide range of spinning temperatures to evaluate their potential to yield, after proper heat

  15. Fast acquisition of multidimensional NMR spectra of solids and mesophases using alternative sampling methods.

    PubMed

    Lesot, Philippe; Kazimierczuk, Krzysztof; Trébosc, Julien; Amoureux, Jean-Paul; Lafon, Olivier

    2015-11-01

    Unique information about the atom-level structure and dynamics of solids and mesophases can be obtained by the use of multidimensional nuclear magnetic resonance (NMR) experiments. Nevertheless, the acquisition of these experiments often requires long acquisition times. We review here alternative sampling methods, which have been proposed to circumvent this issue in the case of solids and mesophases. Compared to the spectra of solutions, those of solids and mesophases present some specificities because they usually display lower signal-to-noise ratios, non-Lorentzian line shapes, lower spectral resolutions and wider spectral widths. We highlight herein the advantages and limitations of these alternative sampling methods. A first route to accelerate the acquisition time of multidimensional NMR spectra consists in the use of sparse sampling schemes, such as truncated, radial or random sampling ones. These sparsely sampled datasets are generally processed by reconstruction methods differing from the Discrete Fourier Transform (DFT). A host of non-DFT methods have been applied for solids and mesophases, including the G-matrix Fourier transform, the linear least-square procedures, the covariance transform, the maximum entropy and the compressed sensing. A second class of alternative sampling consists in departing from the Jeener paradigm for multidimensional NMR experiments. These non-Jeener methods include Hadamard spectroscopy as well as spatial or orientational encoding of the evolution frequencies. The increasing number of high field NMR magnets and the development of techniques to enhance NMR sensitivity will contribute to widen the use of these alternative sampling methods for the study of solids and mesophases in the coming years. Copyright © 2015 John Wiley & Sons, Ltd.

  16. Mesoscopic structure and properties of liquid crystalline mesophase pitch and its transformation into carbon fiber.

    PubMed

    Mochida, Isao; Yoon, Seong-Ho; Korai, Yozo

    2002-01-01

    The history and present state of the art in the chemistry of mesophase pitch, which is an important precursor for carbon fiber and other high-performance industrial carbons, are reviewed relative to their structural properties. The structural concepts in both microscopic and macroscopic views are summarized in terms of the sp(2) carbon hexagonal plane as a basic unit common to graphitic materials, its planar stacking in clusters, and cluster assembly into microdomains and domains, the latter of which reflect the isochromatic unit of optical anisotropy. Such a series of structural units is described in a semiquantitative manner corresponding to the same units of graphitic materials, although the size and stacking height of the hexagonal planes (graphitic sheets) are very different. Mesophase pitch is a liquid crystal material whose basic structural concepts are maintained in the temperature range of 250 to 350 degrees C. The melt flow and thermal properties are related to its micro- and mesoscopic structure. The structure of mesophase-pitch-based carbon fiber of high tensile strength, modulus, and thermal conductivity has been formed through spinning, and has inherited the same structural concepts of mesophase pitch. Stabilization settles the structure in successive heat treatments up to 3000 degrees C. Carbonization and graphitization enable growth of the hexagonal planes and their stacking into units of graphite. Such growth is governed and controlled by the alignment of micro- and mesoscopic structures in the mesophase pitch, which define the derived carbon materials as nanostructural materials. Their properties are controlled by the nanoscopic units that are expected to behave as nanomaterials when appropriately isolated or handled.

  17. Changes in the microstructure and characteristics of carbon/carbon composites with mesophase mesocarbon microbeads added during graphitization

    SciTech Connect

    Hu, H.L.; Ko, T.H.; Ku, W.S.

    2005-12-05

    Carbon/carbon (C/C) composites were prepared from oxidative PAN fiber felts, a resol-type phenolic resin, and mesophase pitch derived from coal tar. In this study, the effects on mesocarbon microbeads (MCMBs), flexural strength, flexural moduli, electric conductivity, and thermal conductivity of C/C composites with a mesophase content ranging from 0 to 30 wt % were examined during pyrolysis. The results show that the C/C composite with the addition of 10-30 wt % mesophase had a higher density, greater stacking size, and higher preferred orientation than the C/C composites without any mesophase during heat treatment. These composites also exhibited an improvement in flexural strength from 19.7 to 30.3%. The flexural moduli of these composites with mesophase added increased by 15.1 to 31.3% compared to that with no mesophase added. These composites also showed improved electric conductivity, from 15.1 to 43.7%, and thermal conductivity, from 12 to 31.3%.

  18. Formulation and characterization of a liquid crystalline hexagonal mesophase region of phosphatidylcholine, sorbitan monooleate, and tocopherol acetate for sustained delivery of leuprolide acetate.

    PubMed

    Báez-Santos, Yahira M; Otte, Andrew; Mun, Ellina A; Soh, Bong-Kwan; Song, Chang-Geun; Lee, Young-Nam; Park, Kinam

    2016-11-30

    Although liquid crystal (LC) systems have been studied before, their utility in drug delivery applications has not been explored in depth. This study examined the development of a 1-month sustained release formulation of leuprolide acetate using an in situ-forming LC matrix. The phase progression upon water absorption was tested through construction of ternary phase diagrams of phosphatidylcholine, sorbitan monooleate, and tocopherol acetate (TA) at increasing water content. Small angle X-ray scattering revealed the presence of lamellar and hexagonal mesophases. The physicochemical characteristics and in vitro drug release were evaluated as a function of the ternary component ratio and its resultant phase behavior. Formulations with increased water uptake capacity displayed greater drug release and enhanced erodability. Removal of TA resulted in increased water uptake capacity and drug release, where 8% (w/w) TA was determined as the critical concentration threshold for divergence of release profiles. In conclusion, characterization of the resultant HII mesophase region provided information of the impact the individual components have on the physicochemical properties and potential drug release mechanisms. This high mitigating impact of TA on drug release indicates the use of TA as a tailoring agent, broadening the therapeutic applications of this LC system. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Aligned nanostructured polymers by magnetic-field-directed self-assembly of a polymerizable lyotropic mesophase.

    PubMed

    Tousley, Marissa E; Feng, Xunda; Elimelech, Menachem; Osuji, Chinedum O

    2014-11-26

    Magnetic-field-directed assembly of lyotropic surfactant mesophases provides a scalable approach for the fabrication of aligned nanoporous polymers by templated polymerization. We develop and characterize a lyotropic liquid crystalline system containing hexagonally packed cylindrical micelles of a polymerizable surfactant in a polymerizable solvent. The system exhibits negative magnetic anisotropy, resulting in the degenerate alignment of cylindrical micelles perpendicular to the magnetic field. Sample rotation during field alignment is used to effectively break this degeneracy and enable the production of uniformly well-aligned mesophases. High-fidelity retentions of the hexagonal structure and alignment were successfully achieved in polymer films produced upon UV exposure of the reactive system. The success of this effort provides a route for the fabrication of aligned nanoporous membranes suitable for highly selective separations, sensing, and templated nanomaterial synthesis.

  20. Magnetic materials based on iron dispersed in graphitic matrices II. High temperatures and mesophase pitch

    NASA Astrophysics Data System (ADS)

    Dyakonov, Alexander J.; Jack McCormick, B.; Kahol, Pawan K.; Hamdeh, Hussein H.

    1997-03-01

    Ferromagnetic materials based on iron incorporated into pitch were synthesized, and characterized by magnetic methods (Faraday), Mössbauer spectroscopy, SEM, and XRD. A graphitic-type structure was observed to form at 350-1650°C. The important role of a mesophase structure of a pitch-precursor in the iron carbonyl absorption and anisotropic structure of the resulting iron containing material was found.

  1. Mesophase pitch-based carbon fiber for improved inflammability of CFRP

    SciTech Connect

    Nakagoshi, Akira; Tomonoh, Shigeki; Sakamoto, Yosihiro

    1995-10-01

    Carbon Fiber Reinforced Plastics (CFRP) are extensively used because of their favorable physical properties such as high strength-to-weight ratio and small thermal expansion. However, flammability of CFRP has limited their application especially in the transportation and industrial field. Exposed to flame, CFRP laminates made of PAN-based carbon fibers burst into flame in short time, while CFRP laminates made from mesophase pitch-based carbon fibers don`t burst into flame. This paper describes the experimental results of local heating test by gas burner. When the flame temperature was 1,000 C, a CFRP laminate made from PAN-based carbon fiber burned within 40 sec. Under the same condition, a CFRP laminate made from mesophase pitch-based carbon fiber didn`t burn in 10 min. The matrix resin of both laminates was 250 F curable epoxy resin. This behavior mainly depends upon the thermal conductivity of the carbon fibers. The mesophase pitch-based carbon fibers have high thermal conductivity, so they can diffuse thermal energy and lower laminate surface temperature. On the other hand, PAN-based carbon fibers have low thermal conductivity, so they can`t diffuse thermal energy enough, and the laminates made from them burn easily. Mechanical properties of CFRP during local heating test in comparison with Aluminum plate are also discussed.

  2. Interface tuning and stabilization of monoglyceride mesophase dispersions: Food emulsifiers and mixtures efficiency.

    PubMed

    Serieye, Sébastien; Méducin, Fabienne; Milošević, Irena; Fu, Ling; Guillot, Samuel

    2017-06-15

    Several food surfactants were examined as possible efficient emulsifiers for liquid crystalline monolinolein-based particles and as alternative choices to the non-food-grade emulsifier conventionally used Pluronic® F127. We described a food emulsifiers' toolbox, investigating their ability to emulsify mesophases (stabilization capacity, particle size, zeta potential) and their impact on internal nanostructures (from swelling to drastic modifications). Among the selected surfactants, sucrose stearate (S1670) was found to be the best candidate for replacing in a long term F127 as an efficient stabilizer of lipid particles. The emulsification performed by mixing F127 with S1670 or sodium caseinate (NaCas), and S1670/NaCas helped to discriminate their respective role in the particles and so their efficiency for the stabilization. In case of S1670 as co-emulsifier no strong structural modification was observed, while using F127 (25wt% NaCas) an unexpected hexagonal mesophase was highlighted in self-assemblies. The evolution of zeta potentials by varying the mesophase and the emulsifier also informed about the distribution of co-surfactants in the particles. We thus reported submicronic nanostructured systems (from 100 to 350nm) that were fully food-grade and possibly contained limonene, with a surface charge from -70 to -5mV.

  3. Crystallizing membrane proteins for structure-function studies using lipidic mesophases.

    PubMed

    Caffrey, Martin

    2011-06-01

    The lipidic cubic phase method for crystallizing membrane proteins has posted some high-profile successes recently. This is especially true in the area of G-protein-coupled receptors, with six new crystallographic structures emerging in the last 3½ years. Slowly, it is becoming an accepted method with a proven record and convincing generality. However, it is not a method that is used in every membrane structural biology laboratory and that is unfortunate. The reluctance in adopting it is attributable, in part, to the anticipated difficulties associated with handling the sticky viscous cubic mesophase in which crystals grow. Harvesting and collecting diffraction data with the mesophase-grown crystals is also viewed with some trepidation. It is acknowledged that there are challenges associated with the method. However, over the years, we have worked to make the method user-friendly. To this end, tools for handling the mesophase in the pico- to nano-litre volume range have been developed for efficient crystallization screening in manual and robotic modes. Glass crystallization plates have been built that provide unparalleled optical quality and sensitivity to nascent crystals. Lipid and precipitant screens have been implemented for a more rational approach to crystallogenesis, such that the method can now be applied to a wide variety of membrane protein types and sizes. In the present article, these assorted advances are outlined, along with a summary of the membrane proteins that have yielded to the method. The challenges that must be overcome to develop the method further are described.

  4. Structural and optical investigations of TGBA and TGBC mesophases exhibiting cylindrical and cone-like domain textures

    NASA Astrophysics Data System (ADS)

    Ribeiro, A. C.; Oswald, L.; Nicoud, J. F.; Guillon, D.; Galerne, Y.

    1998-02-01

    The characterization by optical microscopy, X-ray diffraction and differential scanning calorimetry of two new liquid crystalline compounds is presented. The compounds under consideration incorporate in their molecules two chiral centres (one asymmetric carbon and one asymmetric sulphur of a sulphinate group). While the carbon chirality is fixed in the R configuration the sulphur chirality may be either in the S or in the R configuration. A TGBA mesophase in a large temperature domain is evidenced for one of the two diastereomers, while both TGBA and TGBC mesophases are observed in a similar temperature domain for the other one. For both diastereomers and in both mesophases it is possible to observe the coexistence of two different types of optical textures, namely planar cholesteric textures and developable domains. The latter are coiled in a different way than proposed in an earlier publication. More precisely, they form cylindrical or cone-like domains with double-twist properties as observed in the blue phases. The pitch of the helix in the TGB mesophases is evaluated by means of optical reflection observations in samples exhibiting the planar cholesteric textures. For both diastereomers it is also possible to evaluate structural parameters related to the organization within the TGBA mesophases. Finally, the induced phase transition TGBC-SC* is studied by the application of an AC electric field.

  5. Sodium diclofenac and cell-penetrating peptides embedded in H(II) mesophases: physical characterization and delivery.

    PubMed

    Cohen-Avrahami, Marganit; Libster, Dima; Aserin, Abraham; Garti, Nissim

    2011-09-01

    Glycerol monooleate (GMO)-based mesophases offer extensive prospects for incorporation of various bioactive molecules. This work deals with the solubilization of selected cell-penetrating peptides (CPPs) together with sodium diclofenac (Na-DFC) within the H(II) mesophase for transdermal applications. The effect of CPPs such as RALA (an amphipatic CPP), penetratin (PEN), and oligoarginine (NONA) on Na-DFC skin permeation kinetics to provide controlled release and tune the drug transdermal diffusion was studied. The location of the drug and the CPPs within the mesophase was probed by DSC and FTIR. Na-DFC was found to be located at the interfacial region between the surfactant chains, leading to denser H(II) mesophase. The hydrophilic NONA was intercalated into the aqueous cylinders and caused their swelling. It induced a significant decrease in the hydrogen binding between the GMO carbonyls and their surrounding. The amphiphilic PEN was entrapped within two different regions, depending on its concentration. PEN and NONA improved Na-DFC permeation by 100%, whereas RALA enhanced permeation by 50%. When estimating Na-DFC migration rate out of the mesophase toward surrounding aqueous media, it appeared to be slower with the CPPs. The peptides were not involved at this diffusion-controlled step. It seems that their effect on skin permeation is based on their specific interaction with the skin.

  6. A macroscopic H+ and Cl- ions pump via reconstitution of EcClC membrane proteins in lipidic cubic mesophases.

    PubMed

    Speziale, Chiara; Salvati Manni, Livia; Manatschal, Cristina; Landau, Ehud M; Mezzenga, Raffaele

    2016-07-05

    Functional reconstitution of membrane proteins within lipid bilayers is crucial for understanding their biological function in living cells. While this strategy has been extensively used with liposomes, reconstitution of membrane proteins in lipidic cubic mesophases presents significant challenges related to the structural complexity of the lipid bilayer, organized on saddle-like minimal surfaces. Although reconstitution of membrane proteins in lipidic cubic mesophases plays a prominent role in membrane protein crystallization, nanotechnology, controlled drug delivery, and pathology of diseased cells, little is known about the molecular mechanism of protein reconstitution and about how transport properties of the doped mesophase mirror the original molecular gating features of the reconstituted membrane proteins. In this work we design a general strategy to demonstrate correct functional reconstitution of active and selective membrane protein transporters in lipidic mesophases, exemplified by the bacterial ClC exchanger from Escherichia coli (EcClC) as a model ion transporter. We show that its correct reconstitution in the lipidic matrix can be used to generate macroscopic proton and chloride pumps capable of selectively transporting charges over the length scale of centimeters. By further exploiting the coupled chloride/proton exchange of this membrane protein and by combining parallel or antiparallel chloride and proton gradients, we show that the doped mesophase can operate as a charge separation device relying only on the reconstituted EcClC protein and an external bias potential. These results may thus also pave the way to possible applications in supercapacitors, ion batteries, and molecular pumps.

  7. A macroscopic H+ and Cl− ions pump via reconstitution of EcClC membrane proteins in lipidic cubic mesophases

    PubMed Central

    Speziale, Chiara; Salvati Manni, Livia; Manatschal, Cristina; Landau, Ehud M.; Mezzenga, Raffaele

    2016-01-01

    Functional reconstitution of membrane proteins within lipid bilayers is crucial for understanding their biological function in living cells. While this strategy has been extensively used with liposomes, reconstitution of membrane proteins in lipidic cubic mesophases presents significant challenges related to the structural complexity of the lipid bilayer, organized on saddle-like minimal surfaces. Although reconstitution of membrane proteins in lipidic cubic mesophases plays a prominent role in membrane protein crystallization, nanotechnology, controlled drug delivery, and pathology of diseased cells, little is known about the molecular mechanism of protein reconstitution and about how transport properties of the doped mesophase mirror the original molecular gating features of the reconstituted membrane proteins. In this work we design a general strategy to demonstrate correct functional reconstitution of active and selective membrane protein transporters in lipidic mesophases, exemplified by the bacterial ClC exchanger from Escherichia coli (EcClC) as a model ion transporter. We show that its correct reconstitution in the lipidic matrix can be used to generate macroscopic proton and chloride pumps capable of selectively transporting charges over the length scale of centimeters. By further exploiting the coupled chloride/proton exchange of this membrane protein and by combining parallel or antiparallel chloride and proton gradients, we show that the doped mesophase can operate as a charge separation device relying only on the reconstituted EcClC protein and an external bias potential. These results may thus also pave the way to possible applications in supercapacitors, ion batteries, and molecular pumps. PMID:27313210

  8. Characterization of two new stable block copolymer mesophases by synchrotron small-angle scattering

    NASA Astrophysics Data System (ADS)

    Burger, C.; Micha, M. A.; Oestreich, S.; Förster, S.; Antonietti, M.

    1998-05-01

    Block copolymers made of polystyrene and fluorinated blocks represent a new class of polymers with a very strong incompatibility between the two blocks. They exhibit new stable block copolymer mesophases which are not considered in the phase diagrams of diblock copolymers in the strong and super-strong segregation regime. The solid-state structures of two polymers with different compositions are characterized by synchrotron small-angle X-ray scattering and transmission electron microscopy, thus proving the existence of a quadratically perforated layer phase and a 2D phase of sanidically degenerated cylinders.

  9. Development of mesophasic microreservoir-based transdermal drug delivery system of propranolol.

    PubMed

    Omray, L K; Kohli, S; Khopade, A J; Patil, S; Gajbhiye, Asmita; Agrawal, G P

    2008-09-01

    The mesophasic microreservoir comprises lyotrophic liquid crystals. The liquid crystals were prepared of Brij-35, cetosteryl alcohol and propranolol and evaluated for parameters viz. anisotropy, size and size distribution and drug entrapment efficiency. Subsequent to this liquid crystals based transdermal drug delivery system (TDS) was prepared by incorporating liquid crystals in previously prepared matrix based transdermal patch and evaluated for stability studies like temperature, humidity and aging. The system was also studied for tensile strength, moisture content, water vapor transmission, drug content, anisotropy and In vitro drug release studies.

  10. Evaluating the link between self-assembled mesophase structure and drug release.

    PubMed

    Phan, Stephanie; Fong, Wye-Khay; Kirby, Nigel; Hanley, Tracey; Boyd, Ben J

    2011-12-12

    Lipid-based liquid crystalline materials are of increasing interest for use as drug delivery systems. The intricate nanostructure of the reversed bicontinuous cubic (V(2)) and inverse hexagonal (H(2)) liquid crystal matrices have been shown to provide diffusion controlled release of actives of varying size and polarity. In this study, we extend the understanding of release to other self-assembled phases, the micellar cubic phase (I(2)) and inverse micelles (L(2)). The systems are comparable as they were all prepared from the one lipid, glyceryl monooleate (GMO), which sequentially forms all four phases with increasing hexadecane (HD) content in excess water. Phase identity was confirmed by small angle X-ray scattering (SAXS). SAXS data indicated that four mesophases were formed with increasing HD content at 25°C: V(2) phase (Pn3m space group) formed at 0-4% (w/w) HD, H(2) phase formed at 4-25% (w/w) HD, I(2) phase (Fd3m space group) formed at 25-40% (w/w) HD and finally L(2) phase formed at >40% (w/w) HD. Analogous compositions using phytantriol rather than GMO as the core lipid did not produce the I(2) phase, with only V(2) to H(2) to L(2) transitions being apparent with increasing HD concentration. In order to relate the liquid crystal phase structure to drug release rate, in vitro release tests were conducted by incorporating radio-labelled glucose as a model hydrophilic drug into the four GMO-based mesophases. It was found that the drug release followed first-order diffusion kinetics and was fastest from V(2) followed by L(2), H(2), and I(2). Drug release was shown to be significantly faster from bicontinuous cubic phase than the other mesophases, indicating that the state of the water compartments, whether open or closed, has a great influence on the rate of drug release. It is envisioned that liquid crystalline mesophases with slower release characteristics will more likely have potential applications as sustained release drug delivery systems, and hence

  11. Membrane Protein Structure Determination Using Crystallography and Lipidic Mesophases - Recent Advances and Successes

    PubMed Central

    Caffrey, Martin; Li, Dianfan; Dukkipati, Abhiram

    2012-01-01

    The crystal structure of the β2-adrenergic receptor in complex with an agonist and its cognate G protein has just recently been solved. It is now possible to explore in molecular detail the means by which this paradigmatic transmembrane receptor binds agonist, communicates the impulse or signalling event across the membrane and sets in motion a series of G protein-directed intracellular responses. The structure was determined using crystals of the ternary complex grown in a rationally designed lipidic mesophase by the so-called in meso method. The method is proving to be particularly useful in the G protein-coupled receptor field where the structures of thirteen distinct receptor types have been solved in the past five years. In addition to receptors, the method has proven useful with a wide variety of integral membrane protein classes that include bacterial and eukaryotic rhodopsins, a light harvesting complex II (LHII), photosynthetic reaction centers, cytochrome oxidases, β-barrels, an exchanger, and an integral membrane peptide. This attests to the versatility and range of the method and supports the view that the in meso method should be included in the arsenal of the serious membrane structural biologist. For this to happen however, the reluctance in adopting it attributable, in part, to the anticipated difficulties associated with handling the sticky, viscous cubic mesophase in which crystals grow must be overcome. Harvesting and collecting diffraction data with the mesophase-grown crystals is also viewed with some trepidation. It is acknowledged that there are challenges associated with the method. Over the years, we have endeavored to establish how the method works at a molecular level and to make it user-friendly. To these ends, tools for handling the mesophase in the pico- to nano-liter volume range have been developed for highly efficient crystallization screening in manual and robotic modes. Methods have been implemented for evaluating the functional

  12. Structural characterization and molecular order of rodlike mesogens with three- and four-ring core by XRD and 13C NMR spectroscopy.

    PubMed

    Reddy, M Kesava; Reddy, K Subramanyam; Yoga, K; Prakash, M; Narasimhaswamy, T; Mandal, A B; Lobo, Nitin P; Ramanathan, K V; Rao, D S Shankar; Prasad, S Krishna

    2013-05-09

    Structural characterizations using XRD and (13)C NMR spectroscopy of two rodlike mesogens consisting of (i) three phenyl ring core with a polar cyano terminal and (ii) four phenyl ring core with flexible dodecyl terminal chain are presented. The three-ring-core mesogen with cyano terminal exhibits enantiotropic smectic A phase while the four-ring mesogen reveals polymesomorphism and shows enantiotropic nematic, smectic C, and tilted hexatic phases. The molecular organization in the three-ring mesogen is found to be partial bilayer smectic Ad type, and the interdigitation of the molecules in the neighboring layers is attributed to the presence of the polar terminal group. For the four-ring mesogen, the XRD results confirm the existence of the smectic C and the tilted hexatic mesophases. A thermal variation of the layer spacing across the smectic C phase followed by a discrete jump at the transition to the tilted hexatic phase is also observed. The tilt angles have been estimated to be about 45° in the smectic C phase and about 40° in tilted hexatic phase. (13)C NMR results indicate that in the mesophase the molecules are aligned parallel to the magnetic field. From the (13)C-(1)H dipolar couplings determined from the 2D experiments, the overall order parameter for the three-ring mesogen in its smectic A phase has been estimated to be 0.72 while values ranging from 0.88 to 0.44 have been obtained for the four-ring mesogen as it passes from the tilted hexatic to the nematic phase. The orientations of the different rings of the core unit with respect to each other and also with respect to the long axis of the molecule have also been obtained.

  13. Three dielectric constants and orientation order parameters in nematic mesophases

    NASA Astrophysics Data System (ADS)

    Yoon, Hyung Guen; Jeong, Seung Yeon; Kumar, Satyendra; Park, Min Sang; Park, Jung Ok; Srinivasarao, M.; Shin, Sung Tae

    2011-03-01

    Temperature dependence of the three components ɛ1 , ɛ2 , and ɛ3 of dielectric constant and orientation order parameters in the nematic phase of mesogens with rod, banana, and zero-order dendritic shape were measured using the in-plane and vertical switching geometries, and micro-Raman technique. Results on the well-known uniaxial (Nu) nematogens, E7 and 5CB, revealed two components ɛ1 = ~ɛ| | and ɛ2 = ~ɛ3 = ~ɛ⊥ , as expected. The three dielectric constants were different for two azo substituted (A131 and A103) and an oxadiazole based (ODBP-Ph-C12) bent core mesogens, and a Ge core tetrapode. In some cases, two of the components became the same indicating a loss of biaxiality at temperatures coinciding with the previously reported Nu to biaxial nematic transition. This interpretation is substantiated by micro-Raman measurements of the uniaxial and biaxial nematic order parameters. Supported by the US Department of Energy, Basic Energy Sciences grant ER46572 and by Samsung Electronics Corporation.

  14. Modulation of physical properties of reverse hexagonal mesophases: a dielectric spectroscopy study.

    PubMed

    Mishraki, Tehila; Ben Ishai, Paul; Babukh, Dmitry; Aserin, Abraham; Feldman, Yuri; Garti, Nissim

    2013-04-15

    The structural, dynamic, and kinetic aspects of the HII systems based on glycerol monooleate (GMO), phosphatidylcholine (PC), triacylglycerol (TAG), and water were investigated by dielectric spectroscopy in a frequency range of 10(-2)-10(6) Hz, and a temperature range of 290-320 K. Three distinct processes as well as a temperature-activated dc conductivity were detected and examined. These were assigned to the reorientation of the GMO polar heads, the tangential movement of counterions at the interface, the transport of TAGs through the lipids tails, and the ion mobility within the water cylinders. Upon addition of PC, the critical temperature (T0) of the dehydration of the GMO headgroups increased. The optimal concentration found for structural stabilization of the HII mesophase was 10 wt% PC, since it imparted the strongest bonding at the interfacial layer and increased the association between the lipid tails. Within the HII cluster, TAG percolated and shifted between the hexagonal rods themselves. The present study demonstrated the benefit of controlling the critical temperature of the HII mesophase partial dehydration and softening, as well as the percolation of TAGs. These factors influence the diffusion mode of embedded drugs in the physiological temperature range. Copyright © 2013. Published by Elsevier Inc.

  15. On the use of mesophase pitch for the preparation of hierarchical porous carbon monoliths by nanocasting

    NASA Astrophysics Data System (ADS)

    Adelhelm, Philipp; Cabrera, Karin; Smarsly, Bernd M.

    2012-02-01

    A detailed study is given on the synthesis of a hierarchical porous carbon, possessing both meso- and macropores, using a mesophase pitch (MP) as the carbon precursor. This carbon material is prepared by the nanocasting approach involving the replication of a porous silica monolith (hard templating). While this carbon material has already been tested in energy storage applications, various detailed aspects of its formation and structure are addressed in this study. Scanning electron microscopy (SEM), Hg porosimetry and N2 physisorption are used to characterize the morphology and porosity of the carbon replica. A novel approach for the detailed analysis of wide-angle x-ray scattering (WAXS) from non-graphitic carbons is applied to quantitatively compare the graphene microstructures of carbons prepared using MP and furfuryl alcohol (FA). This WAXS analysis underlines the importance of the carbon precursor in the synthesis of templated porous carbon materials via the nanocasting route. Our study demonstrates that a mesophase pitch is a superior precursor whenever a high-purity, low-micropore-content and well-developed graphene structure is desired.

  16. Influence of mesophase activation conditions on the specific capacitance of the resulting carbons

    NASA Astrophysics Data System (ADS)

    Mora, E.; Ruiz, V.; Santamaría, R.; Blanco, C.; Granda, M.; Menéndez, R.; Juarez-Galán, J. M.; Rodríguez-Reinoso, F.

    Mesophase pitch AR24 was directly activated with KOH using different proportions of the activating agent and activation temperatures, to study the effect on the textural characteristics of the resultant activated carbons and how these characteristics influence their behaviour as electrodes in supercapacitors. The textural properties of the activated carbons were studied by gas adsorption and immersion calorimetry. The results indicate that all the carbons produced were mainly microporous, with pore size around 1 nm. The behaviour of these carbons as electrodes in supercapacitors was studied from galvanostatic charge-discharge cycles. The specific capacitance values obtained were very high, reaching 400 and 200 F g -1 at low and high current densities respectively, for the sample activated with (5:1) KOH to mesophase ratio. Nevertheless, the reasons for this high capacitance values cannot be explained only on the basis of the textural characteristics of the activated carbons, as the results indicated that other factors might be also playing a significant role in their electrochemical behaviour.

  17. Geometry induced sequence of nanoscale Frank–Kasper and quasicrystal mesophases in giant surfactants

    SciTech Connect

    Yue, Kan; Huang, Mingjun; Marson, Ryan L.; He, Jinlin; Huang, Jiahao; Zhou, Zhe; Wang, Jing; Liu, Chang; Yan, Xuesheng; Wu, Kan; Guo, Zaihong; Liu, Hao; Zhang, Wei; Ni, Peihong; Wesdemiotis, Chrys; Zhang, Wen-Bin; Glotzer, Sharon C.; Cheng, Stephen Z. D.

    2016-11-28

    Frank–Kasper (F-K) and quasicrystal phases were originally identified in metal alloys and only sporadically reported in soft materials. These unconventional sphere-packing schemes open up possibilities to design materials with different properties. The challenge in soft materials is how to correlate complex phases built from spheres with the tunable parameters of chemical composition and molecular architecture. Here, we report a complete sequence of various highly ordered mesophases by the self-assembly of specifically designed and synthesized giant surfactants, which are conjugates of hydrophilic polyhedral oligomeric silsesquioxane cages tethered with hydrophobic polystyrene tails. We show that the occurrence of these mesophases results from nanophase separation between the heads and tails and thus is critically dependent on molecular geometry. Variations in molecular geometry achieved by changing the number of tails from one to four not only shift compositional phase boundaries but also stabilize F-K and quasicrystal phases in regions where simple phases of spheroidal micelles are typically observed. These complex self-assembled nanostructures have been identified by combining X-ray scattering techniques and real-space electron microscopy images. Brownian dynamics simulations based on a simplified molecular model confirm the architecture-induced sequence of phases. Our results demonstrate the critical role of molecular architecture in dictating the formation of supramolecular crystals with “soft” spheroidal motifs and provide guidelines to the design of unconventional self-assembled nanostructures.

  18. X-ray Transparent Microfluidic Chip for Mesophase-Based Crystallization of Membrane Proteins and On-Chip Structure Determination

    SciTech Connect

    Khvostichenko, Daria S.; Schieferstein, Jeremy M.; Pawate, Ashtamurthy S.; Laible, Philip D.; Kenis, Paul J. A.

    2014-10-01

    ABSTRACT: Crystallization from lipidic mesophase matrices is a promising route to diffraction-quality crystals and structures of membrane proteins. The microfluidic approach reported here eliminates two bottlenecks of the standard mesophase-based crystallization protocols: (i) manual preparation of viscous mesophases and (ii) manual harvesting of often small and fragile protein crystals. In the approach reported here, protein-loaded mesophases are formulated in an X-ray transparent microfluidic chip using only 60 nL of the protein solution per crystallization trial. The X-ray transparency of the chip enables diffraction data collection from multiple crystals residing in microfluidic wells, eliminating the normally required manual harvesting and mounting of individual crystals. We validated our approach by on-chip crystallization of photosynthetic reaction center, a membrane protein from Rhodobacter sphaeroides, followed by solving its structure to a resolution of 2.5 Å using X-ray diffraction data collected on-chip under ambient conditions. A moderate conformational change in hydrophilic chains of the protein was observed when comparing the on-chip, room temperature structure with known structures for which data were acquired under cryogenic conditions.

  19. The effect of cation structure on the mesophase architecture of self-assembled and polymerized imidazolium-based ionic liquids.

    SciTech Connect

    Batra, D.; Seifert, S.; Firestone, M. A.; Materials Science Division

    2007-01-01

    The binary phase behavior of a series of imidazolium-based ionic liquids (ILs) has been investigated. In particular, the effect of two structural modifications of the imidazolium cation, alkyl chain length, and the introduction of a polymerizable acryloyl group at the alkyl chain terminus, has been studied using small angle X-ray scattering. Upon increasing water content, the non-polymerizable IL, 1-decyl-3-methylimidazolium chloride, adopts mesophase structures of predominately two-dimensional (2D) hexagonal symmetry, including structures intermediate in character between lamellae and 2D hexagonal micelles. Introduction of a photopolymerizable acryloyl functional group to form 1-(10-(acryloyloxy)decyl)-3-methylimidazolium chloride produces a rod-coil IL cation that yields self-assembled mesophases in which the formation of tetragonal morphologies is favored. Covalent linking of the IL cations by UV-induced polymerization converts the lyotropic mesophase into three-dimensional biocontinuous chemical gels. Reducing the alkyl chain length, as in the polymerizable IL cation 1-(8-(acryloyloxy)octyl)-3-methylimidazolium chloride, severely reduces the self-assembled mesophase order, and triggers the formation of only weakly ordered one-dimensional lamellar structures.

  20. X-ray transparent microfluidic chip for mesophase-based crystallization of membrane proteins and on-chip structure determination

    DOE PAGES

    Khvostichenko, Daria S.; Schieferstein, Jeremy M.; Pawate, Ashtamurthy S.; ...

    2014-08-21

    Crystallization from lipidic mesophase matrices is a promising route to diffraction-quality crystals and structures of membrane proteins. The microfluidic approach reported here eliminates two bottlenecks of the standard mesophase-based crystallization protocols: (i) manual preparation of viscous mesophases and (ii) manual harvesting of often small and fragile protein crystals. In the approach reported here, protein-loaded mesophases are formulated in an X-ray transparent microfluidic chip using only 60 nL of the protein solution per crystallization trial. The X-ray transparency of the chip enables diffraction data collection from multiple crystals residing in microfluidic wells, eliminating the normally required manual harvesting and mounting ofmore » individual crystals. In addition, we validated our approach by on-chip crystallization of photosynthetic reaction center, a membrane protein from Rhodobacter sphaeroides, followed by solving its structure to a resolution of 2.5 Å using X-ray diffraction data collected on-chip under ambient conditions. A moderate conformational change in hydrophilic chains of the protein was observed when comparing the on-chip, room temperature structure with known structures for which data were acquired under cryogenic conditions.« less

  1. Structural rearrangements and interaction within H(II) mesophase induced by cosolubilization of vitamin E and ascorbic acid.

    PubMed

    Bitan-Cherbakovsky, Liron; Yuli-Amar, Idit; Aserin, Abraham; Garti, Nissim

    2009-11-17

    We investigated the effect of ascorbic acid (AA) cosolubilized with vitamin E (VE) on reverse hexagonal (H(II)) mesophase. The H(II) phase comprises monoolein (GMO)/d-alpha-tocopherol (VE) in a ratio of 90/10 by weight and 12.5 wt % water. The macrostructural characteristics of this system were determined by polarized light microscopy and small-angle X-ray scattering measurements. We used differential scanning calorimetry and attenuated total reflectance Fourier transform infrared to characterize the microstructure, the vibration of the functional groups, and the location of the AA guest molecule. AA was incorporated to the system in two steps: 1-4 wt % AA and 5-6 wt % AA. We compared this system to one containing tricaprylin as the oil phase, as previously reported. These measurements revealed that AA is localized first in the water rich-core and in the interface, and acts as a chaotropic molecule that decreases the water melting point. When a larger quantity of AA (5-6 wt %) is added, the system is saturated, and the AA is located in the inner cylinder and manifested by more moderate distortion. The addition of AA also causes alteration in the behavior of the GMO hydrocarbon chains and makes them more flexible. Further addition of AA caused the GMO hydrocarbon chain to be more solvated by the VE hydrocarbon chain and enabled additional migration of VE; hence a decrease in the hydrophobic melting temperature occurred (similar to tricaprylin). Increasing the amount of AA weakened the bonding between the GMO and water and created new bonds between AA and GMO and AA with water.

  2. Tuning the crystalline and mesophase structure of olefin block copolymer through self-nucleation and annealing treatments.

    PubMed

    Fan, Jiashu; Zhang, Qinglong; Feng, Jiachun

    2015-06-28

    As a type of novel semi-crystalline block copolymers, the final properties of olefin block copolymers (OBCs) greatly depend on the crystalline and phase-separated structures. In the present work, we systematically investigated the influence of self-nucleation and annealing on the lamellar and mesophase-separated structure of OBCs. According to the crystalline and melting behavior after self-nucleation and annealing treatments, four different regimes can be recognized with the self-seeding temperature Ts varying from 125 to 109 °C. In regime A, only self-nucleation occurs, while it coexists with lamellar thickening in regime B. In regime C, there is only lamellar thickening behavior. The lamellar thickening induced inconsecutive lamellar crystals observed revealed that the rearrangement of the hard blocks, which are next to the soft blocks and trapped in the intermediate regime between crystalline and amorphous phases, into neighboring lamellar crystals should be the mechanism for the lamellar thickening of the OBCs. Surprisingly, no lamellar thickening occurs and a new small melting peak appears at lower temperatures in regime D. Considering the block dispersity of OBCs, the emergence of a small melting peak at lower temperatures can be attributed to the crystallization of the ethylene sequence with relatively weaker crystallization abilities, which are not able to crystallize in a standard crystalline state. Based on these findings, we gained some new understandings on lamellar thickening behavior of OBCs and established the self-nucleation and annealing process as a powerful tool for tuning the crystalline and phase-separated structures of OBCs.

  3. Single-walled carbon nanotube buckypaper and mesophase pitch carbon/carbon composites

    NASA Astrophysics Data System (ADS)

    Park, Jin Gyu; Yun, Nam Gyun; Park, Young Bin; Liang, Richard; Lumata, Lloyd; Brooks, James; Zhang, Chuck; Wang, Ben; High-Performance Materials Institute, Fsu Collaboration; National High Magnetic Field Laboratory, Fsu Collaboration

    2011-03-01

    Carbon/carbon composites consisting of single-walled carbon nanotube (SWCNT) buckypaper (BP) and mesophase pitch resin have been produced through impregnation of BP with pitch using toluene as a solvent. Drying, stabilization and carbonization processes were performed sequentially, and repeated to increase the pitch content. Voids in the carbon/carbon composite samples decreased with increasing impregnation process cycles. Electrical conductivity and density of the composites increased with carbonization by two to three times that of pristine BP. These results indicate that discontinuity and intertube contact barriers of SWCNTs in the BP are partially overcome by the carbonization process of pitch. The temperature dependence of the Raman shift shows that mechanical strain is increased since carbonized pitch matrix surrounds the nanotubes. High-Performance Materials Institute, NSF DMR-0602859, NSF DMR-0654118.

  4. Antipolar and Anticlinic Mesophase Order in Chromatin Induced by Nucleosome Polarity and Chirality Correlations

    NASA Astrophysics Data System (ADS)

    Garcés, R.; Podgornik, R.; Lorman, V.

    2015-06-01

    Contrary to the usual "rigid supermolecular assembly" paradigm of chromatin structure, we propose to analyze its eventual ordered state in terms of symmetry properties of individual nucleosomes that give rise to mesophase order parameters, like in many other soft-matter systems. Basing our approach on the Landau-de Gennes phenomenology, we describe the mesoscale order in chromatin by antipolar and anticlinic correlations of chiral individual nucleosomes. This approach leads to a unifying physical picture of a whole series of soft locally ordered states with different apparent structures, including the recently observed heteromorphic chromatin, stemming from the antipolar arrangement of nucleosomes complemented by their chiral twisting. Properties of these states under an external force field can reconcile apparently contradictory results of single-molecule experiments.

  5. The curvature elastic-energy function of the lipid-water cubic mesophase

    NASA Astrophysics Data System (ADS)

    Chung, Hesson; Caffrey, Martin

    1994-03-01

    CELL and lipid membranes are able to bend, as manifested during membrane fusion and the formation of non-lamellar lyotropic mesopbases in water. But there is an energy cost to bending of lipid layers, called the curvature elastic energy. Although the functional form of this energy is known1, a complete quantitative knowledge of the curvature elastic energy, which is central to predicting the relative stability of the large number of phases that lipid membranes can adopt, has been lacking. Here we use X-ray synchrotron diffraction measurements of the variation of lattice parameter with pressure and temperature for the periodic Ia3d (Q230) cubic phase of hydrated monoolein to calculate the complete curvature elastic-energy function for the lipid cubic mesophase. This allows us to predict the stabilities of different cubic and lamellar phases for this system as a function of composition.

  6. Effect of reduction on graphitization behavior of mesophase pitch-derived carbon fibers

    NASA Astrophysics Data System (ADS)

    Kim, Y. A.; Muramatsu, H.; Kojima, M.; Hayashi, T.; Kim, C.; Endo, M.; Dresselhaus, M. S.

    2005-06-01

    Chemically reduced solid-state mesophase pitch carbon fibers below 1000 °C in a flow of hydrogen gas were treated up to 3000 °C in an argon atmosphere in order to evaluate the effect of hydrogen on the graphitization behavior. Major phenomena observed during the reduction process are chemical transformation from an ether to a hydroxyl group (corresponding to the rupture of the C-O-C bond) and their subsequent evolution as gases. Finally, oversupplied hydrogen might be utilized to satisfy the dangling bond. For the sample heat treated at 3000 °C, the low crystallinity indicates that hydrogen atoms covalently bonded to the end planes of graphitic layers act as an effective barrier to crystallite growth.

  7. Characteristics of mesophase pitch-based carbon fibers as anode materials for lithium secondary cells

    SciTech Connect

    Tamaki, Toshio

    1995-12-31

    Mesophase pitch-based Carbon Fibers (MPCF) have been investigated as anode materials for lithium secondary cells by examining their physical and electrochemical properties. Discharge capacity and initial charge-discharge efficiency of the materials were studied in relation to the heat treatment temperatures of MPCF. Carbon fiber which was heat treated at about 3,000 C gave the highest discharge capacity (over 300 mAh/g), good efficiency (92%) and superior current capability (600 mA/g). Carbon fiber heat treated at less than 1,000 C, also has superior discharge capacity (over 500 mAh/g) at the first cycle, however efficiency was relatively low. Some of the relationships between structure of MPCF and electrochemical properties are discussed.

  8. Charge-discharge characteristics of mesophase-pitch-based carbon fibers for lithium cells

    SciTech Connect

    Imanishi, N.; Kashiwagi, H.; Ichikawa, T.; Takeda, Y.; Yamamoto, O. ); Inagaki, M. )

    1993-02-01

    Mesophase-pitch-based carbon fibers were heat-treated at high temperatures (2,600 or 2,800 C) and examined as anodes for lithium secondary batteries. Four types of carbon fibers were used whose cross-sectional views are: a radial texture with wedge (type A), a radial texture with fine zigzag layers (type B), a double texture (type C), and a concentric texture (type D). Lithium could not be deintercalated after the first lithium intercalation in the type A carbon fiber. The structure of the type A fiber was destroyed during lithium intercalation. The other three types of carbon fibers showed good rechargeability on the first cycle, but demonstrated different behavior after 30 cycles. The highest lithium intercalation and deintercalation capacity was observed for the radially oriented carbon fiber (type B). The x-ray results showed a reversible change in the lattice along the c-axis during the intercalation and deintercalation cycle.

  9. Modelling of single bubble growth in carbon nanofibre filled mesophase pitch during carbonization

    NASA Astrophysics Data System (ADS)

    Calebrese, Christopher; Schadler, Linda S.; Lewis, Daniel J.

    2010-06-01

    A single bubble growth model is presented for bubble growth in mesophase pitch during carbonization. This model is distinguished from typical polymer foaming models in its design to be used over a wider temperature range, its accounting for mass transfer from the liquid to the bubble, and the incorporation of reaction sites in the melt which produce volatile gases. The effect of nanofibre loading on growth is investigated in terms of viscosity, density and volatile concentration. It is found that the viscosity change is the controlling factor in altering the bubble growth rate in this system. Comparison with experimental data shows that a single bubble growth model is a reasonable assumption for carbon nanofibre loading of 1 wt% or below.

  10. Structural analysis of the B-doped mesophase pitch-based graphite fibers by Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Endo, M.; Kim, C.; Karaki, T.; Tamaki, T.; Nishimura, Y.; Matthews, M. J.; Brown, S. D. M.; Dresselhaus, M. S.

    1998-10-01

    Milled B-doped mesophase pitch-based carbon fibers (mMPCF's) prepared from a melt-blown petroleum mesophase pitch precursor material have been developed for enhanced Li uptake capacity in Li ion batteries. Raman spectroscopy has been used to investigate the structure of graphitized and B-doped mMPCF's using 632.8-nm HeNe laser excitation. The B-doped mMPCF's show a strong Raman peak near 1330 cm-1, a well-defined peak at 1620 cm-1, and the disappearance of the second-order 2660 cm-1 band. Furthermore, it is shown that the E2g2 graphite Raman band at 1580 cm-1 is shifted to 1590 cm-1 due to B doping. The appearance of a new weak Raman band in the B-doped mMPCF's near 1320 cm-1 is closely related to the B-C stretching mode in the graphite lattice. These results are associated with the breakdown of the k=0 selection rules by a local distortion of the graphite lattice due to substitutional boron doping. On the basis of the integrated intensity ratio R of the disorder-induced line near 1330 cm-1 to the Raman line near 1590 cm-1 after 2.66 at. % boron doping, it is suggested that the substitutional boron in the mMPCF's is homogeneously distributed within the graphene layer in the fiber form. The crystallite domain size La parallel and perpendicular to the fiber axis on the surface of the fiber is estimated to be about 60 Å, which could correspond to the distance between boron atoms substituted for C atoms in a graphene layer of the fibers.

  11. Dielectric, calorimetric and mesophase properties of 1''-(2',4-difluorobiphenyl-4'-yloxy)-9''-(4-cyanobiphenyl-4'-yloxy) nonane: an odd liquid crystal dimer with a monotropic mesophase having the characteristics of a twist-bend nematic phase.

    PubMed

    Sebastián, N; López, D O; Robles-Hernández, B; de la Fuente, M R; Salud, J; Pérez-Jubindo, M A; Dunmur, D A; Luckhurst, G R; Jackson, D J B

    2014-10-21

    This paper reports a novel liquid crystal phase having the characteristics of a twist-bend nematic phase formed by a non-symmetric ether-linked liquid crystal dimer. The dimer 1''-(2',4-difluorobiphenyl-4'-yloxy)-9''-(4-cyanobiphenyl-4'-yloxy) nonane (FFO9OCB) exhibits two liquid-crystalline phases on cooling at a sufficiently high rate from the isotropic phase. The high temperature mesophase has been reported in the literature as nematic and confirmed in this study. The other mesophase is metastable and can be supercooled giving rise to a glassy state. Its identification and characterization are based on optical textures, broadband dielectric spectroscopy, calorimetry, measurements of both splay and bend elastic constants in the nematic phase and miscibility studies. It is concluded that the low temperature mesophase exhibits the characteristics of a twist-bend nematic phase. Dielectric measurements enable us to obtain the static permittivity and information about the molecular dynamics in the isotropic phase, in the nematic mesophase and across the isotropic-to-nematic phase transition. Two orientations, parallel and perpendicular to the director, have been investigated. In the high temperature nematic mesophase, the dielectric anisotropy is found to be positive. Measurements of the parallel component of the dielectric permittivity are well-explained by the molecular theory of dielectric relaxation in nematic dimers (M. Stocchero, A. Ferrarini, G. J. Moro, D. A. Dunmur and G. R. Luckhurst, J. Chem. Phys., 2004, 121, 8079). The dimer is modelled as a mixture of cis and trans conformers and the model allows an estimate of their relative populations at each temperature. The nematic-to-isotropic phase transition has been exhaustively studied from the accurate evolution of the heat capacity and the static dielectric permittivity data. It has been concluded that the transition is first order in nature, but close to tricritical. The nature of the nematic-to-the novel

  12. Experimental study and modeling of swelling and bubble growth in carbon nanofiber filled mesophase pitch during carbonization

    NASA Astrophysics Data System (ADS)

    Calebrese, Christopher

    Graphite and all carbon bipolar plates show corrosion resistance in fuel cells and provide good electrical conductivity. These materials typically need to be individually machined, a time consuming and costly process. Mesophase pitch is used to manufacture carbon fibers and carbon-carbon composites. This material provides a good starting point for the production of a moldable, all carbon bipolar plate. However, processing of mesophase pitch to produce all carbon materials requires a time intensive oxidation step to prevent swelling during carbonization. In this work, carbon nanofibers were used to reduce swelling in mesophase pitch. It was found that the increase in viscosity with the addition of carbon nanofibers was responsible for the reduction in swelling. The influence of the filler became apparent above the percolation threshold. At loadings below the percolation threshold, the swelling of the mesophase pitch was not reduced after carbonization. The swelling of the mesophase pitch at a given carbon nanofiber loading was also dependent on the length of the carbon nanofibers. Longer carbon nanofibers led to greater increases in the viscosity of the melt and thus led to greater reduction in swelling. The final carbon product was evaluated for use as a low temperature fuel cell bipolar plate material. Constraining the mesophase pitch during carbonization led to a final product with strength and electrical conductivity comparable to current composite bipolar plate materials. The addition of micron size chopped glass fibers with a softening point near 850°C and carbon nanofibers led to a final product with air permeability less than that of graphite. A spherically symmetric, single bubble growth model was also developed. The model included temperature dependence, liquid to bubble mass transfer and reactions in the system. Results from simulations showed that that the increase in viscosity due to the addition of carbon nanofibers slows the growth of bubbles, but

  13. Not Only Columns: High Hole Mobility in a Discotic Nematic Mesophase Formed by Metal-Containing Porphyrin-Core Dendrimers.

    PubMed

    Concellón, Alberto; Marcos, Mercedes; Romero, Pilar; Serrano, José Luis; Termine, Roberto; Golemme, Attilio

    2017-01-24

    We report a new family of multifunctional liquid-crystalline porphyrin-core dendrimers that have coumarin functional groups around the porphyrin core. Porphyrin metalation strongly affects the photophysical properties, and therefore Zn(II) and Cu(II) derivatives have also been prepared. All the synthesized dendrimers form a nematic discotic mesophase. Their high tendency for homeotropic alignment makes these dendrimers excellent candidates for device applications, owing to their easy processability, spontaneous alignment between electrodes, and self-healing of defects because of their dynamic nature. The charge mobility values of these materials are the highest ever reported for a nematic discotic phase. Moreover, these values are similar to the highest values reported for ordered columnar mesophases, and this shows that a supramolecular organization in columns is not necessary to achieve high charge mobility. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Characteristics of coke carbon modified with mesophase-pitch as a negative electrode for lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Sato, Yuichi; Kikuchi, Yasuo; Nakano, Takeshi; Okuno, Gaku; Kobayakawa, Koichi; Kawai, Takanobu; Yokoyama, Akira

    To increase the charge-discharge capacity of carbon electrodes for lithium ion secondary batteries, coke carbon, a relatively cheap material, was modified with mesophase-pitch carbon by a heat treatment. While coke carbon powder, mesophase-pitch, and a mixture thereof (4:1 by weight) supplied between 0 and 1.5 V vs. Li/Li + an initial discharge capacity of about 295 mAh/g, 310 mAh/g, and 310 mAh/g, respectively, the modified coke deintercalated 400 mA h/g of lithium with a high degree of reversibility. The difference in capacity between the modified carbon and mixture are discussed based on the shape of their current-potential curves and their galvanostatic charge-discharge curves.

  15. Host Lipid and Temperature as Important Screening Variables for Crystallizing Integral Membrane Proteins in Lipidic Mesophases. Trials with Diacylglycerol Kinase

    PubMed Central

    Li, Dianfan; Shah, Syed T. A.; Caffrey, Martin

    2013-01-01

    A systematic study of the crystallization of an α-helical, integral membrane enzyme, diacylglycerol kinase, DgkA, using the lipidic cubic mesophase or in meso method is described. These trials have resulted in the production of blocky, rhombohedron-shaped crystals of diffraction quality currently in use for structure determination. Dramatic improvements in crystal quality were obtained when the identity of the lipid used to form the mesophase bilayer into which the protein was reconstituted as a prelude to crystallogenesis was varied. These monoacylglycerol lipids incorporated fatty acyl chains ranging from 14 to 18 carbon atoms long with cis olefinic bonds located toward the middle of the chain. Best crystals were obtained with a lipid that had an acyl chain 15 carbon atoms long with the double bond between carbons 7 and 8. It is speculated that the effectiveness of this lipid derives from hydrophobic mismatch between the target integral membrane protein and the bilayer of the host mesophase. Low temperature (4 °C) worked in concert with the short chain lipid to provide high quality crystals. Recommended screening strategies for crystallizing membrane proteins that include host lipid type and low temperature are made on the basis of this and related in meso crystallization trials. PMID:23956688

  16. Membrane Protein Crystallization in Lipidic Mesophases. Hosting Lipid Effects on the Crystallization and Structure of a Transmembrane Peptide

    SciTech Connect

    Hfer, Nicole; Aragao, David; Lyons, Joseph A.; Caffrey, Martin

    2011-09-28

    Gramicidin is an apolar pentadecapeptide antibiotic consisting of alternating d- and l-amino acids. It functions, in part, by creating pores in membranes of susceptible cells rendering them leaky to monovalent cations. The peptide should be able to traverse the host membrane either as a double-stranded, intertwined double helix (DSDH) or as a head-to-head single-stranded helix (HHSH). Current structure models are based on macromolecular X-ray crystallography (MX) and nuclear magnetic resonance (NMR). However, the HHSH form has only been observed by NMR. The shape and size of the different gramicidin conformations differ. We speculated therefore that reconstituting it into a lipidic mesophase with bilayers of different microstructures would preferentially stabilize one form over the other. By using such mesophases for in meso crystallogenesis, the expectation was that at least one would generate crystals of gramicidin in the HHSH form for structure determination by MX. This was tested using commercial and in-house synthesized lipids that support in meso crystallogenesis. Lipid acyl chain lengths were varied from 14 to 18 carbons to provide mesophases with a range of bilayer thicknesses. Unexpectedly, all lipids produced high-quality, structure-grade crystals with gramicidin only in the DSDH conformation.

  17. Deconvoluting the Effect of the Hydrophobic and Hydrophilic Domains of an Amphiphilic Integral Membrane Protein in Lipid Bicontinuous Cubic Mesophases.

    PubMed

    van 't Hag, Leonie; Shen, Hsin-Hui; Lu, Jingxiong; Hawley, Adrian M; Gras, Sally L; Drummond, Calum J; Conn, Charlotte E

    2015-11-10

    Lipidic bicontinuous cubic mesophases with encapsulated amphiphilic proteins are widely used in a range of biological and biomedical applications, including in meso crystallization, as drug delivery vehicles for therapeutic proteins, and as biosensors and biofuel cells. However, the effect of amphiphilic protein encapsulation on the cubic phase nanostructure is not well-understood. In this study, we illustrate the effect of incorporating the bacterial amphiphilic membrane protein Ag43, and its individual hydrophobic β(43) and hydrophilic α(43) domains, in bicontinuous cubic mesophases. For the monoolein, monoalmitolein, and phytantriol cubic phases with and without 8% w/w cholesterol, the effect of the full length amphiphilic protein Ag43 on the cubic phase nanostructure was more significant than the sum of the individual hydrophobic β(43) and hydrophilic α(43) domains. Several factors were found to potentially influence the impact of the hydrophobic β(43) domain on the cubic phase internal nanostructure. These include the size of the hydrophobic β(43) domain relative to the thickness of the lipid bilayer, as well as its charge and diameter. The size of the hydrophilic α(43) domain relative to the water channel radius of the cubic mesophase was also found to be important. The secondary structure of the Ag43 proteins was affected by the hydrophobic thickness and physicochemical properties of the lipid bilayer and the water channel diameter of the cubic phase. Such structural changes may be small but could potentially affect membrane protein function.

  18. Membrane Protein Crystallization in Lipidic Mesophases. Hosting lipid affects on the crystallization and structure of a transmembrane peptide

    PubMed Central

    Höfer, Nicole; Aragão, David; Lyons, Joseph A.; Caffrey, Martin

    2012-01-01

    Gramicidin is an apolar pentadecapeptide antibiotic consisting of alternating D-and L-amino acids. It functions, in part, by creating pores in membranes of susceptible cells rendering them leaky to monovalent cations. The peptide should be able to traverse the host membrane either as a double stranded, intertwined double helix (DSDH) or as a head-to-head single stranded helix (HHSH). Current structure models are based on macromolecular X-ray crystallography (MX) and nuclear magnetic resonance (NMR). However, the HHSH form has only been observed by NMR. The shape and size of the different gramicidin conformations differ. We speculated therefore that reconstituting it into a lipidic mesophase with bilayers of different microstructures would preferentially stabilize one form over the other. By using such mesophases for in meso crystallogenesis the expectation was that at least one would generate crystals of gramicidin in the HHSH form for structure determination by MX. This was tested using commercial and in-house synthesised lipids that support in meso crystallogenesis. Lipid acyl chain lengths were varied from 14 to 18 carbons to provide mesophases with a range of bilayer thicknesses. Unexpectedly, all lipids produced high quality, structure-grade crystals with gramicidin only in the DSDH conformation. PMID:22933857

  19. Evaporation-Induced Self-Assembly of Hybrid Bridged Silsesquioxane Film and Particulate Mesophases with Integral Organic Functionality

    SciTech Connect

    LU,YUNFENG; FAN,HONGYOU; DOKE,NILESH; LOY,DOUGLAS A.; ASSINK,ROGER A.; LAVAN,DAVID A.; BRINKER,C. JEFFREY

    2000-06-12

    Since the discovery of surfactant-templated silica mesophases, the development of organic modification schemes to impart functionality to the pore surfaces has received much attention. Most recently, using the general class of compounds referred to as bridged silsesquioxanes (RO){sub 3}Si-R{prime}-Si(OR){sub 3} (Scheme 1), three research groups have reported the formation of a new class of poly(bridgedsilsesquioxane) mesophases BSQMs with integral organic functionality. In contrast to previous hybrid mesophases where organic ligands or molecules are situated on pore surfaces, this class of materials necessarily incorporates the organic constituents into the framework as molecularly dispersed bridging ligands. Although it is anticipated that this new mesostructural organization should result in synergistic properties derived from the molecular scale mixing of the inorganic and organic components, few properties of BSQMs have been measured. In addition samples prepared to date have been in the form of granular precipitates, precluding their use in applications like membranes, fluidics, and low k dielectric films needed for all foreseeable future generations of microelectronics.

  20. Membrane Protein Crystallization in Lipidic Mesophases. Hosting lipid affects on the crystallization and structure of a transmembrane peptide.

    PubMed

    Höfer, Nicole; Aragão, David; Lyons, Joseph A; Caffrey, Martin

    2011-04-06

    Gramicidin is an apolar pentadecapeptide antibiotic consisting of alternating D-and L-amino acids. It functions, in part, by creating pores in membranes of susceptible cells rendering them leaky to monovalent cations. The peptide should be able to traverse the host membrane either as a double stranded, intertwined double helix (DSDH) or as a head-to-head single stranded helix (HHSH). Current structure models are based on macromolecular X-ray crystallography (MX) and nuclear magnetic resonance (NMR). However, the HHSH form has only been observed by NMR. The shape and size of the different gramicidin conformations differ. We speculated therefore that reconstituting it into a lipidic mesophase with bilayers of different microstructures would preferentially stabilize one form over the other. By using such mesophases for in meso crystallogenesis the expectation was that at least one would generate crystals of gramicidin in the HHSH form for structure determination by MX. This was tested using commercial and in-house synthesised lipids that support in meso crystallogenesis. Lipid acyl chain lengths were varied from 14 to 18 carbons to provide mesophases with a range of bilayer thicknesses. Unexpectedly, all lipids produced high quality, structure-grade crystals with gramicidin only in the DSDH conformation.

  1. Unit cell structure of water-filled monoolein into inverted hexagonal (H(II)) mesophase modeled by molecular dynamics.

    PubMed

    Kolev, Vesselin L; Ivanova, Anela N; Madjarova, Galia K; Aserin, Abraham; Garti, Nissim

    2014-05-22

    The study investigates the unit cell structure of inverted hexagonal (H(II)) mesophase composed of monoolein (1-monoolein, GMO) and water using atomistic molecular dynamics methods without imposing any restraints on lipid and water molecules. Statistically meaningful and very contrast images of the radial mass density distribution, scrutinizing also the separate components water, monoolein, the polar headgroups of the lipids, the double bond, and the termini of the hydrocarbon chain (the tail), are obtained. The lipid/water interface structure is analyzed based on the obtained water density distribution, on the estimated number of hydrogen bonds per monoolein headgroup, and on the headgroup-water radial distribution functions. The headgroup mass density distribution demonstrates hexagonal shape of the monoolein/water interface that is well-defined at higher water/monoolein ratios. Water interacts with the headgroups by forming a three-layer diffusive mass density distribution, and each layer's shape is close to hexagonal, which is an indication of long-range structural interactions. It is found that the monoolein headgroups form a constant number of hydrogen bonds leaving an excessive amount of water molecules outside the first lipid coordination sphere. Furthermore, the quantity of water at the monoolein/water interface increases steadily upon extension of the unit cell, so the interface should have a very dynamic structure. Investigation of the hydrocarbon residues reveals high compression and well-expressed structuring of the tails. The tails form a very compressed and constrained structure of defined layers across the unit cell with properties corresponding to a more densely packed nonpolar liquid (oil). Due to the hexagonal shape the 2D packing frustration is constant and does not depend on the water content. All reported structural features are based on averaging of the atomic coordinates over the time-length of the simulation trajectories. That kind of

  2. Harvesting and cryo-cooling crystals of membrane proteins grown in lipidic mesophases for structure determination by macromolecular crystallography.

    PubMed

    Li, Dianfan; Boland, Coilín; Aragao, David; Walsh, Kilian; Caffrey, Martin

    2012-09-02

    An important route to understanding how proteins function at a mechanistic level is to have the structure of the target protein available, ideally at atomic resolution. Presently, there is only one way to capture such information as applied to integral membrane proteins (Figure 1), and the complexes they form, and that method is macromolecular X-ray crystallography (MX). To do MX diffraction quality crystals are needed which, in the case of membrane proteins, do not form readily. A method for crystallizing membrane proteins that involves the use of lipidic mesophases, specifically the cubic and sponge phases(1-5), has gained considerable attention of late due to the successes it has had in the G protein-coupled receptor field(6-21) (www.mpdb.tcd.ie). However, the method, henceforth referred to as the in meso or lipidic cubic phase method, comes with its own technical challenges. These arise, in part, due to the generally viscous and sticky nature of the lipidic mesophase in which the crystals, which are often micro-crystals, grow. Manipulating crystals becomes difficult as a result and particularly so during harvesting(22,23). Problems arise too at the step that precedes harvesting which requires that the glass sandwich plates in which the crystals grow (Figure 2)(24,25) are opened to expose the mesophase bolus, and the crystals therein, for harvesting, cryo-cooling and eventual X-ray diffraction data collection. The cubic and sponge mesophase variants (Figure 3) from which crystals must be harvested have profoundly different rheologies(4,26). The cubic phase is viscous and sticky akin to a thick toothpaste. By contrast, the sponge phase is more fluid with a distinct tendency to flow. Accordingly, different approaches for opening crystallization wells containing crystals growing in the cubic and the sponge phase are called for as indeed different methods are required for harvesting crystals from the two mesophase types. Protocols for doing just that have been

  3. Mesophase and size manipulation of itraconazole liquid crystalline nanoparticles produced via quasi nanoemulsion precipitation.

    PubMed

    Mugheirbi, Naila A; Tajber, Lidia

    2015-10-01

    The fabrication of drug nanoparticles (NPs) with process-mediated tunable properties and performances continues to grow rapidly during the last decades. This study investigates the synthesis and phase tuning of nanoparticulate itraconazole (ITR) mesophases using quasi nanoemulsion precipitation from acetone/water systems to seek out an alternative pathway to the nucleation-based NP formation. ITR liquid crystalline (LC) phases were formed and nematic-smectic mesomorphism was achieved via controlling solvent:antisolvent temperature difference (ΔTS:AS). The use of ΔTS:AS=49.5°C was associated with a nematic assembly, while intercalated smectic A layering was observed at ΔTS:AS=0°C, with both phases confined in the nanospheres at room temperature. The quasi emulsion system has not been investigated at the nanoscale to date and in contrary to the microscale, quasi nanoemulsion was observed over the solvent:antisolvent viscosity ratios of 1:7-1:1.4. Poly(acrylic acid) in the solvent phase exhibited a concentration dependent interaction when ITR formed NPs. This nanodroplet-based approach enabled the preparation of a stable ITR nanodispersion using Poloxamer 407 at 80°C, which was unachievable before using precipitation via nucleation. Findings of this work lay groundwork in terms of rationalised molecular assembly as a tool in designing pharmaceutical LC NPs with tailored properties. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. Molecular dynamics approach to water structure of HII mesophase of monoolein

    NASA Astrophysics Data System (ADS)

    Kolev, Vesselin; Ivanova, Anela; Madjarova, Galia; Aserin, Abraham; Garti, Nissim

    2012-02-01

    The goal of the present work is to study theoretically the structure of water inside the water cylinder of the inverse hexagonal mesophase (HII) of glyceryl monooleate (monoolein, GMO), using the method of molecular dynamics. To simplify the computational model, a fixed structure of the GMO tube is maintained. The non-standard cylindrical geometry of the system required the development and application of a novel method for obtaining the starting distribution of water molecules. A predictor-corrector schema is employed for generation of the initial density of water. Molecular dynamics calculations are performed at constant volume and temperature (NVT ensemble) with 1D periodic boundary conditions applied. During the simulations the lipid structure is kept fixed, while the dynamics of water is unrestrained. Distribution of hydrogen bonds and density as well as radial distribution of water molecules across the water cylinder show the presence of water structure deep in the cylinder (about 6 Å below the GMO heads). The obtained results may help understanding the role of water structure in the processes of insertion of external molecules inside the GMO/water system. The present work has a semi-quantitative character and it should be considered as the initial stage of more comprehensive future theoretical studies.

  5. Development of mesophase pitch derived mesoporous carbons through a commercially nanosized template.

    PubMed

    Qiao, W M; Song, Y; Hong, S H; Lim, S Y; Yoon, S-H; Korai, Y; Mochida, I

    2006-04-11

    Mesoporous carbons (MCs) with a high surface area (up to 900 m2/g), large pore volume (up to 2.1 cm3/g), high mesopore ratio (94%), and high yield (70%) were successfully prepared from an AR mesophase pitch, using a commercially nanosized silica template. The removal of the template provided some larger mesopores of 25-50 nm (pore I) with a surface area of ca. 300 m2/g, while the successive carbonization opened the closed pores within the carbon body to give smaller mesopores of 2-10 nm (pore II) with a similar surface area. During the carbonization of pitch precursor, the evaporation of volatile components swells the carbon to introduce the second mesopores among the domains and even microdomain units because of their rearrangements and overlappings in the process. The addition of iron salt with the silica template resulted in a remarkable increase of the surface area (ca. 300 m2/g) by introducing mesopores of 3-5 nm. The resultant MCs maintained some graphitizable natures derived from the anisotropic precursor. Their graphitization at 2400 degrees C provided the graphitic structure with large surface areas (270-460 m2/g) and mesoporosity.

  6. High-capacity lithium-ion cells using graphitized mesophase-pitch-based carbon fiber anodes

    NASA Astrophysics Data System (ADS)

    Ohsaki, Takahisa; Kanda, Motoya; Aoki, Yoshiyasu; Shiroki, Hiroyuki; Suzuki, Shintaro

    We have developed high-capacity lithium-ion cells using graphitized mesophase-pitch-based carbon fiber (MCF) as an anode material. The graphitized MCF is a highly graphitized carbon fiber with a radial-like texture in the cross section. This structure contributes to the rapid diffusion of lithium ions inside the carbon fiber. The diffusion coefficient of lithium ions in the graphitized MCF was one order of magnitude larger than those for graphite, resulting in an excellent high-rate performance of the carbon electrode. The graphitized MCF anode showed larger capacity, a higher rate capability, and better reversibility than the graphite anode. The 863448 size (8.6 mm × 34 mm × 48 mm) prismatic cell with the graphitized MCF anode exhibited a large capacity of > 1000 mAh. At 3 A discharge, the prismatic cell had 95% of its capacity at 0.5 A discharge with a mid-discharge voltage of 3.35 V. The cell maintained > 85% of its initial capacity after 500 cycles and showed high capacity at -20 °C. It has thus been demonstrated that the prismatic cell using the graphitized MCF anode has excellent performance, and is an attractive choice for the power sources of cellular phones and other appliances.

  7. Rechargeable lithium-ion cells using graphitized mesophase-pitch-based carbon fiber anodes

    SciTech Connect

    Takami, Norio; Satoh, Asako; Hara, Michikazu; Ohsaki, Takahisa

    1995-08-01

    The electrochemistry of lithium intercalation into a graphitized mesophase-pitch-based carbon fiber with a radial-like texture used as the anode material in rechargeable lithium-ion cells was characterized. The radial-like texture in the cross section of the carbon fiber contributed to the rapid diffusion of lithium ions, resulting in the high rate capability. The anode performance of the graphitized carbon fiber was superior to that of the graphite. Experimental flat-plate C/LiCoO{sub 2} lithium-ion cells using the graphitized carbon fiber anode exhibited a high mid-discharge voltage of 3.7 V, a high rate capability, and a long cycle life of more than 400 cycles at 2 mA/cm{sup 2} mA/cm{sup 2} during charge-discharge cycling between 4.2 and 2.7 V. The long cycle life obtained for the cell was due to no significant change in resistance associated with the passivating films on the graphitized carbon fiber with extended cycles. It was also demonstrated that A size C/LiCoO{sub 2} cells using the graphitized carbon fiber anode have excellent rate performance at discharge currents between 0.25 and 3 A, a large discharge capacity of 0.95 Ah, and a high energy density of 310 Wh/dm{sup 3} and 120 Wh/kg.

  8. Phospholipid-based nonlamellar mesophases for delivery systems: bridging the gap between empirical and rational design.

    PubMed

    Martiel, Isabelle; Sagalowicz, Laurent; Mezzenga, Raffaele

    2014-07-01

    Phospholipids are ubiquitous cell membrane components and relatively well-accepted ingredients due to their natural origin. Phosphatidylcholine (PC) in particular offers a promising alternative to monoglycerides for lyotropic liquid crystalline (LLC) delivery system applications in the food, cosmetics and pharmaceutical industries, provided its strong tendency to form zero-mean curvature lamellar mesophases in water can be overcome. Higher negative curvatures are usually reached through the addition of a third lipid component, forming a ternary diagram phospholipid/water/oil. The initial part of this work summarizes the potential advantages and the challenges of phospholipid-based delivery system applications. In the next part, various ternary PC/water/oil systems are discussed, with a special emphasis on the PC/water/cyclohexane and PC/water/α-tocopherol systems. We report that R-(+)-limonene has a quantitatively similar effect as cyclohexane. The last part is devoted to the theoretical interpretation of the observed phase behaviors. A fruitful parallel is drawn with PC polymer-like reverse micelles, leading to a thermodynamic description in terms of interfacial bending energy. Investigations at the molecular level are reviewed to help in bridging the empirical and theoretical approaches. Predictive rules are finally derived from this wide-ranging overview, thereby opening the way to a future rational design of PC-based LLC delivery systems.

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

    NASA Astrophysics Data System (ADS)

    Golmohammadi, Mojdeh; Rey, Alejandro D.

    2010-07-01

    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 (⊥,∥), (ii) prolate (⊥,∥), (iii) scalene O(⊥,∥), and (iv) scalene P(⊥,∥), where the symbols (⊥,∥) 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 ⊥nematic→biaxial nematic→uniaxial∥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 (⊥⇄∥) 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

  10. Isomorphism Within the Hexagonal Columnar Mesophase of Molecular and Macromolecular Self- and Co-Assembled Columns Containing Tapered Groups

    DTIC Science & Technology

    1994-06-30

    ttni " O-m ’mm OFFICE OF NAVAL RESEARCH CONTRACT N00014-89-J- 1828 O R &T Code 3132080 Abstract Report #3 ISOMORPHISM WITHIN THE HEXAGONAL COLUMNAR...MESOPHASE OF MOLECULAR AND MACROMOLECULAR SELF- AND CO-ASSEMBLED COLUMNS CONTAINING TAPERED GROUPS by D. Tomazos, R . Out, J. Heck, G. Johansson, V...Containing Tapered Grouls 6. AUTHOR(S) D. Tomazos, R . Out, J. Heckc, G. Johansson, V. Percec, and M. Moeller 7. PERFORMING ORGANIZATION NAME(S) AND

  11. Imaging liquid crystalline mesophases in vivo and in vitro: measuring molecular birefringence and order parameter in liquid crystals

    NASA Astrophysics Data System (ADS)

    Zhou, Yu-Ming; Newton, Richard H.; Haffegee, J.; Brown, Jacki Y.; Ross, Stephen; Bolton, John P.; Ho, Mae-Wan

    1996-12-01

    A recent technique optimizing the detection of small birefringences typical of biological liquid crystals has been described elsewhere. Here, we derive a liner relationship between color intensity, molecular birefringence and degree of phase alignment, based on which, a quantitative image analysis is developed. The image analysis is used to define the dynamics of the phase transition-like increase in color intensity accompanying the condensation of the body-wall musculature in the maturing Drosophila larva, to map the orientation of the collagen fibers in the intervertebral disc, and to investigate mesophases of pork skin collagen assembled in vitro.

  12. Effect of hygroscopicity of the metal salt on the formation and air stability of lyotropic liquid crystalline mesophases in hydrated salt-surfactant systems.

    PubMed

    Albayrak, Cemal; Barım, Gözde; Dag, Ömer

    2014-11-01

    It is known that alkali, transition metal and lanthanide salts can form lyotropic liquid crystalline (LLC) mesophases with non-ionic surfactants (such as CiH2i+1(OCH2CH2)jOH, denoted as CiEj). Here we combine several salt systems and show that the percent deliquescence relative humidity (%DRH) value of a salt is the determining parameter in the formation and stability of the mesophases and that the other parameters are secondary and less significant. Accordingly, salts can be divided into 3 categories: Type I salts (such as LiCl, LiBr, LiI, LiNO3, LiClO4, CaCl2, Ca(NO3)2, MgCl2, and some transition metal nitrates) have low %DRH and form stable salt-surfactant LLC mesophases in the presence of a small amount of water, type II salts (such as some sodium and potassium salts) that are moderately hygroscopic form disordered stable mesophases, and type III salts that have high %DRH values, do not form stable LLC mesophases and leach out salt crystals. To illustrate this effect, a large group of salts from alkali and alkaline earth metals were investigated using XRD, POM, FTIR, and Raman techniques. Among the different salts investigated in this study, the LiX (where X is Cl(-), Br(-), I(-), NO3(-), and ClO4(-)) and CaX2 (X is Cl(-), and NO3(-)) salts were more prone to establish LLC mesophases because of their lower %DRH values. The phase behavior with respect to concentration, stability, and thermal behavior of Li(I) systems were investigated further. It is seen that the phase transitions among different anions in the Li(I) systems follow the Hofmeister series.

  13. Crystallizing Membrane Proteins in the Lipidic Mesophase. Experience with Human Prostaglandin E2 Synthase 1 and an Evolving Strategy

    PubMed Central

    2015-01-01

    The lipidic mesophase or in meso method for crystallizing membrane proteins has several high profile targets to its credit and is growing in popularity. Despite its success, the method is in its infancy as far as rational crystallogenesis is concerned. Consequently, significant time, effort, and resources are still required to generate structure-grade crystals, especially with a new target type. Therefore, a need exists for crystallogenesis protocols that are effective with a broad range of membrane protein types. Recently, a strategy for crystallizing a prokaryotic α-helical membrane protein, diacylglycerol kinase (DgkA), by the in meso method was reported (Cryst. Growth. Des.2013, 13, 2846−2857). Here, we describe its application to the human α-helical microsomal prostaglandin E2 synthase 1 (mPGES1). While the DgkA strategy proved useful, significant modifications were needed to generate structure-quality crystals of this important therapeutic target. These included protein engineering, using an additive phospholipid in the hosting mesophase, performing multiple rounds of salt screening, and carrying out trials at 4 °C in the presence of a tight binding ligand. The crystallization strategy detailed here should prove useful for generating structures of other integral membrane proteins by the in meso method. PMID:24803849

  14. Anodic performance and mechanism of mesophase-pitch-derived carbons in lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Mochida, Isao; Ku, Cha-Hun; Yoon, Seong-Ho; Korai, Yozo

    The anodic performance of soft carbons prepared from synthetic mesophase pitches by heat-treatment at 500 to 1200°C are investigated in order to clarify their mechanism for the insertion of lithium ions. It is found that the insertion mechanism for soft carbon heat-treated at low temperatures is divided into the following three cases: (i) lithium ions partially charge transferred on the surface of hexagonal planes or in the unstacked carbon layers to be charged and discharged at 0.25 to 0.8 V (Type I); (ii) intercalated into carbon layers up to a higher stage to be charged and discharged at 0.0 to 0.25 V (Type II); (iii) inserted into the microspaces located at the edges of carbon clusters to be charged at 0.0 to 0.1 V and discharged at 0.8 to 2.0 V (Type III). Lithium ions of Types I and II are charged and discharged reversibly, hence, the capacity is stable with cycling. By contrast, the capacity of Type III ions decreases gradually with cycle number. The irreversible charge-discharge and poor cycle stability of Type III ions suggest some chemical reactions during charge-discharge that increase the discharge potential and modify the carbon structure. Bonding of carbon planes at facing edges in the anisotropic carbon may be responsible for the poor cycle stability. The capacity of Type II ions increases gradually with heat-treatment which graphitizes carbon to allow intercalation. By contrast, the capacities of Types I and III ions are decreased gradually and sharply, respectively, by heat-treatment. The progress of graphitization densifies the carbon and reduces the free surface of the hexagonal sheet and the charging to such sites. The performance of Type III ions reflects the characteristic of anisotropic carbon in which the clusters are aligned to have more faced edges than those in isotropic carbon. The heat-treatment combines the edges to enlarge considerably the hexagonal plane in this temperature range.

  15. Kinetics and Mechanism of Lipid Mesophase Structural Changes Induced by Pressure and X-Radiation Damage

    NASA Astrophysics Data System (ADS)

    Cheng, Anchi

    1995-01-01

    damage. We found that x-ray damage effects dramatic changes in structure and mesophase behavior of hydrated lipid. Damage severity is sensitive to lipid headgroup identity and to lipid hydration. These results have improved our understanding of this undesirable process and have served to alert the community to the nature and severity of the problem.

  16. NMR and Raman spectroscopy monitoring of proton/deuteron exchange in aqueous solutions of ionic liquids forming hydrogen bond: a role of anions, self-aggregation, and mesophase formation.

    PubMed

    Klimavicius, Vytautas; Gdaniec, Zofia; Kausteklis, Jonas; Aleksa, Valdemaras; Aidas, Kestutis; Balevicius, Vytautas

    2013-09-05

    The H/D exchange process in the imidazolium-based room temperature ionic liquids (RTILs) 1-decyl-3-methyl-imidazolium bromide- and chloride ([C10mim][Br] and [C10mim][Cl]) in D2O solutions of various concentrations was studied applying (1)H, (13)C NMR, and Raman spectroscopy. The time dependencies of integral intensities in NMR spectra indicate that the H/D exchange in [C10mim][Br] at very high dilution (10(-4) mole fraction of RTIL) runs only slightly faster than in [C10mim][Cl]. The kinetics of this process drastically changes above critical aggregation concentration (CAC). The time required to reach the apparent reaction saturation regime in the solutions of 0.01 mole fraction of RTIL was less 10 h for [C10mim][Br], whereas no such features were seen for [C10mim][Cl] even tens of days after the sample was prepared. The H/D exchange was not observed in the liquid crystalline gel mesophase. The role of anions, self-aggregation (micellization), and mesophase formation has been discussed. Crucial influence of Br(-) and Cl(-) anions on the H/D exchange rates above CAC could be related to the short-range ordering and molecular microdynamics, in particular that of water molecules. The concept of the conformational changes coupled with the H/D exchange in imidazolium-based ionic liquids with longer hydrocarbon chains can be rejected in the light of (13)C NMR experiment. The revealed changes in (13)C NMR spectra are caused by the secondary ((13)C) isotope effects not being the signal shifts due to the conformational trans-gauche transition.

  17. Characterization of Lipid-Templated Silica and Hybrid Thin Film Mesophases by Grazing Incidence Small-Angle X-ray Scattering

    PubMed Central

    Dunphy, Darren R.; Alam, Todd M.; Tate, Michael P.; Hillhouse, Hugh W.; Smarsly, Bernd; Collord, Andrew D.; Carnes, Eric; Baca, Helen K.; Köhn, Ralf; Sprung, Michael; Wang, Jin; Brinker, C. Jeffrey

    2009-01-01

    The nanostructure of silica and hybrid thin film mesophases templated by phospholipids via an evaporation-induced self-assembly (EISA) process was investigated by grazing-incidence small-angle X-ray scattering (GISAXS). Diacyl phosphatidylcholines with two tails of 6 or 8 carbons were found to template 2D hexagonal mesophases, with the removal of lipid from these lipid/silica films by thermal or UV/O3 processing resulting in a complete collapse of the pore volume. Monoacyl phosphatidylcholines with single tails of 10–14 carbons formed 3D micellular mesophases; the lipid was found to be extractable from these 3D materials, yielding a porous material. In contrast to pure lipid/silica thin film mesophases, films formed from the hybrid bridged silsesquioxane precursor bis(triethoxysilyl)ethane exhibited greater stability toward (both diacyl and monoacyl) lipid removal. Ellipsometric, FTIR, and NMR studies show that the presence of phospholipid suppresses siloxane network formation, while actually promoting condensation reactions in the hybrid material. 1D X-ray scattering and FTIR data were found to be consistent with strong interactions between lipid headgroups and the silica framework. PMID:19496546

  18. Transitions between mesophases involving cubic phases in the surfactant-water systems. Epitaxial relations and their consequences in a geometrical framework

    NASA Astrophysics Data System (ADS)

    Clerc, M.; Levelut, A. M.; Sadoc, J. F.

    1991-10-01

    In order to approach the fascinating structure of the cubic mesophases, we study phase transitions involving them and another mesophases with simpler structures. In the first part, we give some results obtained in the C_{12}EO_6/water binary system, that exhibits the most frequent case of bicontinuous cubic mesophase, with space group Ia3d, and two transitions toward the hexagonal and lamellar mesophases. X-ray scattering experiments and some optical observations in polarized light are presented for oriented single-domains of the mesophases. In the second part, we propose some topological arguments to explain the transformations involved at these two transitions and propose some possible fluctuations associated with them. les phases cubiques dans les systèmes eau/savon sont un exemple tout à fait remarquable d'organisation moléculaire entre liquides. Nous présentons ici une étude de transitions de phases entre elles et d'autres phases de structure beaucoup moins complexe, en montrant comment la structure cubique peut se déduire de celle des autres. Dans la première partie, nous présentons les résultats obtenus pour le système modèle C_{12}EO_6/eau, qui offre le cas le plus fréquent de phase cubique bicontinue, de groupe d'espace Ia3d, ainsi que deux transitions vers les phases hexagonale et lamellaire. Des clichés de diffraction des rayons X aux petits angles ont été obtenus pour des échantillons orientés de ces phases, mettant en particulier en évidence les fluctuations des structures observées, par la présence de “diffusions diffuses" entre les réflexions de Bragg. Dans la seconde partie, nous exposons une analyse détaillée des changements de topologie intervenant lors de ces deux transitions, puis discutons des fluctuations pouvant leur être associées, à la lumière des observations précédentes.

  19. 7Li-nuclear magnetic resonance observations of lithium insertion into coke carbon modified with mesophase-pitch

    NASA Astrophysics Data System (ADS)

    Sato, Yuichi; Tanuma, Ken-ichi; Takayama, Toshio; Kobayakawa, Koichi; Kawai, Takanobu; Yokoyama, Akira

    Lithium intercalation into coke carbon modified with mesophase-pitch and heat-treated at 800, 1000, and 3000°C was observed using solid-state 7Li-nuclear magnetic resonance ( 7Li-NMR) spectroscopy. It was found that the fully lithiated state charged to 0 V in the modified coke heat-treated at 3000°C showed a peak at about 45 ppm; on the other hand, two peaks appeared at about 45 and 16-17 ppm in the modified coke heat-treated below 1000°C. The peak appearing at 45 ppm indicated that Li-GIC is present in the first stage, and the peak at about 16-17 ppm indicated that the lithium stored in the modified part has an ionic character greater than in the coke part and is not a lithium cluster. The lithiated states charged to 0.1 and 0.2 V and discharged to 0.1, 0.2 and 1.5 V from the charged state (0 V) are also described.

  20. Characteristics of boron doped mesophase pitch-based carbon fibers as anode materials for lithium secondary cells

    SciTech Connect

    Tamaki, Toshio; Kawamura, Toshifumi; Yamazaki, Yoshinori

    1998-07-01

    Mesophase pitch-based Carbon Fibers(MCF) have been investigated as anode materials for lithium secondary cells by examining their physical and electrochemical properties. Discharge capacity and initial charge-discharge efficiency of the materials were studied in relation to the heat treatment temperatures of MCF. MCF heat treated at about 3,000 C gave high discharge capacity over 310mAh/g, good efficiency (93%) and superior current capability of 600mA/g (6mA/cm2). On the other hand, to improve the battery capacity, Boron was doped to the fiber about several {degree} by adding B{sub 4}C to the pre-carbonized milled fibers and then heat-treated up to 3,000 C in Ar. Then heat treated at 2,500 C under vacuum condition to remove remained B{sub 4}C. The structure of Boron-doped fibers was characterized and compared with that of non-doped standard fibers, and also Li ion battery performances are evaluated. The Boron-doped MCF indicated improvement in graphitization and increased discharge capacity as high as 360mAh/g. The voltammograms of both fibers are different from each other. The cell mechanism is discussed based on the unique structure of Boron-doping to the MCF is very effective for the battery performance.

  1. How Peptide Molecular Structure and Charge Influence the Nanostructure of Lipid Bicontinuous Cubic Mesophases: Model Synthetic WALP Peptides Provide Insights.

    PubMed

    van 't Hag, Leonie; Li, Xu; Meikle, Thomas G; Hoffmann, Søren V; Jones, Nykola C; Pedersen, Jan Skov; Hawley, Adrian M; Gras, Sally L; Conn, Charlotte E; Drummond, Calum J

    2016-07-12

    Nanostructured bicontinuous lipidic cubic phases are used for the encapsulation of proteins in a range of applications such as in meso crystallization of transmembrane proteins and as drug delivery vehicles. The retention of the nanoscale order of the cubic phases subsequent to protein incorporation, as well as retention of the protein structure and function, is essential for all of these applications. Herein synthetic peptides (WALP21, WALPS53, and WALPS73) with a common α-helical hydrophobic domain, but varying hydrophilic loop size, were designed to systematically examine the effect of peptide structure and charge on bicontinuous cubic phases. The effect of the cubic phases on the secondary structure of the peptides was also investigated. The incorporation of the WALP peptides in cubic phases formed by a range of lipids showed that hydrophobic mismatch of the peptides with the lipid bilayers, the hydrophilic domain size, and peptide charge were all significant factors determining the response of the lipid nanomaterial to protein insertion. As charge repulsion had the most significant effect on the phase transitions observed, we suggest that buffer pH and salt concentration must be carefully considered to ensure cubic mesophase retention. Importantly, the WALP peptides were found to have a different conformation depending on the local lipid environment. Such structural changes could potentially affect membrane protein function, which is crucial for both current and prospective applications.

  2. A Model of Chevrons in Smectic C^* Liquid Crystals: Uniform and Twisted ``Soliton'' States

    NASA Astrophysics Data System (ADS)

    Limat, Laurent

    1995-06-01

    We consider a simplified model of the chevron structure observed in thin cells of ferroelectric smectic liquid crystals, based on a generalization of the “uniaxial” (or “nematic”) approximation of orientation elasticity. This model allows for the conciliation of the continuous nature of the layers with the matching conditions postulated by Clark, and takes large rotations of the c-director into account. When the layer tilt angle is small compared to the molecular cone angle, we show that the structure of the “uniform” states reduces to the “soliton” solution found by Nakagawa. Within the same limit “twisted” states are investigated by a perturbation calculation and by qualitative energy considerations. The results suggest the existence of asymmetrical c-director distributions similar to those observed in recent experiments: in these states, the c-director splay remains mainly localized in one half of the cell, the increase of splay energy being compensated by a reduction of the “folding energy” localized in the chevron core. On discute un modèle simplifié de la structure en chevron observée dans les cristaux liquides smectiques ferroélectriques en cellules minces, basé sur une légère généralisation de l'approximation “uniaxiale” (ou “nématique”) de l'élasticité d'orientation. Ce modèle permet de réconcilier la nature continue des couches avec les conditions de raccordement postulées par Clark et prend en compte de fortes rotations de la projection du directeur sur le plan des couches. On montre que lorsque l'angle d'inclinaison des couches est faible devant l'angle du cône moléculaire, la structure, des états “uniformes” est donnée par la solution de type “soliton” découverte par Nakagawa. Dans la même limite, on étudie les états “tordus” par un calcul de perturbation complété par des arguments énergétiques plus qualitatifs. Ces deux approches suggèrent l'existence de distributions asymétriques de la torsion du directeur moléculaire similaires à celles observées dans des expériences récentes: dans ces états, la torsion se localiserait dans une demi-épaisseur de cellule, l'augmentation d'énergie étant compensée par une réduction de l'énergie de coeur du chevron.

  3. Chiral smectic-A and smectic-C phases with de Vries characteristics

    NASA Astrophysics Data System (ADS)

    Yadav, Neelam; Panov, V. P.; Swaminathan, V.; Sreenilayam, S. P.; Vij, J. K.; Perova, T. S.; Dhar, R.; Panov, A.; Rodriguez-Lojo, D.; Stevenson, P. J.

    2017-06-01

    Infrared and dielectric spectroscopic techniques are used to investigate the characteristics of two chiral smectics, namely, 1,1,3,3,5,5,5-heptamethyltrisiloxane 1-[4'-(undecyl-1-oxy)-4-biphenyl(S,S)-2-chloro-3-methylpentanoate] (MS i3M R11 ) and tricarbosilane-hexyloxy-benzoic acid (S)-4'-(1-methyl-hexyloxy)-3'-nitro-biphenyl-4-yl ester (W599). The orientational features and the field dependencies of the apparent tilt angle and the dichroic ratio for homogeneous planar-aligned samples were calculated from the absorbance profiles obtained at different temperatures especially in the smectic-A* phase of these liquid crystals. The dichroic ratios of the C-C phenyl ring stretching vibrations were considered for the determination of the tilt angle at different temperatures and different voltages. The low values of the order parameter obtained with and without an electric field applied across the cell in the Sm -A* phase for both smectics are consistent with the de Vries concept. The generalized Langevin-Debye model introduced in the literature for explaining the electro-optical response has been applied to the results from infrared spectroscopy. The results show that the dipole moment of the tilt-correlated domain diverges as the transition temperature from Sm -A* to Sm -C* is approached. The Debye-Langevin model is found to be extremely effective in confirming some of the conclusions of the de Vries chiral smectics and gives additional results on the order parameter and the dichroic ratio as a function of the field across the cell. Dielectric spectroscopy finds large dipolar fluctuations in the Sm -A* phase for both compounds and again these confirm their de Vries behavior.

  4. Anisotropy of electrostatic interaction in free-standing smectic-C* films

    NASA Astrophysics Data System (ADS)

    Ulyanov, S. V.

    2017-06-01

    The correlation function of the director fluctuations in a free-standing smectic ferroelectric film is calculated theoretically. In the functional of free energy, the anisotropy of the Coulomb interaction of polarization charges is taken into account. The results of calculations were used to obtain the angular dependences of scattered light intensity. It has been shown that for relatively thick films, the anisotropy of the Coulomb interaction of polarization charges can change significantly the scattered light intensity.

  5. Lyotropic mesophases formed by solutions of sodium strearate in glycerol and water

    NASA Astrophysics Data System (ADS)

    Wang, Qingbing; Joshi, Leela; Satyendra Kumar, Satyendra; Yaravoy, Yury; Teanoosh, Moaddel

    2004-03-01

    Solutions of sodium stearate in concentrations ranging from 1 to 20 wt %, in glycerol and glycerol + water exhibit two phases between room temperature and 100 °C for all mixtures. In the high temperature phase, the solutions flow easily while they form a gel phase with unique elastic properties in the low temperature phase. Small angle neutron and x-ray scattering measurements performed on partially deutrated samples reveal structural details of these solutions. The high temperature phase is found to be an isotropic dispersion of micellar aggregates, the lower temperature phase possesses more complex structure. These results augmented with results from differential scanning calorimetry, NMR proton relaxation and other techniques will be presented. Supported by Unilever Research, USA.

  6. Effect of Mesophase Order on the Dynamics of Side Group Liquid Crystalline Polymers

    SciTech Connect

    Auad, M.L.; Kempe, M.D.; Kornfield, J.A.; Rendon, S.; Burghardt, W.R.; Yoon, K.

    2010-07-13

    Rheology and X-ray scattering were employed to probe the viscoelastic properties and structural transitions of model cyano-biphenyl-based side-group liquid-crystalline polymers (SGLCPs) with molecular weights ranging from 91 to 1900 kg/mol. Temperature-dependent rheological data show a rapid change in dynamics over a small temperature range. Small-angle X-ray scattering reveals these changes to be associated with an isotropic to smectic transition with an appreciable biphasic region. The presence of a biphasic region is attributed to inhomogeneity in chain structure resulting from incomplete attachment of mesogens to every monomeric unit in the SGLCP polymer. While isotropic and smectic phase data may be separately time-temperature shifted to create master curves for the individual phases, we argue against attempts to achieve superposition between the two phases in the high-frequency regime, since smectic ordering may not simply slow the dynamics but also increase the modulus of the sample. Molecular weight has a strong influence on rheology in the isotropic phase, where an entanglement plateau emerges; however, the smectic-phase rheology is dominated by the layer structure and is fairly insensitive to molecular weight.

  7. Structural Phase Diagram for Multi-lamellar Tubular Deformations of Lipid Mesophases

    NASA Astrophysics Data System (ADS)

    Tayebi, Lobat; Parikh, Atul

    2011-03-01

    Stable multi-lamellar cylindrical tubules protrude readily from concentrated mass of amphiphilic molecules in response to a variety of external stresses. Using energetic considerations, we have developed an phase diagram, predicting various types of morphologies of equilibrium multilamellar tubular deformations that stabilize for a broad range of their bending rigidity and surface tension values. Tubular morphologies are described in terms of core radius(rc) and number of lamellae(N). Results of the calculations reveal that emergent tubular morphologies can be classified into three major classes: (1) thin tethers (small rc and low N); (2) solid tubes (high N); and (3) hollow tubes (large rc and and low N). Experimental validation of these predictions is obtained in experiments involving hydration of dry stack lipids Here, tubular deformations, referred to as myelin figures, of all predicted morphologies form in separate populations. Furthermore, the phase diagram also sheds light on a long-standing question of the determinants of the thickness of such myelin figures.

  8. Facile synthesis of mesophase pitch/exfoliated graphite nanoplatelets nanocomposite and its application as anode materials for lithium-ion batteries

    SciTech Connect

    Yang Yishuang; Wang Chengyang; Chen Mingming; Shi Zhiqiang; Zheng Jiaming

    2010-09-15

    Mesophase pitch (MP)/exfoliated graphite nanoplatelets (GNPs) nanocomposite has been prepared by an efficient method with an initiation of graphite intercalation compounds (GIC). X-ray diffraction, optical microscopy, high-resolution transmission electron microscopy and scanning electron microscopy analysis techniques are used to characterize the samples. It is observed that GIC has exfoliated completely into GNPs during the formation of MP/GNPs nanocomposite and the GNPs are distributed uniformly in MP matrix, which represent a conductive path for a movement of electrons throughout the composites. Electrochemical tests demonstrate that the carbonized MP/GNPs nanocomposite displays higher capacity and better cycle performance in comparison with the pure carbonized MP. It is concluded that such a large improvement of electrochemical performance within the nanocomposite may in general be related to the enhanced electronic conductivity, which is achieved by good dispersion of GNPs within MP matrix and formation of a 3D network of GNPs. - Graphical abstract: Uniform mesophase pitch/exfoliated graphite nanoplatelets nanocomposite has been efficiently fabricated with an initiation of graphite intercalation compounds. The as-prepared composite electrode exhibited high electrochemical performance for Li-ion batteries.

  9. Exploring the in meso crystallization mechanism by characterizing the lipid mesophase microenvironment during the growth of single transmembrane α-helical peptide crystals.

    PubMed

    van 't Hag, Leonie; Knoblich, Konstantin; Seabrook, Shane A; Kirby, Nigel M; Mudie, Stephen T; Lau, Deborah; Li, Xu; Gras, Sally L; Mulet, Xavier; Call, Matthew E; Call, Melissa J; Drummond, Calum J; Conn, Charlotte E

    2016-07-28

    The proposed mechanism for in meso crystallization of transmembrane proteins suggests that a protein or peptide is initially uniformly dispersed in the lipid self-assembly cubic phase but that crystals grow from a local lamellar phase, which acts as a conduit between the crystal and the bulk cubic phase. However, there is very limited experimental evidence for this theory. We have developed protocols to investigate the lipid mesophase microenvironment during crystal growth using standard procedures readily available in crystallography laboratories. This technique was used to characterize the microenvironment during crystal growth of the DAP12-TM peptide using synchrotron small angle X-ray scattering (SAXS) with a micro-sized X-ray beam. Crystal growth was found to occur from the gyroid cubic mesophase. For one in four crystals, a highly oriented local lamellar phase was observed, providing supporting evidence for the proposed mechanism for in meso crystallization. A new observation of this study was that we can differentiate diffraction peaks from crystals grown in meso, from peaks originating from the surrounding lipid matrix, potentially opening up the possibility of high-throughput SAXS analysis of in meso grown crystals.This article is part of the themed issue 'Soft interfacial materials: from fundamentals to formulation'.

  10. Facile synthesis of mesophase pitch/exfoliated graphite nanoplatelets nanocomposite and its application as anode materials for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Yang, Yi-Shuang; Wang, Cheng-Yang; Chen, Ming-Ming; Shi, Zhi-Qiang; Zheng, Jia-Ming

    2010-09-01

    Mesophase pitch (MP)/exfoliated graphite nanoplatelets (GNPs) nanocomposite has been prepared by an efficient method with an initiation of graphite intercalation compounds (GIC). X-ray diffraction, optical microscopy, high-resolution transmission electron microscopy and scanning electron microscopy analysis techniques are used to characterize the samples. It is observed that GIC has exfoliated completely into GNPs during the formation of MP/GNPs nanocomposite and the GNPs are distributed uniformly in MP matrix, which represent a conductive path for a movement of electrons throughout the composites. Electrochemical tests demonstrate that the carbonized MP/GNPs nanocomposite displays higher capacity and better cycle performance in comparison with the pure carbonized MP. It is concluded that such a large improvement of electrochemical performance within the nanocomposite may in general be related to the enhanced electronic conductivity, which is achieved by good dispersion of GNPs within MP matrix and formation of a 3D network of GNPs.

  11. 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.

  12. Chiral supramolecular order revealed during the formation of calf thymus and phage DNA crystals.

    PubMed

    Vidal, Benedicto de Campos; Mello, Maria Luiza S

    2017-09-01

    The control of DNA packaging has been reported to be dependent on an ordered liquid-crystalline state. However, the textural characteristics that are typical of crystals and that resemble mesophases have not been reported for highly polymerized or even shorter types of DNA filaments under in vitro conditions that favor crystallization. Because DNA crystals are expected to exhibit particular textural optical anisotropies, pure and highly polymerized calf thymus DNA and simpler λ phage DNA were crystallized from solution drops and were analyzed using high-performance polarization microscopy with and without differential interference contrast (DIC) optics. Both types of DNA formed crystals that exhibited chiral supramolecular textures resembling the twist-grain boundary (TGB) columnar mesophases described for liquid crystals and exhibited intrinsic negative birefringence. To the best of our knowledge, this is the first observation using polarization/interference optics of pure DNA crystals that have TGB columnar mesophase-like textural characteristics. A comparison of the crystals formed from the highly polymerized calf thymus DNA and those formed from the shorter phage DNA strands revealed textural differences. Compared to the phage DNA crystals, the crystals of highly polymerized thymus DNA exhibited a more intertwisted columnar distribution and a fibrous texture between their columnar structures. In addition, a form birefringence phenomenon was detected only in the thymus DNA crystals. These characteristics are presumed to reflect the higher level of supramolecular order, self-assembly and chirality in highly polymerized calf thymus DNA crystals relative to that of crystals formed from the simpler, shorter, λ phage DNA. The higher-order supramolecular organization revealed here for in vitro DNA preparations raises the possibility that this structure could also occur, possibly to a smaller degree, during DNA self-aggregation under specific in vivo conditions

  13. Tyrosine-Based Ionic Liquid Crystals: Switching from a Smectic A to a Columnar Mesophase by Exchange of the Spherical Counterion.

    PubMed

    Neidhardt, Manuel M; Wolfrum, Manpreet; Beardsworth, Stuart; Wöhrle, Tobias; Frey, Wolfgang; Baro, Angelika; Stubenrauch, Cosima; Giesselmann, Frank; Laschat, Sabine

    2016-11-07

    Synthetic strategies were developed to prepare l-tyrosine-based ionic liquid crystals with structural variations at the carboxylic and phenolic OH groups as well as the amino functionality. Salt metathesis additionally led to counterion variation. The liquid-crystalline properties were investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and X-ray diffraction (WAXS, SAXS). The symmetrical ILC chlorides bearing the same alkyl chain at both the ester and ether but either an acyclic or cyclic guanidinium group displayed enantiotropic SmA2 mesophases with phase widths of 31-88 K irrespective of the head group. It was particularly the replacement of chloride in the acyclic guanidinium ILC by hexafluorophosphate that induced a phase change from SmA2 to Colr . This phase change was attributed to a higher curvature of the interface due to the larger anion, which increased the effective head group cross-sectional area of the amphiphilic ILC. The unsymmetrical acyclic guanidinium chlorides, bearing a constant C14 ester and variable alkyl chains on the phenolic position, formed enantiotropic SmA2 phases. The derivative with the largest difference in chain lengths, however, displayed a Colr phase, resulting from discoid aggregates of the cone-shaped guanidinium chloride. The results are discussed in terms of the packing parameters, which indicate that the phase behaviour of the thermotropic tyrosine-based ILCs shows analogies to those of lyotropic liquid crystals.

  14. The phase diagram of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine/sucrose in the dry state. Sucrose substitution for water in lamellar mesophases.

    PubMed

    Hentschel, M; Miethe, P; Meyer, H W

    1989-04-14

    The phase diagram of the binary system, 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC)/sucrose, was determined by DSC. In contrast to dry DPPC, which exhibits chain melting at 342.5 K, the main feature of the DPPC/sucrose system is eutectic melting at 320 K. This was supported earlier by Crowe, J.H., Crowe, L.M. and Chapman, D. (Science 223 (1984) 701-703), who reported a drastic decrease in the chain-melting temperature of the dry lipid in the presence of some mono- and disaccharides. Electron microscopy suggests that the phase structures on either side of the phase transition are of the lamellar type. Definite sugar saturation concentrations can be derived from this phase diagram. Up to about 17 mol% sucrose, i.e., 1 mol of sucrose per 5 mol of lipid is adopted by DPPC in the low-temperature phase Lc. In the high-temperature phase Lm the saturation concentration is well above 90 mol% sucrose at 320 K (eutectic point) but decreases with increasing temperature. The lower limit of 50 mol% sucrose is reached at 455 K. At this temperature, peritectic melting of sucrose occurs. Because of some similarities in the phase diagrams of DPPC/sucrose and DPPC/water, it is possible to understand the sucrose substitution for water in dry lamellar mesophases.

  15. Effect of pressure on the stability, phase behaviour and transformation kinetics between structures of lyotropic lipid mesophases and model membrane systems

    NASA Astrophysics Data System (ADS)

    Winter, R.; Erbes, J.; Czeslik, C.; Gabke, A.

    1998-12-01

    Lipids, which provide valuable model systems for membranes, display a variety of polymorphic phases, depending on their molecular structure and environmental conditions. By use of x-ray and neutron diffraction, infrared spectroscopy and calorimetry, the temperature and pressure dependent structure and phase behaviour of several lipid systems, differing in chain configuration and headgroup structure, have been studied. Besides lamellar phases also non-lamellar phases, such as the inverted hexagonal 0953-8984/10/49/036/img1 phase and bicontinuous cubic phases, have been investigated. Hydrostatic pressure has been used as a physical parameter for studying the stability and energetics of lyotropic mesophases, but also because high pressure is an important feature of certain natural membrane environments (e.g., marine biotopes) and because the high-pressure phase behaviour of biomolecules is of biotechnological interest. Neutron scattering in combination with the H/D contrast variation technique has been used to the study of lateral organization of phase-separated binary lipid mixtures with distinct mixing properties. Within their two-phase coexistence regions large-scale concentration fluctuations appear, and the morphology of these fluctuations can be characterized as a complex heterogeneous system of coexisting clusters having fractal-like properties. By using the pressure-jump relaxation technique in combination with time-resolved synchrotron x-ray diffraction, the kinetics of different lipid phase transformations were also investigated. The time constants for completion of the transitions are dependent on the direction of the transition, the symmetry and topology of the structures involved, and also on the pressure-jump amplitude. In several cases also intermediate structures can be detected under non-equilibrium conditions.

  16. Electric-field-induced unwinding of ferroelectric helix in thin smectic C* layers with soft and rigid anchoring of molecules

    SciTech Connect

    Dolganov, P. V.; Zhilin, V. M. Dolganov, V. K.; Kats, E. I.

    2008-09-15

    The unwinding of a helical structure in thin films of a ferroelectric smectic liquid crystal (LC) by an external electric field has been theoretically studied using a discrete model in which every LC layer is characterized by a two-dimensional vector {xi}{sub i} (describing the orientation of molecules) and by the polarization P{sub i}. It is established that the unwinding of the LC helix in thin films significantly differs from the well-known behavior of thick samples. In particular, discrete intermediate states (differing by an integer or half-integer number of turns) are formed in thin films for both weak and strong anchoring of molecules to a substrate surface. The physical factor responsible for this behavior is the presence of near-surface regions with thicknesses below the helix pitch and the corresponding uncompensated polarization.

  17. Effect of metallic silver nanoparticles on the alignment and relaxation behaviour of liquid crystalline material in smectic C* phase

    NASA Astrophysics Data System (ADS)

    Vimal, Tripti; Kumar Gupta, Swadesh; Katiyar, Rohit; Srivastava, Atul; Czerwinski, Michal; Krup, Katarzyna; Kumar, Sandeep; Manohar, Rajiv

    2017-09-01

    The influence of silver nanoparticles dispersed in a Ferroelectric Liquid Crystal (FLC) on the properties of the resultant composite system has been investigated by thermal, electro-optical, and dielectric methods. We show that the concentration of thiol capped silver nanoparticles is a critical factor in governing the alignment of nanoparticles (NPs) in the host FLC. The orientation of NPs in composite samples affects the ordering of the LC (Liquid Crystal) phase and consequently changes the various phase transition temperatures of the host LC. Formation of self-assembled 2D (two dimensional) arrays of nanoparticles is observed for high concentration of dopant in the LC, oriented perpendicular to the direction of rubbing. We propose that the molecular interaction between the thiol capped NPs and LC molecules is the key factor behind such an arrangement of NPs. Orientation of NPs has affected the relaxation behaviour and various other material parameters, significantly. A noteworthy change in DC conductivity articulates our proposed idea of the formation of 2D array of NPs perpendicular to the direction of rubbing. This comprehensive study endorses the importance of dopant concentration in modifying the properties of the host LC material.

  18. Molecular Engineering of Liquid-Crystalline Polymers by Living Polymerization. 18. SC* Mesophase in Copolymers of (2S, 3S)-(+)-2-Chloro-3- Methylpentyl 4’-(Omega-Vinyloxyalkyloxy) biphenyl-4-carboxylate with Undecanyl and Octyl Alkyl Groups

    DTIC Science & Technology

    1991-11-20

    carboxylate with Undecanyl and Octyl Alkyl Groups by D T IC Virgil Percec and Qiang Zheng .LECTE Department of Macromolecular Science DECO 3 1991 Case...ficatton) s* Mesophase in Copolymers of (2S, 3S)-(+)-2-Chloro-3-MethylpentyI 4 ’-(WO-Vinyloxyalkyloxy) biphenyl-4- carboxylate with Undecanyl and Octyl...number) The synthesis and living cationic polymerization of (2S, 3S)-(+)-2-chloro-3-mnethylpentyl 4’-( 11 - vIn y loxy undecanyloxy)bipheny 1-4- carboxyl

  19. Columnar benzoperylene-hexa- and tetracarboxylic imides and esters: synthesis, mesophase stabilisation and observation of charge-transfer interactions between electron-donating esters and electron-accepting imides.

    PubMed

    Kelber, Julien; Achard, Marie-France; Garreau-de Bonneval, Bénédicte; Bock, Harald

    2011-07-11

    Benzo[ghi]perylene 1,2,4,5,10,11-hexacarboxylic trialkylimide and dialkylimido-dialkyl ester derivatives, displaying a thermodynamically stable hexagonal columnar liquid-crystalline phase at room temperature, have been obtained by the use of previously unexplored chiral racemic α-branched alkylimide functions. One of the trialkylimides described here is the first room temperature columnar solely oligo-alkylimide-substituted arene, and thus constitutes a prototype case of self-assembling organic acceptor materials. As the related hexacarboxylic hexaesters are found to exhibit only a weak tendency to form columnar mesophases, benzo[ghi]perylene 1,2,5,10-tetracarboxylic tetraalkyl esters have been synthesized by regioselective oxidative Diels-Alder addition of maleic anhydride to 3,10-dicyanoperylene, and a room temperature hexagonal columnar mesophase was obtained with branched alkyl chains. The acceptor-type electronic properties of the tri- and diimides have been found to be considerably more pronounced than those of the hexa- and tetracarboxylic esters, and to approach those of the prototype acceptor material C(60). The formation of bathochromically absorbing donor-acceptor complexes was observed with a di- or triimide as acceptor and a tetraester as donor, but not with a hexaester as donor. Exploiting the non-negligible differences in reduction and oxidation potentials between all four types of materials, the minimum HOMO energy difference necessary for charge-transfer-complex formation has been determined to lie between 0.29 and 0.35 eV.

  20. Synthesis, crystal structures, mesomorphic and photo-luminescent properties of 1,3,4-thia(oxa)diazole-based compounds with a terminal methoxy or methylthio group

    NASA Astrophysics Data System (ADS)

    Han, Jie; Chang, Xiao-Yong; Wang, Yan-Mei; Pang, Mei-Li; Meng, Ji-Ben

    2009-11-01

    A series of aromatically 2,5-disubstituted 1,3,4-thia(oxa)diazoles with a terminal methoxy or methylthio group were synthesized and characterized by means of 1H NMR, 13C NMR, MS and elemental analysis. The X-ray crystal structures of compounds 1a and 3b revealed that both of them adopted layered arrangement without short intermolecular interactions. The liquid crystal properties have been investigated by means of polarizing optical microscopy (POM), differential scanning calorimetry (DSC), variable temperature X-ray diffraction (VXRD) and thermogravimetric analysis (TGA). All compounds (except 2a and 2b) exhibited various mesophases (nematic, smectic C and/or smectic A) with wide temperature ranges and good thermal stability. In CH 2Cl 2 solution, all these compounds displayed a room temperature emission with λmax at 371-425 nm and quantum yields of 0.25-0.83. The effect of the sulfur and oxygen atoms on mesomorphic and photo-luminescent properties was discussed according to the positions in the central heterocyclic rings and the terminal groups.

  1. Fuller Revealed

    NASA Image and Video Library

    2015-03-16

    MESSENGER's low-altitude campaign has enabled imaging of Fuller crater (named after American architect Buckminster Fuller) in greater detail than previously possible. The top left panel shows an image of Fuller, with the crater rim outlined in pink and the edge of a low-altitude broadband MDIS image in green. The large panel applies a different stretch to the same MDIS broadband image in the first panel, revealing details of the shadowed surface inside Fuller! In particular, as highlighted with yellow arrows in the bottom left panel, the image reveals a region inside Fuller that is lower in reflectance. The edge of the low-reflectance region has a sharp and well-defined boundary, even when imaged at 46 m/pixel, suggesting that the low-reflectance material is sufficiently young to have preserved a sharp boundary against lateral mixing by impact cratering. Models for surface and near-surface temperature within Fuller crater predict a region that is sufficiently cold to host long-lived water ice beneath the surface but too hot to support water ice at the surface. The low-reflectance region revealed in the images matches the thermal characteristics expected for a lag deposit of volatile, organic-rich material that overlies the water ice. http://photojournal.jpl.nasa.gov/catalog/PIA19244

  2. Molecular Engineering of Liquid Crystal Polymers by Lining Polymerization. 16. Tailor-Made sC* Mesophase in Copolymers of 4-((S-(-)-2- Methyl-1-Butyl)Oxycarbonyl)-4’-omega-Oxyalkyl-1-Vinyl Ether)Biphenyl With Undecanyl and Octyl Alkyl Groups

    DTIC Science & Technology

    1991-10-30

    4-{ [S-(-)-2-Methyl- l -Butyl]Oxycarbonyl) -4’-(W-Oxyalkyl- 1 -Vinyl Ethcr)Biphenyl with Undecanyl and Octyl Alkyl Groups 12. PERSONAL AUTHOR(S...polymerization lower than 40 and polydispersities 1.15 were synthesized and characterized by differential scanning calorimetry (DSC) and thermal optical...an enantiotropic unidentified sx mesophase. Copolymers of 14-8 with 4-{[S(-)2-methyl- l -butyll oxycarbonyl)- 4 ’-( l - oxyuindecanyl-lI-vinyl ether

  3. Revealing Rembrandt

    PubMed Central

    Parker, Andrew J.

    2014-01-01

    The power and significance of artwork in shaping human cognition is self-evident. The starting point for our empirical investigations is the view that the task of neuroscience is to integrate itself with other forms of knowledge, rather than to seek to supplant them. In our recent work, we examined a particular aspect of the appreciation of artwork using present-day functional magnetic resonance imaging (fMRI). Our results emphasized the continuity between viewing artwork and other human cognitive activities. We also showed that appreciation of a particular aspect of artwork, namely authenticity, depends upon the co-ordinated activity between the brain regions involved in multiple decision making and those responsible for processing visual information. The findings about brain function probably have no specific consequences for understanding how people respond to the art of Rembrandt in comparison with their response to other artworks. However, the use of images of Rembrandt's portraits, his most intimate and personal works, clearly had a significant impact upon our viewers, even though they have been spatially confined to the interior of an MRI scanner at the time of viewing. Neuroscientific studies of humans viewing artwork have the capacity to reveal the diversity of human cognitive responses that may be induced by external advice or context as people view artwork in a variety of frameworks and settings. PMID:24795552

  4. Modeling the field control of the surface electroclinic effect near continuous and first-order smectic-A* to smectic-C* transitions.

    PubMed

    Zappitelli, Kara; Hipolite, Dana N; Saunders, Karl

    2014-02-01

    We present and analyze a model for the combination of bulk and surface electroclinic effects in the smectic-A* (Sm-A*) phase near a Sm-A*-Sm-C* transition. As part of our analysis we calculate the dependence of the surface tilt on external electric field and show that it can be eliminated, or even reversed from its zero-field value, as demonstrated in previous experimental work on a system (W415) with a continuous Sm-A*-Sm-C* transition. We also analyze, for the first time, the combination of bulk and surface electroclinic effects in systems with a first-order Sm-A*-Sm-C* transition. The variation of surface tilt with electric field in this case is much more dramatic, with discontinuities and hysteresis. With regard to technological, e.g., display, applications, this could be a feature to be avoided or potentially exploited. Near each type of Sm-A*-Sm-C* transition we obtain the temperature dependence of the field required to eliminate surface tilt. Additionally, we analyze the effect of varying the system's enantiomeric excess, showing that it strongly affects the field dependence of surface tilt, in particular, near a first-order Sm-A*-Sm-C* transition. In this case, increasing enantiomeric excess can change the field dependence of surface tilt from continuous to discontinuous. Our model also allows us to calculate the variation of layer spacing in going from surface to bulk, which in turn allows us to estimate the strain resulting from the difference between the surface and bulk layer spacing. We show that for certain ranges of applied electric field, this strain can result in layer buckling, which reduces the overall quality of the liquid crystal cell. For de Vries materials, with small tilt-induced change in layer spacing, the induced strain for a given surface tilt should be smaller. However, we argue that this may be offset by the fact that de Vries materials, which typically have Sm-A*-Sm-C* transitions near a tricritical point, will generally have larger surface tilt.

  5. Formation of smectic phases in binary liquid crystal mixtures with a huge length ratio

    PubMed Central

    Knecht, Friederike; Hartley, C Scott; Roberts, Jeffrey C; Lemieux, Robert P; Giesselmann, Frank

    2012-01-01

    Summary A system of two liquid-crystalline phenylpyrimidines differing strongly in molecular length was studied. The phase diagram of these two chemically similar mesogens, with a length ratio of 2, was investigated, and detailed X-ray diffraction and electrooptical measurements were performed. The phase diagram revealed a destabilization of the nematic phase, which is present in the pure short compound, while the smectic state was stabilized. The short compound forms smectic A and smectic C phases, whereas the longer compound forms a broad smectic C phase and a narrow higher-ordered smectic phase. Nevertheless, in the mixtures, the smectic C phase is destabilized and disappears rapidly, whereas smectic A is the only stable phase observed over a broad concentration range. In addition, the smectic translational order parameters as well as the tilt angles of the mixtures are reduced. The higher-ordered smectic phase of the longer mesogen was identified as a smectic F phase. PMID:23019439

  6. Mesomorphic and dielectric properties of esters useful for formulation of nematic mixtures for dual frequency addressing system

    NASA Astrophysics Data System (ADS)

    Ziobro, D.; Kula, P.; Dziaduszek, J.; Filipowicz, M.; DĄbrowski, R.; Parka, J.; Czub, J.; Urban, S.; Wu, S. T.

    2009-03-01

    Mesomorphic and dielectric properties of three homologous series of two and three ring fluorosubstituted esters are described. They are 4-cyano-3-fluorophenyl 4-alkyloxy-2-fluorobenzoates, 4-cyano-3-fluorophenyl 4-(4-alkylbenzoyloxy)-2-fluorobenzoates and 3-fluoro-4-cyanophenyl, or 3-fluoro-4-isothiocyanatophenyl or 3,4-difluorophenyl 4'-alkyl-2,3-difluoro-biphenyl-4-carboxylates. The compounds exhibit the nematic mesophase accompanied by the smectic A or smectic C mesophase in some cases. Most of them show strong dependence of the dielectric anisotropy Δɛ upon frequency, at low frequencies Δɛ reaches a value ˜200, while at high frequencies a small negative dielectric anisotropy appears.

  7. Methods for producing mesophase pitch binder pitch

    SciTech Connect

    Lewis, I.C.

    1984-02-14

    A method of producing a pitch or a coke, comprising reacting an aromatic hydrocarbon with anhydrous AlCl/sub 3/ and an acid salt of an organic amine which acid salt reduces the activity of the AlCl/sub 3/, and is miscible with the AlCl/sub 3/ to form a molten eutectic salt mixture reactive with the aromatic hydrocarbon.

  8. Solubilization of nutraceuticals into reverse hexagonal mesophases.

    PubMed

    Amar-Yuli, Idit; Aserin, Abraham; Garti, Nissim

    2008-08-21

    The solubilization of four bioactive molecules with different polarities, in three reverse hexagonal (HII) systems has been investigated. The three HII systems were a typical reverse hexagonal composed of glycerol monooleate (GMO)/tricaprylin/water and two fluid hexagonal systems containing either 2.75 wt % Transcutol or ethanol as a fourth component. The phase behavior of the liquid crystalline phases in the presence of ascorbic acid, ascorbyl palmitate, D-alpha-tocopherol and D-alpha-tocopherol acetate were determined by small-angle X-ray scattering (SAXS) and optical microscopy. Differential scanning calorimetry (DSC) and Fourier-transform infrared (FT-IR) techniques were utilized to follow modifications in the thermal behavior and in the vibrations of different functional groups upon solubilizing the bioactive molecules. The nature of each guest molecule (in both geometry and polarity) together with the different HII structures (typical and fluids) determined the corresponding phase behavior, swelling or structural transformations and its location in the HII structures. Ascorbic acid was found to act as a chaotropic guest molecule, localized in the water-rich core and at the interface. The AP was also a chaotropic guest molecule with its head located in the vicinity of the GMO headgroup while its tail embedded close to the surfactant tail. D-alpha-tocopherol and D-alpha-tocopherol acetate were incorporated between the GMO tails; however, the D-alpha-tocopherol was located closer to the interface. Once Transcutol or ethanol was present and upon guest molecule incorporation, partial migration was detected.

  9. Shear alignment of lamellar mesophase systems

    NASA Astrophysics Data System (ADS)

    Jaju, S. J.; Kumaran, V.

    2015-11-01

    Mixtures of oil, water and surfactants form different microphases. Some of these phases, e.g. lamellar, hexagonal phases, lead to complex rheological behaviour at macroscale due to inherent anisotropy and irregularities in the microstructures. We present a comprehensive simulation study to examine the structure-rheology relationship in lamellar phase flow. At mesoscale, Reynolds number (Re), Schmidt number (Sc), Ericksen number (Er), extent of segregation between hydrophilic and hydrophobic components (r), ratio of viscosity of the two components (Δμ /μ0), and system size to layer width ratio (L / λ) complete the lamellar phase description. We have used lattice Boltzmann simulations to study a two dimensional lamellar phase system of moderate size. The domains and grain boundaries seen at low Sc are replaced by isolated edge dislocations at high Sc. The alignment mechanism does not change with changes in layer bending moduli (Er), viscosity contrast or r. Increasing segregation, increases disorder; this however does not lead to higher resistance to flow. At high Er, the shear tries homogenise the concentration field and disrupt layer formation. We see significantly higher peak viscosity at low Er at high viscosity contrast and due to defect pinning. The authors would like to thank the Department of Science and Technology, Government of India for financial support, and Supercomputer Education and Research Centre at Indian Institute of Science for the computational resources.

  10. Shear alignment of a disordered lamellar mesophase.

    PubMed

    Kumaran, V; Raman, D S S

    2011-03-01

    The shear alignment of an initially disordered lamellar phase is examined using lattice Boltzmann simulations of a mesoscopic model based on a free-energy functional for the concentration modulation. For a small shear cell of width 8λ, the qualitative features of the alignment process are strongly dependent on the Schmidt number Sc=ν/D (ratio of kinematic viscosity and mass diffusion coefficient). Here, λ is the wavelength of the concentration modulation. At low Schmidt number, it is found that there is a significant initial increase in the viscosity, coinciding with the alignment of layers along the extensional axis, followed by a decrease at long times due to the alignment along the flow direction. At high Schmidt number, alignment takes place due to the breakage and reformation of layers because diffusion is slow compared to shear deformation; this results in faster alignment. The system size has a strong effect on the alignment process; perfect alignment takes place for a small systems of width 8λ and 16λ, while a larger system of width 32λ does not align completely even at long times. In the larger system, there appears to be a dynamical steady state in which the layers are not perfectly aligned--where there is a balance between the annealing of defects due to shear and the creation due to an instability of the aligned lamellar phase under shear. We observe two types of defect creation mechanisms: the buckling instability under dilation, which was reported earlier, as well as a second mechanism due to layer compression.

  11. Revealing the potential of Didodecyldimethylammonium bromide as efficient scaffold for fabrication of nano liquid crystalline structures.

    PubMed

    Kanwar, Rohini; Kaur, Gurpreet; Mehta, S K

    2016-03-01

    To exploit the potential of Didodecyldimethylammonium bromide (D12DAB) as a core lipidic constituent, an attempt was made to fabricate and optimize cationic nanostructured lipid carriers (cNLCs) using a cost-effective microemulsification methodology. Designed composition was optimized by studying the effect of different microemulsion components on D12DAB cNLCs characteristics. ​Spherical shaped D12DAB cNLCs were obtained with an average size of ∼160 nm and zeta potential of +30.2 mV. Differential Scanning Calorimetry (DSC) depicted the presence of thermotropic character, whereas polarized optical microscopy confirmed the mesophase like behavior of D12DAB based cNLCs. In addition, hemolysis analysis revealed that the toxicity was concentration dependent as LC50 was reached at a concentration of 50 μg/mL of cNLCs. This class of cNLCs is expected to become a potent candidate for a broad spectrum of medicaments as carriers, targeting for pharmaceutical and medicinal purposes, due to the combination of a hard lipid with a soft lipid, where the liquid crystalline structure of the lipid co-exists.

  12. How Are Preferences Revealed?

    PubMed Central

    Beshears, John; Choi, James J.; Laibson, David; Madrian, Brigitte C.

    2009-01-01

    Revealed preferences are tastes that rationalize an economic agent’s observed actions. Normative preferences represent the agent’s actual interests. It sometimes makes sense to assume that revealed preferences are identical to normative preferences. But there are many cases where this assumption is violated. We identify five factors that increase the likelihood of a disparity between revealed preferences and normative preferences: passive choice, complexity, limited personal experience, third-party marketing, and intertemporal choice. We then discuss six approaches that jointly contribute to the identification of normative preferences: structural estimation, active decisions, asymptotic choice, aggregated revealed preferences, reported preferences, and informed preferences. Each of these approaches uses consumer behavior to infer some property of normative preferences without equating revealed and normative preferences. We illustrate these issues with evidence from savings and investment outcomes. PMID:24761048

  13. US weapons secrets revealed

    SciTech Connect

    Norris, R.S.; Arkin, W.M.

    1993-03-01

    Extraordinary details have only recently been revealed about the struggle over the control of early U.S. nuclear weapons and their initial deployments abroad. The information comes from a newly declassified top secret report, part of a larger study, The History of the Strategic Arms Competition, 1945-1972, commissioned by Defense Secretary James R. Schlisinger in summer 1974.

  14. Revealing power in truth

    PubMed Central

    Lee, Kelley

    2015-01-01

    Jeremy Shiffman’s editorial appropriately calls on making all forms of power more apparent and accountable, notably productive power derived from expertise and claims to moral authority. This commentary argues that relationships based on productive power can be especially difficult to reveal in global health policy because of embedded notions about the nature of power and politics. Yet, it is essential to recognize that global health is shot through with power relationships, that they can take many forms, and that their explicit acknowledgement should be part of, rather than factored out of, any reform of global health governance. PMID:25844390

  15. The Universe Revealed

    NASA Astrophysics Data System (ADS)

    Spence, Pam

    1998-10-01

    The Universe is a bewildering place to the uninitiated. The concepts and theories that govern space seem complex and often contradictory. The Universe Revealed provides the keys to unlocking the wonders of the cosmos. Elegantly written and lavishly illustrated, it begins with the Sun and stretches through our solar system into deepest space. Lucid prose, written by many of the people who have shaped our current thinking on space, and spectacular photographs make the physics of the Universe accessible and provide a solid background for understanding the most recent astronomical discoveries. Covering the most intriguing features of the cosmos, the topics discussed range from the Earth and global warming to cosmic collisions and the size of the Universe. Major sections examine the Solar System, stars, galaxies, cosmology, and the observational techniques used by astronomers, both amateur and professional. The Universe Revealed represents the collaboration of internationally renowned experts in astronomy and cosmology, with contributions from authors including David Malin, F. Duccio Macchetto, Iain Nicholson, Neil Bone, Ian Ridpath, Seth Shostak, Mike Lancaster, Steve Miller, Ken Croswell, Geoff McNamara, and Steven Young. This extraordinary blend of astronomy, astrophysics, and cosmology, will appeal to amateur and armchair astronomers alike.

  16. Mysterious Blob Galaxies Revealed

    NASA Image and Video Library

    2005-01-11

    This image composite shows a giant galactic blob (red) and the three merging galaxies NASA's Spitzer Space Telescope discovered within it (yellow). Blobs are intensely glowing clouds of hot hydrogen gas that envelop faraway galaxies. They are about 10 times as large as the galaxies they surround. Visible-light images reveal the vast extent of blobs, but don't provide much information about their host galaxies. Using its heat-seeking infrared eyes, Spitzer was able to see the dusty galaxies tucked inside one well-known blob located 11 billion light-years away. The findings reveal three monstrously bright galaxies, trillions of times brighter than the Sun, in the process of merging together. Spitzer also observed three other blobs located in the same cosmic neighborhood, all of which were found to be glaringly bright. One of these blobs is also known to be a galactic merger, only between two galaxies instead of three. It remains to be seen whether the final two blobs studied also contain mergers. The Spitzer data were acquired by its multiband imaging photometer. The visible-light image was taken by the Blanco Telescope at the Cerro Tololo Inter-American Observatory, Chile. http://photojournal.jpl.nasa.gov/catalog/PIA07220

  17. Gusev's Rim Revealed

    NASA Technical Reports Server (NTRS)

    2004-01-01

    NASA's Mars Exploration Rover Spirit took this panoramic camera image on sol 91 (April 5, 2004). Spirit is looking to the southeast, and through the martian haze has captured the rim of Gusev Crater approximately 80 kilometers (49.7 miles) away on the horizon.

    The right side of this image reveals the portion of the crater edge that descends into the mouth of Ma'adim Vallis, a channel that opens into Gusev Crater. Spirit is currently traveling toward the informally named 'Columbia Hills,' which lie to the left of the region pictured here.

    This image is similar to a panoramic camera image taken on sol 68, but Gusev's ridge is more visible here because the atmospheric dust caused by winter dust storms has settled. Scientists expect to get even clearer images than this one in upcoming sols.

    This image has been modified to make the crater rim more visible.

  18. Ancient River revealed

    NASA Astrophysics Data System (ADS)

    Recent flights of the Spaceborne Imaging Radar-C/X-band Synthetic Aperture Radar (SIR-C/X-SAR) mission aboard the space shuttle Endeavour discovered a previously unknown branch of an ancient river. The images, released at AGU's Spring Meeting, show the river channel buried under thousands of years worth of windblown sand in a region of North Africa's Sahara Desert near the Kufra Oasis in southeast Libya, centered at 23.3°N latitude, 22.9°E longitude. The image from the flight last October reveals a system of old, now inactive stream valleys, called “paleodrainage systems,” which carried running water northward across the Sahara during periods of wetter climate.

  19. Synthesis and Thermotropic Studies of Two Novel Series of Kinked Liquid Crystals: 2-(4′-Alkoxybiphen-4-yl)-6-methylquinolines and 2-(6-Alkoxynaphthalen-2-yl)-6-methylquinolines

    PubMed Central

    Chia, Win-Long; Kuo, Ker-Non; Lin, Shao-Hsun

    2014-01-01

    Two novel homologous series of kinked (Z-shaped) liquid crystalline compounds were synthesized using a short two-step reaction. Yields of 30%–40% and 51%–57% were obtained for 2-(4′-alkoxybiphen-4-yl)-6-methylquinolines (nO-PPQMe, n = 3–8) and 2-(6-alkoxynaphthalen-2-yl)-6-methylquinolines (iO-NpQMe, i = 3–7), respectively. Spectral analyses agreed with the expected structures. The thermotropic behaviors of these compounds were investigated using polarized optical microscopy and differential scanning calorimetry. An enantiotropic nematic phase appeared to be the main mesophase in these two series of kinked liquid crystalline compounds, and an additional enantiotropic smectic C phase appeared when n = 8. PMID:24798752

  20. Photochromism and diffraction grating in cyanoazobenzene polymer films

    NASA Astrophysics Data System (ADS)

    Serwadczak, M.; Wübbenhorst, M.; Kucharski, S.

    2006-08-01

    Two series of photochromic copolymathacrylates containing cyanoazobenzene chromophores as side chains were described. The series with shorter ethylene spacer between mesogen and main polymethacrylate chain was amorphous, whereas the second one with longer ethoxyethylene spacer was liquid crystalline forming smectic C mesophase above Tg. The materials were deposited on glass substrates via spin coating and casting technique to provide thin transparent films. The reversible change of refractive index of the films on illumination with white light was determined by ellipsometry. The difference of real part of the refractive index of the sample was in the range 0.0067-0.0210 depending on the polymer. Formation of diffraction grating was achieved by two beam coupling arrangement using a 532 nm laser diode . The diffraction efficiency for the first order diffraction was in the range of 1.5-2.1% for the homopolymers.

  1. Structure and elastic properties of smectic liquid crystalline elastomer films.

    PubMed

    Stannarius, R; Köhler, R; Dietrich, U; Lösche, M; Tolksdorf, C; Zentel, R

    2002-04-01

    Mechanical measurements, x-ray investigations, and optical microscopy are employed to characterize the interplay of chemical composition, network topology, and elastic response of smectic liquid crystalline elastomers (LCEs) in various mesophases. Macroscopically ordered elastomer films of submicrometer thicknesses were prepared by cross linking freely suspended smectic polymer films. The cross-linked material preserves the mesomorphism and phase transitions of the precursor polymer. The elastic response of the smectic LCE is entropic, and the corresponding elastic moduli are of the order of MPa. In the tilted ferroelectric smectic-C* phase, the network structure plays an important role. Due to the coupling of elastic network deformations to the orientation of the mesogenic groups in interlayer cross-linked materials (mesogenic cross-linker units), the stress-strain characteristics is found to differ qualitatively from that in the other phases.

  2. The Climate Revealed

    NASA Astrophysics Data System (ADS)

    Burroughs, William

    1999-10-01

    El Niño, La Niña, global warming--terms that crop up frequently in current media coverage of anomalous weather conditions: a spring thaw in January in New York City...a snowstorm in Bakersfield, California...winterlike temperatures in Miami. Such phenomena as these and reports of devastating droughts, floods, and storms around the world bring home the fact of how deeply climate affects our daily lives--and of our inability to control the consequences of climatic events. Extraordinarily timely, The Climate Revealed explores the human-climate "relationship" in all its fascinating complexity. Packed with 250 beautiful, full-color photographs, the volume travels the globe to provide a detailed portrait of individual climate zones from the polar icecaps to the fiercest deserts. The expert and highly accessible text uncovers the essential elements--earth, air, fire and water--that make up the world's various climates. William Burroughs reveals the dramatic discoveries and techniques of historians and archaeologists in their search to understand climates of the past. In the book's conclusion he considers the future and presents every facet of the current environmental debate. With its detailed coverage of the past, present, and future, this marvelous work is essential reading for all those who want to understand one of the most critical facets of life, climate. William Burroughs is a well known and successful science author who has written four books on the weather including Does the Weather Really Matter? (1997), Weather Cycles: Real or Imaginary (1992), and Watching the World's Weather (1991), all published by Cambridge University Press.

  3. Structure-property relations in siloxane-based main chain liquid crystalline elastomers and related linear polymers

    NASA Astrophysics Data System (ADS)

    Ren, Wanting

    2007-12-01

    Soft materials have attracted much scientific and technical interest in recent years. In this thesis, attention has been placed on the underpinning relations between molecular structure and properties of one type of soft matter---main chain liquid crystalline elastomers (MCLCEs), which may have application as shape memory or as auxetic materials. In this work, a number of siloxane-based MCLCEs and their linear polymer analogues (MCLCEs) with chemical variations were synthesized and examined. Among these chemical variations, rigid p-phenylene transverse rod and flat-shaped anthraquinone (AQ) mesogenic monomers were specifically incorporated. Thermal and X-ray analysis found a smectic C phase in most of our MCLCEs, which was induced by the strong self-segregation of siloxane spacers, hydrocarbon spacers and mesogenic rods. The smectic C mesophase of the parent LCE was not grossly affected by terphenyl transverse rods. Mechanical studies of MCLCEs indicated the typical three-region stress-strain curve and a polydomain-to-monodomain transition. Strain recovery experiments of MCLCEs showed a significant dependence of strain retentions on the initial strains but not on the chemical variations, such as the crosslinker content and the lateral substituents on mesogenic rods. The MCLCE with p-phenylene transverse rod showed a highly ordered smectic A mesophase at room temperature with high stiffness. Mechanical properties of MCLCEs with AQ monomers exhibit a strong dependence on the specific combination of hydrocarbon spacer and siloxane spacer, which also strongly affect the formation of pi-pi stacking between AQ units. Poisson's ratio measurement over a wide strain range found distinct trends of Poisson's ratio as a function of the crosslinker content as well as terphenyl transverse rod loadings in its parent MCLCEs.

  4. Generalized Langevin-Debye model of the field dependence of tilt, birefringence, and polarization current near the de Vries smectic-A* to smectic-C* liquid crystal phase transition.

    PubMed

    Shen, Yongqiang; Wang, Lixing; Shao, Renfan; Gong, Tao; Zhu, Chenhui; Yang, Hong; Maclennan, Joseph E; Walba, David M; Clark, Noel A

    2013-12-01

    In chiral smectic-A (Sm-A) liquid crystals, an applied electric field induces a tilt of the optic axis from the layer normal. When these materials are of the de Vries type, the electroclinic tilt susceptibility is unusually large, with the field-induced director reorientation accompanied by a substantial increase in optical birefringence with essentially no change in the smectic layer spacing. In order to account for the observed electro-optic behavior, we assume that the molecular orientation distribution in the Sm-A has two degrees of freedom: azimuthal orientation and tilt of the molecular long axis from the layer normal, with the tilt confined to a narrow range of angles. We present a generalized Langevin-Debye model of the response of this orientational distribution to applied field that gives a field-induced optic axis tilt, birefringence, and polarization dependence that agrees well with experimental measurements and reproduces the double-peaked polarization current response characteristic of a first-order Sm-A(*)-Sm-C(*) transition. Additionally, we find that the measured field-induced polarization and the Langevin-Debye model predictions can be quantitatively described as pre-transitional behavior near the tricritical point of a recently published generalized 3D XY model of interacting hard rods confined to reorient on a cone in the presence of an applied field.

  5. Titan Casts Revealing Shadow

    NASA Astrophysics Data System (ADS)

    2004-05-01

    A rare celestial event was captured by NASA's Chandra X-ray Observatory as Titan -- Saturn's largest moon and the only moon in the Solar System with a thick atmosphere -- crossed in front of the X-ray bright Crab Nebula. The X-ray shadow cast by Titan allowed astronomers to make the first X-ray measurement of the extent of its atmosphere. On January 5, 2003, Titan transited the Crab Nebula, the remnant of a supernova explosion that was observed to occur in the year 1054. Although Saturn and Titan pass within a few degrees of the Crab Nebula every 30 years, they rarely pass directly in front of it. "This may have been the first transit of the Crab Nebula by Titan since the birth of the Crab Nebula," said Koji Mori of Pennsylvania State University in University Park, and lead author on an Astrophysical Journal paper describing these results. "The next similar conjunction will take place in the year 2267, so this was truly a once in a lifetime event." Animation of Titan's Shadow on Crab Nebula Animation of Titan's Shadow on Crab Nebula Chandra's observation revealed that the diameter of the X-ray shadow cast by Titan was larger than the diameter of its solid surface. The difference in diameters gives a measurement of about 550 miles (880 kilometers) for the height of the X-ray absorbing region of Titan's atmosphere. The extent of the upper atmosphere is consistent with, or slightly (10-15%) larger, than that implied by Voyager I observations made at radio, infrared, and ultraviolet wavelengths in 1980. "Saturn was about 5% closer to the Sun in 2003, so increased solar heating of Titan may account for some of this atmospheric expansion," said Hiroshi Tsunemi of Osaka University in Japan, one of the coauthors on the paper. The X-ray brightness and extent of the Crab Nebula made it possible to study the tiny X-ray shadow cast by Titan during its transit. By using Chandra to precisely track Titan's position, astronomers were able to measure a shadow one arcsecond in

  6. Revealing the Beast Within

    NASA Astrophysics Data System (ADS)

    2003-07-01

    Deeply Embedded Massive Stellar Clusters Discovered in Milky Way Powerhouse Summary Peering into a giant molecular cloud in the Milky Way galaxy - known as W49 - astronomers from the European Southern Observatory (ESO) have discovered a whole new population of very massive newborn stars . This research is being presented today at the International Astronomical Union's 25th General Assembly held in Sydney, Australia, by ESO-scientist João Alves. With the help of infrared images obtained during a period of excellent observing conditions with the ESO 3.5-m New Technology Telescope (NTT) at the La Silla Observatory (Chile), the astronomers looked deep into this molecular cloud and discovered four massive stellar clusters, with hot and energetic stars as massive as 120 solar masses. The exceedingly strong radiation from the stars in the largest of these clusters is "powering" a 20 light-year diameter region of mostly ionized hydrogen gas (a "giant HII region"). W49 is one of the most energetic regions of star formation in the Milky Way. With the present discovery, the true sources of the enormous energy have now been revealed for the first time, finally bringing to an end some decades of astronomical speculations and hypotheses. PR Photo 21a/03 : Colour Composite of W49A (NTT+SOFI). PR Photo 21b/03 : Radio and Near-Infrared Composite of W49A Giant molecular clouds Stars form predominantly inside Giant Molecular Clouds which populate our Galaxy, the Milky Way. One of the most prominent of these is W49 , which has a mass of a million solar masses. It is located some 37,000 light-years away and is the most luminous star-forming region known in our home galaxy: its luminosity is several million times the luminosity of our Sun. A smaller region within this cloud is denoted W49A - this is one of the strongest radio-emitting areas known in the Galaxy . Massive stars are excessive in all ways. Compared to their smaller and ligther brethren, they form at an Olympic speed and

  7. Novel biphenyl-substituted 1,2,4-oxadiazole ferroelectric liquid crystals: synthesis and characterization

    PubMed Central

    Subrao, Mahabaleshwara; Potukuchi, Dakshina Murthy; Sharada Ramachandra, Girish; Bhagavath, Poornima; Bhat, Sangeetha G

    2015-01-01

    Summary Two novel series of unsymmetrically substituted 1,2,4-oxadiazole viz., R.Ox.C*Cn compounds are synthesized and characterized. An optically active, (S)-(+)-methyl 3-hydroxy-2-methylpropionate is used to introduce a chiral center in the molecule. A biphenyl moiety prepared by Suzuki coupling reaction is directly attached to the oxadiazole core at C-5 position. Investigations for the phase behavior revealed that the series with a benzyl group on one end of the oxadiazole core exhibits an 1D orthogonal smectic-A phase while the second series with dodecyl flexible end chain shows orthogonal smectic-A and tilted chiral smectic-C (SmC*) phases over a wide range of temperatures. The smectic-C phase exhibits ferroelectric (FE) polarization switching. The mesomorphic thermal stabilities of these compounds are discussed in the domain of the symmetry and the flexibility of the alkyloxy end chain length attached to the chiral center. PMID:25815075

  8. X-ray study of mesomorphism of bent-core and chromonic mesogens

    NASA Astrophysics Data System (ADS)

    Joshi, Leela Pradhan

    The discovery of thermotropic biaxial nematic phase in bent-core mesogens, have engendered interest in these systems. Also, it undergoes optical switching about 100 times faster than conventional uniaxial nematic liquid crystal. Azo-substituted bent-core compounds, A131 and A103, were investigated as both offer an opportunity to observe their structures and phase transitions from the uniaxial nematic (Nu) to biaxial nematic (Nb) phase and from Nb to the underlying smectic-C (SmC) phase. Plank-like molecular systems are also expected to form Nb phase. Chromonic liquid crystals formed by aqueous solutions of plank-like dye molecules are interesting for their unique self-assembly and structural evolution. They have applications in optical element, coloring in food and textiles, and etc. Both systems were investigated with synchrotron x-ray scattering, polarizing optical microscopy, and differential scanning calorimetry. Temperature dependence of d-spacing and positional order correlations along the director clearly mark the phase boundaries where Nu-Nb transition was approximately 27° below the clearing point. Positional order correlation length of A131 increased from 1.5 in Nu to 3.3 molecular lengths in Nb phase, before it jumps by a factor of at least 5 in SmC phase. The lack of large discontinuous changes in the structural parameters and the subtle signatures in heat capacity establish the second order nature of Nu-Nb and Nb-SmC phase transitions. The chromonic system investigation results provide quantitative information of structural properties in nematic and columnar mesophases. We studied water solutions of (achiral) sunset yellow dye and (chiral and achiral) dihydrochloride salts of perylenebis-dicarboxydiimide. Positional order correlation lengths measurements, parallel and perpendicular to the aggregate axis, revealed that they increase with concentration and decrease with temperature. Temperature dependence of correlation lengths yielded the scission

  9. Comprehensive examination of mesophases formed by DMPC and DHPC mixtures.

    PubMed

    Harroun, Thad A; Koslowsky, Martin; Nieh, Mu-Ping; de Lannoy, Charles-François; Raghunathan, V A; Katsaras, John

    2005-06-07

    Mixtures of long- and short-chain phospholipids, specifically 14:0 and 6:0 phosphatidylcholines (DMPC and DHPC), have been used successfully in NMR studies as magnetically alignable substrates for membrane-associated proteins. However, recent publications have shown that the phase behavior of these mixtures is much more complex than originally thought. Using polarized light microscopy and small-angle neutron scattering, phase diagrams of DMPC/DHPC mixtures at molar ratios of 2, 3.2, and 5 have been determined. Generally, at temperatures below the main-chain melting transition of DMPC (T(M) = 23 degrees C), an isotropic phase of disk-like micelles is found. At high temperatures (T > 50 degrees C), a lamellar phase consisting of either multilamellar vesicles (MLV) or extended lamellae is formed, which at low lipid concentrations (e.g., MLV) coexists with an excess of water. At intermediate temperatures and lipid concentrations, a chiral nematic phase made up of worm-like micelles was observed.

  10. Liquid-Crystalline Mesophases of Plasmid DNA in Bacteria

    NASA Astrophysics Data System (ADS)

    Reich, Ziv; Wachtel, Ellen J.; Minsky, Abraham

    1994-06-01

    Bacterial plasmids may often reach a copy number larger than 1000 per cell, corresponding to a total amount of DNA that may exceed the amount of DNA within the bacterial chromosome. This observation highlights the problem of cellular accommodation of large amounts of closed-circular nucleic acids, whose interwound conformation offers negligible DNA compaction. As determined by x-ray scattering experiments conducted on intact bacteria, supercoiled plasmids segregate within the cells into dense clusters characterized by a long-range order. In vitro studies performed at physiological DNA concentrations indicated that interwound DNA spontaneously forms liquid crystalline phases whose macroscopic structural properties are determined by the features of the molecular supercoiling. Because these features respond to cellular factors, DNA supercoiling may provide a sensitive regulatory link between cellular parameters and the packaging modes of interwound DNA in vivo.

  11. Thermally induced fluid reversed hexagonal (H(II)) mesophase.

    PubMed

    Amar-Yuli, Idit; Wachtel, Ellen; Shalev, Deborah E; Moshe, Hagai; Aserin, Abraham; Garti, Nissim

    2007-12-06

    In the present study we characterized the microstructures of the Lc and HII phases in a glycerol monooleate (GMO)/tricaprylin (TAG)/water mixture as a function of temperature. We studied the factors that govern the formation of a low-viscosity HII phase at relatively elevated temperatures (>35 degrees C). This phase has very valuable physical characteristics and properties. The techniques used were differential scanning calorimetry (DSC), wide- and small-angle X-ray scattering (WAXS and SAXS, respectively), NMR (self-diffusion and (2)H NMR), and Fourier transform infrared (FTIR) spectroscopies. The reverse hexagonal phase exhibited relatively rapid flow of water in the inner channels within the densely packed cylindrical aggregates of GMO with TAG molecules located in the interstices. The existence of two water diffusion peaks reflects the existence of both mobile water and hydration water at the GMO-water interface (hydrogen exchange between the GMO hydroxyls and water molecules). Above 35 degrees C, the sample became fluid yet hexagonal symmetry was maintained. The fluidity of the HII phase is explained by a significant reduction in the domain size and also perhaps cylinder length. This phenomenon was characterized by higher mobility of the GMO, lower mobility of the water, and a significant dehydration process.

  12. The structure of mesophase fiber-forming pitches

    SciTech Connect

    Kirda, V.S.; Khrenkova, T.M.; Zamanova, L.V.; Nikolaeva, L.V.; Fedoseev, S.D.

    1993-12-31

    The structural features of several pitches, obtained from cracking residues and a pitch-like material, have been investigated as to their fiber-forming ability. The residues were obtained by heat treatments of cracking residues of a residual and two types of distillates. Infrared spectroscopy and x-ray diffraction results are discussed.

  13. Why GPCRs behave differently in cubic and lamellar lipidic mesophases

    PubMed Central

    2012-01-01

    Recent successes in the crystallographic determination of structures of transmembrane proteins in the G protein-coupled receptor (GPCR) family have established the lipidic cubic phase (LCP) environment as the medium of choice for growing structure-grade crystals by the method termed “in meso”. The understanding of in meso crystallogenesis is currently at a descriptive level. To enable an eventual quantitative, energy-based description of the nucleation and crystallization mechanism, we have examined the properties of the lipidic cubic phase system and the dynamics of the GPCR rhodopsin reconstituted into the LCP with coarse-grained molecular dynamics simulations with the Martini force-field. Quantifying the differences in the hydrophobic/hydrophilic exposure of the GPCR to lipids in the cubic and lamellar phases, we found that the highly curved geometry of the cubic phase provides more efficient shielding of the protein from unfavorable hydrophobic exposure, which leads to a lesser hydrophobic mismatch and less unfavorable hydrophobic–hydrophilic interactions between the protein and lipid–water interface in the LCP, compared to the lamellar phase. Since hydrophobic mismatch is considered a driving force for oligomerization, the differences in exposure mismatch energies between the LCP and the lamellar structures suggest that the latter provide a more favorable setting in which GPCRs can oligomerize as a prelude to nucleation and crystal growth. These new findings lay the foundation for future investigations of in meso crystallization mechanisms related to the transition from the LCP to the lamellar phase and studies aimed at an improved rational approach for generating structure-quality crystals of membrane proteins. PMID:22931253

  14. Liquid-crystalline nanoparticles: Hybrid design and mesophase structures

    PubMed Central

    Greget, Romain; Dominguez, Cristina; Nagy, Zsuzsanna T; Guillon, Daniel; Gallani, Jean-Louis

    2012-01-01

    Summary Liquid-crystalline nanoparticles represent an exciting class of new materials for a variety of potential applications. By combining supramolecular ordering with the fluid properties of the liquid-crystalline state, these materials offer the possibility to organise nanoparticles into addressable 2-D and 3-D arrangements exhibiting high processability and self-healing properties. Herein, we review the developments in the field of discrete thermotropic liquid-crystalline nanoparticle hybrids, with special emphasis on the relationship between the nanoparticle morphology and the nature of the organic ligand coating and their resulting phase behaviour. Mechanisms proposed to explain the supramolecular organisation of the mesogens within the liquid-crystalline phases are discussed. PMID:22509204

  15. [Nephrocutaneous fistula revealing xanthogranulomatous pyelonephritis].

    PubMed

    Scotté, M; Sibert, L; Soury, P; Lebret, T; Gobet, F; Grise, P; Tenière, P

    1993-01-01

    A patient presented with a reno-cutaneous fistula revealing a xanthogranulomatous pyelonephritis secondary to staghorn calculus. Total nephrectomy was necessary because of renal destruction. This treatment allowed closure of the fistula and a good clinical result.

  16. [Vulvar oedema revealing systemic mastocytosis].

    PubMed

    Deveza, E; Locatelli, F; Girardin, M; Valmary-Degano, S; Daguindau, E; Aubin, F; Humbert, P; Pelletier, F

    2015-11-01

    Systemic mastocytosis is characterised by abnormal proliferation of mast cells in various organs. We report an original case of systemic mastocytosis revealed by vulvar oedema. A 24-year-old patient was examined in the dermatology department for vulvar oedema appearing during sexual intercourse. She presented vasomotor dysfunction of the lower limbs, urticaria on the trunk on exertion, diarrhoea and bone pains. Laboratory tests showed serum tryptase of 29.7μg and plasma histamine at twice the normal value. Myelogram results showed infiltration by dysmorphic mast cells. Screening for c-kit D816V mutation was positive. Duodenal biopsies revealed mast-cell clusters with aggregation involving over 15 mast cells. CD2 staining was inconclusive and CD25 staining could not be done. Trabecular osteopenia was found, and we thus made a diagnosis of indolent systemic mastocytosis (ISM variant Ia) as per the WHO 2008 criteria. Symptomatic treatment was initiated (antiH1, H2, antileukotrienes) and clinical and laboratory follow-up was instituted. The cutaneous signs leading to diagnosis in this patient of systemic mastocytosis involving several organs were seemingly minimal signs associated with mastocyte degranulation. This is the third recorded case of mastocytosis revealed by vulvar oedema and the first case revealing systemic involvement. The two previously reported cases of vulvar oedema revealed cutaneous mastocytosis alone. Mastocytosis, whether systemic or cutaneous, must be included among the differential diagnoses considered in the presence of vulvar oedema. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

  17. Investigation on Thermal and Optical Properties of Hydrogen-Bonded Binary Liquid Crystals

    NASA Astrophysics Data System (ADS)

    Ranjeeth kumar, T.; Sundaram, S.; Vasanthi, T.; Subhasri, P.; Chitravel, T.; Senthil, T. S.; Jayaprakasam, R.; Vijayakumar, V. N.

    2016-12-01

    A homologous series of hydrogen-bonded liquid crystals (HBLCs) are synthesized and characterized. Intermolecular hydrogen bonding occurs between 4-methoxycinnamic acid (4MCA) and p-n-alkyloxy benzoic acids (nOBA, where n = 3, 7 to 12). These binary complexes have been obtained by following well-designed synthesis route. The subsequent binary complexes have been characterized by polarizing optical thermal microscopy (POM), differential scanning calorimetry (DSC), and Fourier transform infrared spectroscopy (FTIR). The present work explains the details of the association between the mesogenic phase behavior and H-bonding in the homologous series of 4MCA + nOBA. Nematic phase is interrelated with the closed dimers between acid molecules through the formation of strong hydrogen bonds. But, high concentrations are linked to the manifestation of smectic phases that disturb the local order of the nematic phase. As a result, the higher-order mesophases are observed in the present binary complex series. The inclusion of nematic LC (4MCA) in the nOBA alters the melting temperature and the clearing temperature as lower than those of the individual. Also, the wide mesophase regions of the present series are identified compared to those of the constituent mesogens. The optical tilt angle of binary mixtures for smectic C phase and thermal stability factors of the mesogenic phases have been discussed.

  18. Ischemic Colitis Revealing Polyarteritis Nodosa

    PubMed Central

    Hamzaoui, Amira; Litaiem, Noureddine; Smiti Khanfir, M.; Ayadi, Sofiene; Nfoussi, Haifa; Houman, M. H.

    2013-01-01

    Ischemic colitis is one of the most common intestinal ischemic injuries. It results from impaired perfusion of blood to the bowel and is rarely caused by vasculitis. We report a case of ischemic colitis revealing polyarteritis nodosa (PAN) in a 55-year-old man. Histological examination of the resected colon led to the diagnosis of PAN. PMID:24382967

  19. Two Unique Glioma Subtypes Revealed.

    PubMed

    Poh, Alissa

    2016-04-01

    A comprehensive analysis of 1,122 diffuse glioma samples from The Cancer Genome Atlas has revealed two new subtypes of this common brain cancer, with molecular and clinical features that diverge from the norm. The study findings also support the use of DNA methylation profiles to improve glioma classification and treatment.

  20. Urticarial vasculitis reveals unsuspected thyroiditis.

    PubMed

    Ferreira, Olga; Mota, Alberto; Baudrier, Teresa; Azevedo, Filomena

    2012-01-01

    A 38-year-old woman presented with erythematous, violaceous plaques with a serpiginous and unusual appearance located on the left shoulder, left thigh, and right buttock, evolving for 5 days, which eventually became generalized. A skin biopsy revealed leukocytoclastic vasculitis and a diagnosis of urticarial vasculitis was made. The complete blood count, biochemistry, complement levels, and other immunological test results were unremarkable. However, antithyroid antibody titers were increased. Despite having normal thyroid function tests and an absence of specific symptoms, the patient underwent a thyroid ultrasound, which revealed features of thyroiditis, and was subsequently referred to an endocrinologist. Several diseases can be associated with urticarial vasculitis, namely infections and autoimmune connective-tissue disorders such as systemic lupus erythematosus and Sjögren syndrome. Thyroiditis is an uncommon association.

  1. Revealing the microstructure of materials

    NASA Technical Reports Server (NTRS)

    Nelson, James A.

    1990-01-01

    The objectives are to demonstrate how the microstructure of materials may be revealed by abrasive polishing and chemical etching, and to illustrate how microstructural information is used to monitor manufacturing processes, provide in-depth inspection, and perform failure analysis. Microstructural analysis is the procedure used to reveal the internal microstructural details of a material or part by sectioning and polishing the cut surface so that it may be examined under a suitable microscope. A printed wiring board was selected as the test material because it contains both metals and nonmetals that have distinctive microstructures, and because this technique is used throughout the electronic industry as a key quality control tool. The three principle component materials in printed circuit boards are glass/epoxy laminates faced with copper foil; copper, deposited by both electroless and electrolytic plating; and tin/lead solder. Sample preparation, mounting, grinding, polishing, and examination and analysis are discussed.

  2. Revealing the microstructure of materials

    NASA Technical Reports Server (NTRS)

    Nelson, James A.

    1990-01-01

    The objectives are to demonstrate how the microstructure of materials may be revealed by abrasive polishing and chemical etching, and to illustrate how microstructural information is used to monitor manufacturing processes, provide in-depth inspection, and perform failure analysis. Microstructural analysis is the procedure used to reveal the internal microstructural details of a material or part by sectioning and polishing the cut surface so that it may be examined under a suitable microscope. A printed wiring board was selected as the test material because it contains both metals and nonmetals that have distinctive microstructures, and because this technique is used throughout the electronic industry as a key quality control tool. The three principle component materials in printed circuit boards are glass/epoxy laminates faced with copper foil; copper, deposited by both electroless and electrolytic plating; and tin/lead solder. Sample preparation, mounting, grinding, polishing, and examination and analysis are discussed.

  3. [Uterine metastasis revealing gastric adenocarcinoma].

    PubMed

    Mambrini, P; Giovanini, M; Seitz, J F; Perrier, H; Allemand, I; Rabia, I; Monges, G; Lebreuil, G

    1995-01-01

    We report a case of metastasis to the uterine corpus revealing a primary gastric adenocarcinoma. A 26-year-old woman suffered from weight loss, vaginal bleeding, abdominal pain. An endometrial curettage showed apparently metastatic adenocarcinoma. The primary site of the tumour was gastric. The upper gastrointestinal endoscopy revealed an ulcus and aspect of linitis plastica in the fundus. Biopsies showed diffuse type adenocarcinoma. Because of extensive disease, laparotomy was not performed and exclusive palliative chemotherapy was started. The patient died 10 months after the diagnosis. Metastasis from primary gastric cancer to the female genital tract are rare and are usually observed in young premenopausal women with diffuse type gastric adenocarcinoma. This case report underlines the interest, for those patients of careful gynaecologic examination at the initial staging and after treatment.

  4. [Seizures revealing phosphocalcic metabolism abnormalities].

    PubMed

    Hmami, F; Chaouki, S; Benmiloud, S; Souilmi, F Z; Abourazzak, S; Idrissi, M; Atmani, S; Bouharrou, A; Hida, M

    2014-01-01

    Hypocalcemia due to hypoparathyroidism produces a broad spectrum of clinical manifestations, but overt symptoms may be sparse. One unusual presentation is onset or aggravation of epilepsy in adolescence revealing hypoparathyroidism. This situation can lead to delayed diagnosis, with inefficacity of the antiepileptic drugs. We report five cases of adolescence-onset epilepsy with unsuccessful antiepileptic therapy, even with gradually increasing dose. Physical examination revealed signs of hypocalcemia, confirmed biologically. Full testing disclosed the origin of the seizures: hypoparathyroidism in three patients and pseudohypoparathyroidism in the other two. In four of five patients, computed tomography showed calcification of the basal ganglia, defining Fahr's syndrome. The patients were treated with oral calcium and active vitamin D (1-alphahydroxy vitamin D3). Seizure frequency progressively decreased and serum calcium levels returned to normal. These cases illustrate the importance of the physical examination and of routine serum calcium assay in patients with new-onset epileptic seizures in order to detect hypocalcemia secondary to hypoparathyroidism.

  5. Structure-revealing data fusion.

    PubMed

    Acar, Evrim; Papalexakis, Evangelos E; Gürdeniz, Gözde; Rasmussen, Morten A; Lawaetz, Anders J; Nilsson, Mathias; Bro, Rasmus

    2014-07-12

    Analysis of data from multiple sources has the potential to enhance knowledge discovery by capturing underlying structures, which are, otherwise, difficult to extract. Fusing data from multiple sources has already proved useful in many applications in social network analysis, signal processing and bioinformatics. However, data fusion is challenging since data from multiple sources are often (i) heterogeneous (i.e., in the form of higher-order tensors and matrices), (ii) incomplete, and (iii) have both shared and unshared components. In order to address these challenges, in this paper, we introduce a novel unsupervised data fusion model based on joint factorization of matrices and higher-order tensors. While the traditional formulation of coupled matrix and tensor factorizations modeling only shared factors fails to capture the underlying structures in the presence of both shared and unshared factors, the proposed data fusion model has the potential to automatically reveal shared and unshared components through modeling constraints. Using numerical experiments, we demonstrate the effectiveness of the proposed approach in terms of identifying shared and unshared components. Furthermore, we measure a set of mixtures with known chemical composition using both LC-MS (Liquid Chromatography - Mass Spectrometry) and NMR (Nuclear Magnetic Resonance) and demonstrate that the structure-revealing data fusion model can (i) successfully capture the chemicals in the mixtures and extract the relative concentrations of the chemicals accurately, (ii) provide promising results in terms of identifying shared and unshared chemicals, and (iii) reveal the relevant patterns in LC-MS by coupling with the diffusion NMR data. We have proposed a structure-revealing data fusion model that can jointly analyze heterogeneous, incomplete data sets with shared and unshared components and demonstrated its promising performance as well as potential limitations on both simulated and real data.

  6. [Endobronchial hamartoma revealed by hemoptysis].

    PubMed

    Smati, Belhassen; Boudaya, Mohamed Sadok; Mestiri, Taher; Djilani, Habiba; Mezni, Faouzi; Kilani, Tarek

    2005-05-01

    Hamartoma is the most frequent benign tumor of the lung. Its endo bronchial location is rare. We report two cases of endo bronchial hamartoma occurring in 2 men aged 68 and 60 years respectively. The two cases were revealed by hemoptysis. Bronchial fibroscopy showed a bud respectively in the left stump and in the lower left bronchus. Treatment consisted in a pneumonectomy and a lower lobectomy. A histological examination confirmed the diagnosis of endo bronchial hamartoma. Diagnosis of endobronchial hamartoma before surgery is difficult. Pulmonary resections are often necessary because of parenchyma lelions caused bronchial obstruction.

  7. Archimedes: Accelerator Reveals Ancient Text

    SciTech Connect

    Bergmann, Uwe

    2004-02-24

    Archimedes (287-212 BC), who is famous for shouting 'Eureka' (I found it) is considered one of the most brilliant thinkers of all times. The 10th-century parchment document known as the 'Archimedes Palimpsest' is the unique source for two of the great Greek's treatises. Some of the writings, hidden under gold forgeries, have recently been revealed at the Stanford Synchrotron Radiation Laboratory at SLAC. An intense x-ray beam produced in a particle accelerator causes the iron in original ink, which has been partly erased and covered, to send out a fluorescence glow. A detector records the signal and a digital image showing the ancient writings is produced. Please join us in this fascinating journey of a 1,000-year-old parchment from its origin in the Mediterranean city of Constantinople to a particle accelerator in Menlo Park.

  8. Revealing ontological commitments by magic.

    PubMed

    Griffiths, Thomas L

    2015-03-01

    Considering the appeal of different magical transformations exposes some systematic asymmetries. For example, it is more interesting to transform a vase into a rose than a rose into a vase. An experiment in which people judged how interesting they found different magic tricks showed that these asymmetries reflect the direction a transformation moves in an ontological hierarchy: transformations in the direction of animacy and intelligence are favored over the opposite. A second and third experiment demonstrated that judgments of the plausibility of machines that perform the same transformations do not show the same asymmetries, but judgments of the interestingness of such machines do. A formal argument relates this sense of interestingness to evidence for an alternative to our current physical theory, with magic tricks being a particularly pure source of such evidence. These results suggest that people's intuitions about magic tricks can reveal the ontological commitments that underlie human cognition.

  9. Revealing hidden genuine tripartite nonlocality

    NASA Astrophysics Data System (ADS)

    Paul, Biswajit; Mukherjee, Kaushiki; Sarkar, Debasis

    2016-11-01

    Nonlocal correlations arising from measurements on tripartite entangled states can be classified into two groups, one genuinely three-way nonlocal and other local with respect to some bipartition. Still, whether a genuinely tripartite entangled quantum state can exhibit genuine three-way nonlocality remains a challenging problem as far as measurement context is concerned. Here we introduce an approach in this regard. We consider three tripartite quantum states, none of which is genuinely three-way nonlocal in a specific Bell scenario (three parties, two measurements per party, two outcomes per measurement), but they can exhibit genuine three-way nonlocality when the initial states are subjected to stochastic local operations and classical communication. So, genuine three-way nonlocality is a resource which can be revealed by using a sequence of measurements.

  10. Plan competitions reveal entrepreneurial talent

    SciTech Connect

    Madison, Alison L.

    2011-05-15

    Monthly economic diversity column for Tri-City Herald business section. Excerpt below: There’s something to be said for gaining valuable real-world experience in a structured, nurturing environment. Take for instance learning to scuba dive in the comfort of my resort pool rather than immediately hanging out with sharks while I figure out little things like oxygen tanks and avoiding underwater panic attacks. Likewise, graduate students are getting some excellent, supportive real-world training through university business plan competitions. These competitions are places where smart minds, new technologies, months of preparation and coaching, and some healthy pre-presentation jitters collide to reveal not only solid new business ideas, but also some promising entrepreneurial talent. In fact, professionals from around our region descend upon college campuses every spring to judge these events, which help to bridge the gap between academics and the real technology and business-driven economy.

  11. Revealing Non-Covalent Interactions

    PubMed Central

    Johnson, Erin R.; Keinan, Shahar; Mori-Sánchez, Paula; Contreras-García, Julia; Cohen, Aron J.; Yang, Weitao

    2010-01-01

    Molecular structure does not easily identify the intricate non-covalent interactions that govern many areas of biology and chemistry, including design of new materials and drugs. We develop an approach to detect non-covalent interactions in real space, based on the electron density and its derivatives. Our approach reveals underlying chemistry that compliments the covalent structure. It provides a rich representation of van der Waals interactions, hydrogen bonds, and steric repulsion in small molecules, molecular complexes, and solids. Most importantly, the method, requiring only knowledge of the atomic coordinates, is efficient and applicable to large systems, such as proteins or DNA. Across these applications, a view of non-bonded interactions emerges as continuous surfaces rather than close contacts between atom pairs, offering rich insight into the design of new and improved ligands. PMID:20394428

  12. Erosion and what it Reveals

    NASA Technical Reports Server (NTRS)

    2003-01-01

    [figure removed for brevity, see original site]

    Released 20 November 2003

    This image is located near the boundary between Syrtis Major and Isidis Planitia. The top of the image shows rough material that has eroded away from the lower portion of the image, revealing an underlying surface that has many small craters. It also reveals an ancient flow lobe that is barely discernable, crossing the southern part of the image (this flow lobe is much easier to see as a smooth region in the context image).

    Image information: VIS instrument. Latitude 16.4, Longitude 77.9 East (282.1 West). 19 meter/pixel resolution.

    Note: this THEMIS visual image has not been radiometrically nor geometrically calibrated for this preliminary release. An empirical correction has been performed to remove instrumental effects. A linear shift has been applied in the cross-track and down-track direction to approximate spacecraft and planetary motion. Fully calibrated and geometrically projected images will be released through the Planetary Data System in accordance with Project policies at a later time.

    NASA's Jet Propulsion Laboratory manages the 2001 Mars Odyssey mission for NASA's Office of Space Science, Washington, D.C. The Thermal Emission Imaging System (THEMIS) was developed by Arizona State University, Tempe, in collaboration with Raytheon Santa Barbara Remote Sensing. The THEMIS investigation is led by Dr. Philip Christensen at Arizona State University. Lockheed Martin Astronautics, Denver, is the prime contractor for the Odyssey project, and developed and built the orbiter. Mission operations are conducted jointly from Lockheed Martin and from JPL, a division of the California Institute of Technology in Pasadena.

  13. Erosion and what it Reveals

    NASA Technical Reports Server (NTRS)

    2003-01-01

    [figure removed for brevity, see original site]

    Released 20 November 2003

    This image is located near the boundary between Syrtis Major and Isidis Planitia. The top of the image shows rough material that has eroded away from the lower portion of the image, revealing an underlying surface that has many small craters. It also reveals an ancient flow lobe that is barely discernable, crossing the southern part of the image (this flow lobe is much easier to see as a smooth region in the context image).

    Image information: VIS instrument. Latitude 16.4, Longitude 77.9 East (282.1 West). 19 meter/pixel resolution.

    Note: this THEMIS visual image has not been radiometrically nor geometrically calibrated for this preliminary release. An empirical correction has been performed to remove instrumental effects. A linear shift has been applied in the cross-track and down-track direction to approximate spacecraft and planetary motion. Fully calibrated and geometrically projected images will be released through the Planetary Data System in accordance with Project policies at a later time.

    NASA's Jet Propulsion Laboratory manages the 2001 Mars Odyssey mission for NASA's Office of Space Science, Washington, D.C. The Thermal Emission Imaging System (THEMIS) was developed by Arizona State University, Tempe, in collaboration with Raytheon Santa Barbara Remote Sensing. The THEMIS investigation is led by Dr. Philip Christensen at Arizona State University. Lockheed Martin Astronautics, Denver, is the prime contractor for the Odyssey project, and developed and built the orbiter. Mission operations are conducted jointly from Lockheed Martin and from JPL, a division of the California Institute of Technology in Pasadena.

  14. APEX reveals glowing stellar nurseries

    NASA Astrophysics Data System (ADS)

    2008-11-01

    Illustrating the power of submillimetre-wavelength astronomy, an APEX image reveals how an expanding bubble of ionised gas about ten light-years across is causing the surrounding material to collapse into dense clumps that are the birthplaces of new stars. Submillimetre light is the key to revealing some of the coldest material in the Universe, such as these cold, dense clouds. Glowing Stellar Nurseries ESO PR Photo 40/08 Glowing Stellar Nurseries The region, called RCW120, is about 4200 light years from Earth, towards the constellation of Scorpius. A hot, massive star in its centre is emitting huge amounts of ultraviolet radiation, which ionises the surrounding gas, stripping the electrons from hydrogen atoms and producing the characteristic red glow of so-called H-alpha emission. As this ionised region expands into space, the associated shock wave sweeps up a layer of the surrounding cold interstellar gas and cosmic dust. This layer becomes unstable and collapses under its own gravity into dense clumps, forming cold, dense clouds of hydrogen where new stars are born. However, as the clouds are still very cold, with temperatures of around -250˚ Celsius, their faint heat glow can only be seen at submillimetre wavelengths. Submillimetre light is therefore vital in studying the earliest stages of the birth and life of stars. The submillimetre-wavelength data were taken with the LABOCA camera on the 12-m Atacama Pathfinder Experiment (APEX) telescope, located on the 5000 m high plateau of Chajnantor in the Chilean Atacama desert. Thanks to LABOCA's high sensitivity, astronomers were able to detect clumps of cold gas four times fainter than previously possible. Since the brightness of the clumps is a measure of their mass, this also means that astronomers can now study the formation of less massive stars than they could before. The plateau of Chajnantor is also where ESO, together with international partners, is building a next generation submillimetre telescope, ALMA

  15. Hubble Images Reveal Jupiter's Auroras

    NASA Technical Reports Server (NTRS)

    1996-01-01

    These images, taken by the Hubble Space Telescope, reveal changes in Jupiter's auroral emissions and how small auroral spots just outside the emission rings are linked to the planet's volcanic moon, Io. The images represent the most sensitive and sharply-detailed views ever taken of Jovian auroras.

    The top panel pinpoints the effects of emissions from Io, which is about the size of Earth's moon. The black-and-white image on the left, taken in visible light, shows how Io and Jupiter are linked by an invisible electrical current of charged particles called a 'flux tube.' The particles - ejected from Io (the bright spot on Jupiter's right) by volcanic eruptions - flow along Jupiter's magnetic field lines, which thread through Io, to the planet's north and south magnetic poles. This image also shows the belts of clouds surrounding Jupiter as well as the Great Red Spot.

    The black-and-white image on the right, taken in ultraviolet light about 15 minutes later, shows Jupiter's auroral emissions at the north and south poles. Just outside these emissions are the auroral spots. Called 'footprints,' the spots are created when the particles in Io's 'flux tube' reach Jupiter's upper atmosphere and interact with hydrogen gas, making it fluoresce. In this image, Io is not observable because it is faint in the ultraviolet.

    The two ultraviolet images at the bottom of the picture show how the auroral emissions change in brightness and structure as Jupiter rotates. These false-color images also reveal how the magnetic field is offset from Jupiter's spin axis by 10 to 15 degrees. In the right image, the north auroral emission is rising over the left limb; the south auroral oval is beginning to set. The image on the left, obtained on a different date, shows a full view of the north aurora, with a strong emission inside the main auroral oval.

    The images were taken by the telescope's Wide Field and Planetary Camera 2 between May 1994 and September 1995.

    This image and

  16. Dilated Cardiomyopathy Revealing Cushing Disease

    PubMed Central

    Marchand, Lucien; Segrestin, Bérénice; Lapoirie, Marion; Favrel, Véronique; Dementhon, Julie; Jouanneau, Emmanuel; Raverot, Gérald

    2015-01-01

    Abstract Cardiovascular impairments are frequent in Cushing's syndrome and the hypercortisolism can result in cardiac structural and functional changes that lead in rare cases to dilated cardiomyopathy (DCM). Such cardiac impairment may be reversible in response to a eucortisolaemic state. A 43-year-old man with a medical past of hypertension and history of smoking presented to the emergency department with global heart failure. Coronary angiography showed a significant stenosis of a marginal branch and cardiac MRI revealed a nonischemic DCM. The left ventricular ejection fraction (LVEF) was estimated as 28% to 30%. Clinicobiological features and pituitary imaging pointed toward Cushing's disease and administration of adrenolytic drugs (metyrapone and ketoconazole) was initiated. Despite the normalization of cortisol which had been achieved 2 months later, the patient presented an acute heart failure. A massive mitral regurgitation secondary to posterior papillary muscle rupture was diagnosed as a complication of the occlusion of the marginal branch. After 6 months of optimal pharmacological treatment for systolic heart failure, as well as treatment with inhibitors of steroidogenesis, there was no improvement of LVEF. The percutaneous mitral valve was therefore repaired and a defibrillator implanted. The severity of heart failure contraindicated pituitary surgery and the patient was instead treated by stereotaxic radiotherapy. This is the first case reporting a Cushing's syndrome DCM without improvement of LVEF despite normalization of serum cortisol levels. PMID:26579807

  17. Chandra Reveals Rich Oxygen Supply

    NASA Technical Reports Server (NTRS)

    2003-01-01

    This striking Chandra X-Ray Observatory image of supernova remnant SNR0103-72.6 reveals a nearly perfect ring about 150 light years in diameter surrounding a cloud of gas enriched in oxygen and shock-heated to millions of degrees Celsius. The ring marks the outer limits of a shock wave produced as material ejected in the supernova explosion collides with the interstellar gas. The size of the ring indicates that we see the supernova remnant as it was about 10,000 years after its progenitor star exploded. Located in the Small Magenellanic Cloud (SMC), SNR 0103-72.6 is about 190,000 light years from Earth. The x-rays take about 190,000 years to reach us from the SMC, so the supernova explosion occurred about 200,000 years ago, as measured on Earth. Scientists have know for years that oxygen and many other elements necessary for life are created in massive stars and dispersed in supernova explosions, but few remnants rich in these elements have been observed. This supernova remnant will hence become an important laboratory for studying how stars forge the elements necessary for life.

  18. Satellites reveal Antarctic mass imbalance

    NASA Astrophysics Data System (ADS)

    Shepherd, A.

    2004-05-01

    Satellite radar observations have revealed a widespread mass imbalance in western Antarctica and rapid thinning of ice shelves at the Antarctic Peninsula. The former shows grounded ice retreat in a region previously considered unstable to such events, and the latter illuminates an ongoing debate as to the mechanism through which ice shelves have disintegrated over the past decade. Both measurements inform us as to the present state of balance of the cryosphere and its interactions with the southern oceans. Since 1992, the Amundsen Sea sector of the West Antarctic Ice Sheet has lost 39 cubic kilometers of its volume each year due to an imbalance between snow accumulation and ice discharge. A flow disturbance is responsible for removing the majority of that ice from the trunks of the Pine Island, Thwaites and Smith glacier drainage systems, raising global sea level by over 1 mm during the past decade alone. The coincidence of rapid ice thinning at the Amundsen Coast and warm circumpolar deep water intrusion in Pine Island Bay, coupled with a ~ 50 cubic kilometre annual freshening of the Ross Sea Gyre downstream, makes ocean melting an attractive proposition for the origin of the regional disturbance. At the same time, the Larsen Ice Shelf surface has lowered by up to 0.27 m per year, in tandem with a period of atmospheric warming and ice shelf collapse. The lowering cannot be explained by increased summer melt-water production alone, and must reflect a loss of basal ice through melting. Ocean temperature measurements close to the ice shelf barrier support this conclusion, making enhanced basal ice melting a likely factor linking the regional climate warming and the successive disintegration of sections of the Larsen Ice Shelf.

  19. Effects of graphene on electro-optic switching and spontaneous polarization of a ferroelectric liquid crystal

    SciTech Connect

    Basu, Rajratan

    2014-09-15

    A small quantity of graphene flakes was doped in a ferroelectric liquid crystal (FLC), and the field-induced ferroelectric electro-optic switching was found to be significantly faster in the FLC + graphene hybrid than that of the pure FLC. Further studies revealed that the suspended graphene flakes enhanced the FLC's spontaneous polarization by improving smectic-C ordering resulting from the π–π electron stacking, and reduced rotation viscosity by trapping some of the free ions of the FLC media. These effects coherently impacted the FLC-switching phenomenon, enabling the FLC molecules to switch faster on reversing an external electric field.

  20. Transitions between paraelectric and ferroelectric phases of bent-core smectic liquid crystals in the bulk and in thin freely suspended films

    NASA Astrophysics Data System (ADS)

    Eremin, Alexey; Floegel, Martin; Kornek, Ulrike; Stern, Stephan; Stannarius, Ralf; Nádasi, Hajnalka; Weissflog, Wolfgang; Zhu, Chenhui; Shen, Yongqiang; Park, Cheol Soo; Maclennan, Joseph; Clark, Noel

    2012-11-01

    We report on the contrasting phase behavior of a bent-core liquid crystal with a large opening angle between the mesogenic units in the bulk and in freely suspended films. Second-harmonic generation experiments and direct observation of director inversion walls in films in an applied electric field reveal that the nonpolar smectic C phase observed in bulk samples becomes a ferroelectric “banana” phase in films, showing that a mesogen with a small steric moment can give a phase with polar order in freely suspended films even when the corresponding bulk phase is paraelectric.

  1. [Cholangitis revealing an intrahepatic Osler's disease].

    PubMed

    Asma, Kochlef; Dalila, Gargouri; Olfa, Bousnina; Malika, Romani; Afef, Kilani; Najet, BelHadg; Jamel, Kharrat; Abdeljabbar, Gorbel; Sarra, Shili; Chiraz, Jemli; Mohamed, Habib Daghfous; Slim, Khlifi; Anis, Ben Maamer; Abdelmajid, Letaïef

    2005-08-01

    Osler Weber Rendu Disease is an hereditary haemorrhagic télangectasia habitually revealed by reccurent bleeding (epistaxis). Hepatic involvement in Osler disease is found in 8 to 31%, manifested by cholestasis. We report an original observation of a cholangitis revealing Osler disease.

  2. Is Self-Disclosure Self-Revealing?

    ERIC Educational Resources Information Center

    Gitter, A. George; Black, Harvey

    1976-01-01

    Based on the factorial analysis of data collected from 260 undergraduates, this study found differences in self-revealing associated with information content, target person, and sex of subject. Gilding was found to be related to self-disclosure and intimate rather than superficial information. Dogmatism did not influence either revealing or…

  3. Revealing Conceptual Understanding of International Business

    ERIC Educational Resources Information Center

    Ashley, Sue; Schaap, Harmen; de Bruijn, Elly

    2017-01-01

    This study aims to identify an adequate approach for revealing conceptual understanding in higher professional education. Revealing students' conceptual understanding is an important step towards developing effective curricula, assessment and aligned teaching strategies to enhance conceptual understanding in higher education. Essays and concept…

  4. REVEAL: Software Documentation and Platform Migration

    NASA Technical Reports Server (NTRS)

    Wilson, Michael A.; Veibell, Victoir T.; Freudinger, Lawrence C.

    2008-01-01

    The Research Environment for Vehicle Embedded Analysis on Linux (REVEAL) is reconfigurable data acquisition software designed for network-distributed test and measurement applications. In development since 2001, it has been successfully demonstrated in support of a number of actual missions within NASA s Suborbital Science Program. Improvements to software configuration control were needed to properly support both an ongoing transition to operational status and continued evolution of REVEAL capabilities. For this reason the project described in this report targets REVEAL software source documentation and deployment of the software on a small set of hardware platforms different from what is currently used in the baseline system implementation. This report specifically describes the actions taken over a ten week period by two undergraduate student interns and serves as a final report for that internship. The topics discussed include: the documentation of REVEAL source code; the migration of REVEAL to other platforms; and an end-to-end field test that successfully validates the efforts.

  5. Crater Formed in 2008 Reveals Subsurface Ice

    NASA Image and Video Library

    2009-09-24

    The High Resolution Imaging Science Experiment camera on NASA Mars Reconnaissance Orbiter reveals subsurface ice in a crater formed in 2008. The impact that dug the crater excavated water ice from beneath the surface.

  6. Hiding personal information reveals the worst

    PubMed Central

    John, Leslie K.; Barasz, Kate; Norton, Michael I.

    2016-01-01

    Seven experiments explore people’s decisions to share or withhold personal information, and the wisdom of such decisions. When people choose not to reveal information—to be “hiders”—they are judged negatively by others (experiment 1). These negative judgments emerge when hiding is volitional (experiments 2A and 2B) and are driven by decreases in trustworthiness engendered by decisions to hide (experiments 3A and 3B). Moreover, hiders do not intuit these negative consequences: given the choice to withhold or reveal unsavory information, people often choose to withhold, but observers rate those who reveal even questionable behavior more positively (experiments 4A and 4B). The negative impact of hiding holds whether opting not to disclose unflattering (drug use, poor grades, and sexually transmitted diseases) or flattering (blood donations) information, and across decisions ranging from whom to date to whom to hire. When faced with decisions about disclosure, decision-makers should be aware not just of the risk of revealing, but of what hiding reveals. PMID:26755591

  7. Hiding personal information reveals the worst.

    PubMed

    John, Leslie K; Barasz, Kate; Norton, Michael I

    2016-01-26

    Seven experiments explore people's decisions to share or withhold personal information, and the wisdom of such decisions. When people choose not to reveal information--to be "hiders"--they are judged negatively by others (experiment 1). These negative judgments emerge when hiding is volitional (experiments 2A and 2B) and are driven by decreases in trustworthiness engendered by decisions to hide (experiments 3A and 3B). Moreover, hiders do not intuit these negative consequences: given the choice to withhold or reveal unsavory information, people often choose to withhold, but observers rate those who reveal even questionable behavior more positively (experiments 4A and 4B). The negative impact of hiding holds whether opting not to disclose unflattering (drug use, poor grades, and sexually transmitted diseases) or flattering (blood donations) information, and across decisions ranging from whom to date to whom to hire. When faced with decisions about disclosure, decision-makers should be aware not just of the risk of revealing, but of what hiding reveals.

  8. Mesomorphic Behavior of Symmetrical and Unsymmetrical Azomethines with Two Imine Groups

    PubMed Central

    Iwan, Agnieszka; Janeczek, Henryk; Jarzabek, Bozena; Rannou, Patrice

    2009-01-01

    Seven symmetrical azomethines with two imine groups (HC=N) were synthesized by condensation of the benzene-1,4-dicarboxaldehyde with five amines (first group: A1-A5) and of the 2,5-thiophenedicarboxaldehyde with two amines (second group: AT1-AT2). Additionally, two unsymmetrical azomethines were obtained by a two step condensation of benzene-1,4-dicarboxaldehyde with pyren-1-amine (1st step) (abbreviated hereinafter as AP1) and then AP1 was reacted with 4-dodecylaniline or 4-hexadecylaniline (2nd step) (third group: AP1A-AP1B). Liquid crystalline properties of the azomethines were studied by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and UV-vis spectroscopy in the function of temperature [UV-vis(T)]. The Wide-Angle X-ray Diffraction (WAXD) technique was used to probe the structural properties of the azomethines. Mesomorphic behavior was observed for symmetrical and unsymmetrical azomethines, obtained from the benzene-1,4-dicarboxaldehyde and symmetrical ones prepared from 2,5-thiophenedicarboxaldehyde and different amines having aliphatic chains. Based on the POM and DSC measurements the following mesophases were detected: nematic, smectic A, smectic C, smectic F (I), smectic G (J).

  9. REVEAL: Software Documentation and Platform Migration

    NASA Technical Reports Server (NTRS)

    Wilson, Michael A.; Veibell, Victoir T.

    2011-01-01

    The Research Environment for Vehicle Embedded Analysis on Linux (REVEAL) is reconfigurable data acquisition software designed for network-distributed test and measurement applications. In development since 2001, it has been successfully demonstrated in support of a number of actual missions within NASA's Suborbital Science Program. Improvements to software configuration control were needed to properly support both an ongoing transition to operational status and continued evolution of REVEAL capabilities. For this reason the project described in this report targets REVEAL software source documentation and deployment of the software on a small set of hardware platforms different from what is currently used in the baseline system implementation. This presentation specifically describes the actions taken over a ten week period by two undergraduate student interns and serves as an overview of the content of the final report for that internship.

  10. Omics strategies for revealing Yersinia pestis virulence

    PubMed Central

    Yang, Ruifu; Du, Zongmin; Han, Yanping; Zhou, Lei; Song, Yajun; Zhou, Dongsheng; Cui, Yujun

    2012-01-01

    Omics has remarkably changed the way we investigate and understand life. Omics differs from traditional hypothesis-driven research because it is a discovery-driven approach. Mass datasets produced from omics-based studies require experts from different fields to reveal the salient features behind these data. In this review, we summarize omics-driven studies to reveal the virulence features of Yersinia pestis through genomics, trascriptomics, proteomics, interactomics, etc. These studies serve as foundations for further hypothesis-driven research and help us gain insight into Y. pestis pathogenesis. PMID:23248778

  11. Comparing SessionStateReveal and EphemeralKeyReveal for Diffie-Hellman Protocols

    NASA Astrophysics Data System (ADS)

    Ustaoglu, Berkant

    Both the "eCK" model, by LaMacchia, Lauter and Mityagin, and the "CK01" model, by Canetti and Krawczyk, address the effect of leaking session specific ephemeral data on the security of key establishment schemes. The CK01-adversary is given a SessionStateReveal query to learn session-specific private data defined by the protocol specification, whereas the eCK-adversary is equipped with an EphemeralKeyReveal query to access all ephemeral private input required to carry session computations. SessionStateReveal cannot be issued against the test session; by contrast EphemeralKeyReveal can be used against the test session under certain conditions. On the other hand, it is not obvious how EphemeralKeyReveal compares to SessionStateReveal. Thus it is natural to ask which model is more useful and practically relevant.

  12. Open chromatin reveals the functional maize genome

    USDA-ARS?s Scientific Manuscript database

    Every cellular process mediated through nuclear DNA must contend with chromatin. As results from ENCODE show, open chromatin assays can efficiently integrate across diverse regulatory elements, revealing functional non-coding genome. In this study, we use a MNase hypersensitivity assay to discover o...

  13. Revealing Student Teacher's Thinking through Dilemma Analysis

    ERIC Educational Resources Information Center

    Talanquer, Vicente; Tomanek, Debra; Novodvorsky, Ingrid

    2007-01-01

    We explore the potential of dilemma analysis as an assessment tool to reveal student teachers' thinking and concerns about their practice. For this purpose we analyze the dilemma analyses completed by 22 student teachers enrolled in our science teacher preparation program over a period of four semesters. Student teachers' dilemmas fall into two…

  14. [Pneumococcal septic arthritis revealing a multiple myeloma].

    PubMed

    Renou, F; Gerber, A; Moiton, M-P; Ferrandiz, D; Yvin, J-L

    2007-03-01

    The most common presenting features of multiple myeloma are bone pain, anemia, renal failure or hypercalcemia. Bacterial infection as the initial presentation of this desease is rare. We report the case of a 62-year-old man with pneumococcal septic arthritis of the knee revealing a multiple myeloma. Pneumococcal infection should lead to a suspicion of underlying illness and especially the multiple myeloma.

  15. Revealing a Child's Pathology: Physicians' Experiences

    ERIC Educational Resources Information Center

    Scelles, Regine; Aubert-Godard, Anne; Gargiulo, Marcela; Avant, Monique; Gortais, Jean

    2010-01-01

    In this study, 12 physicians and 12 care-givers were interviewed using semi-structured interviews. We explored physicians' experiences when they revealed a diagnosis. We also tried to understand which family members the physician was thinking of, with whom they identified themselves, and their first choice of the person to whom they prefer to…

  16. Eye Movements Reveal Dynamics of Task Control

    ERIC Educational Resources Information Center

    Mayr, Ulrich; Kuhns, David; Rieter, Miranda

    2013-01-01

    With the goal to determine the cognitive architecture that underlies flexible changes of control settings, we assessed within-trial and across-trial dynamics of attentional selection by tracking of eye movements in the context of a cued task-switching paradigm. Within-trial dynamics revealed a switch-induced, discrete delay in onset of…

  17. Eye Movements Reveal Dynamics of Task Control

    ERIC Educational Resources Information Center

    Mayr, Ulrich; Kuhns, David; Rieter, Miranda

    2013-01-01

    With the goal to determine the cognitive architecture that underlies flexible changes of control settings, we assessed within-trial and across-trial dynamics of attentional selection by tracking of eye movements in the context of a cued task-switching paradigm. Within-trial dynamics revealed a switch-induced, discrete delay in onset of…

  18. Effect of Enantiomeric Excess on the Phase Behavior of Antiferroelectric Liquid Crystals

    SciTech Connect

    L Pan; B McCoy; S Wang; Z Liu; S Wang; R Pindak; C Huang

    2011-12-31

    Null transmission ellipsometry and resonant x-ray diffraction are employed to study the effect of enantiomeric excess (EE) on the phase behavior of antiferroelectric liquid crystal 10OTBBB1M7. Phase sequence, layer spacing, and pitch of the helical structures of the smectic-C*{sub {alpha}} and smectic-C* phases are studied as a function of temperature and EE. Upon reducing EE, a liquid-gas-type critical point of the smectic-C*{sub {alpha}} to smectic-C* transition is observed, as well as the disappearance of the smectic-C*{sub d4} and the smectic-C*{sub d3} phases. Results are analyzed in a mean-field model.

  19. Revealing interference by continuous variable discordant states.

    PubMed

    Meda, A; Olivares, S; Degiovanni, I P; Brida, G; Genovese, M; Paris, M G A

    2013-08-15

    In general, a pair of uncorrelated Gaussian states mixed in a beam splitter (BS) produces a correlated state at the output. However, when the inputs are identical Gaussian states the output state is equal to the input, and no correlations appear, as the interference had not taken place. On the other hand, since physical phenomena do have observable effects, and the BS is there, a question arises on how to reveal the interference between the two beams. We prove theoretically and demonstrate experimentally that this is possible if at least one of the two beams is prepared in a discordant, i.e., Gaussian correlated, state with a third beam. We also apply the same technique to reveal the erasure of polarization information. Our experiment involves thermal states and the results show that Gaussian discordant states, even when they show a positive Glauber P-function, may be useful to achieve specific tasks.

  20. Revealing Student Teachers' Thinking through Dilemma Analysis

    NASA Astrophysics Data System (ADS)

    Talanquer, Vicente; Tomanek, Debra; Novodvorsky, Ingrid

    2007-06-01

    We explore the potential of dilemma analysis as an assessment tool to reveal student teachers’ thinking and concerns about their practice. For this purpose we analyze the dilemma analyses completed by 22 student teachers enrolled in our science teacher preparation program over a period of four semesters. Student teachers’ dilemmas fall into two main groups: dilemmas about student performance and dilemmas associated with instructional decisions. These dilemmas reveal a variety of concerns that student teachers have about their work. In particular, concerns about lack of student motivation and its consequences on performance and instruction play a central role in student teachers’ thinking. The recognition of common patterns of thought in our student teacher thinking has made us reflect on and re-evaluate important components of the curriculum in our science teacher preparation program.

  1. [Pseudotumoral toxoplasmic cystitis revealing acquired immunodeficiency syndrome].

    PubMed

    Ples, Raluca; Méchaï, Frédéric; Champiat, Bernard; Droupy, Stéphane; Huerre, Michel; Guettier, Catherine; Ferlicot, Sophie

    2011-02-01

    A case of bladder toxoplasmosis in a 57-year-old male Caucasian patient was diagnosed with difficulty due to misleading clinical presentation. The patient presented with pollakiuria and urination burning. Imagery showed pseudotumoral thickening of the vesicle wall. Previously unknown status of HIV infection was found positive through the diagnosis of bladder toxoplasmosis. The patient died rapidly from neurological complications. This is the second published case in which bladder toxoplasmosis reveals an HIV infection.

  2. Satellite altimetry reveals seafloor tectonic fabric

    SciTech Connect

    Mcadoo, D.C.; Marks, K.M. )

    1992-01-01

    Seasat altimeter observations of sea-surface topography have revealed much that was unsuspected about the marine gravity field and seafloor topography, which in conjunction with crustal/upper-mantle density variations generates short wavelength (less than 200-km) marine gravity field fluctuations. Such high-resolution altimeter data is currently available, however, only for 6 percent of the world's ocean surface area; future efforts with Geosat Geodetic Mission and ERS-1 data will expand coverage to the entire world ocean. 4 refs.

  3. Experts reveal catalyst-selection methodologies

    SciTech Connect

    1996-10-14

    Refining catalyst selection procedure were discussed in detail at Oil and Gas Journal`s International Catalyst Conference, Feb. 1--2, in Houston. Marathon Oil Co.`s James P. Wick revealed details of Marathon`s program for review and optimization of fluid catalytic cracking (FCC) and hydrotreating catalysts. And renowned FCC expert Del Tolen outlined a step-by-step procedure for choosing an FCC catalyst. The paper describes Marathon`s program and Tolen`s selection process.

  4. [Pyoderma gangrenosum revealing colonic diverticulitis: Two cases].

    PubMed

    Fongue, J; Brajon, D; Visée, C; Combes, E; Andrac-Meyer, L; Berbis, P

    2015-11-01

    The association of pyoderma gangrenosum (PG) with colonic diverticulitis infection (DI) is relatively unknown. Herein, we describe two cases of PG with full recovery after colonic surgery. Case 1: an 83-year-old man presented with lesions on his legs that had been present for several weeks, and a diagnosis of PG was confirmed histologically. Abdominopelvic computed tomography (CT) performed on account of biological inflammatory syndrome revealed DI complicated by abscesses. Following the failure of two different antibiotic regimens, sigmoidectomy was performed. Postoperatively, the skin lesions healed without local or systemic corticosteroids. Case 2: a 63-year-old woman presented PG resistant to local and systemic corticosteroids and dapsone for several months. A particularly severe flare was accompanied by abdominal pain and inflammatory syndrome. CT revealed perforated sigmoid DI. Sigmoidectomy was performed after failure of drug therapy. The patient's PG subsequently improved and had disappeared without recurrence at 24months. Both of these cases of PG revealed DI. The hypothesis is that DI constituted a source of colonic inflammation, sending out bacterial antigenic stimuli that resulted in PG through deposition of circulating immune complexes. Removal of this inflammatory source appears to have enabled healing of PG. DI must be added to the list of systemic diseases associated with PG. In the case of isolated PG, CT may be used to detect asymptomatic DI. Early diagnosis could prevent serious gastrointestinal complications. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

  5. Superstitious perceptions reveal properties of internal representations.

    PubMed

    Gosselin, Frédéric; Schyns, Philippe G

    2003-09-01

    Everyone has seen a human face in a cloud, a pebble, or blots on a wall. Evidence of superstitious perceptions has been documented since classical antiquity, but has received little scientific attention. In the study reported here, we used superstitious perceptions in a new principled method to reveal the properties of unobservable object representations in memory. We stimulated the visual system with unstructured white noise. Observers firmly believed that they perceived the letter S in Experiment 1 and a smile on a face in Experiment 2. Using reverse correlation and computational analyses, we rendered the memory representations underlying these superstitious perceptions.

  6. Symbiotic conversations are revealed under genetic interrogation.

    PubMed

    Ruby, Edward G

    2008-10-01

    The recent development and application of molecular genetics to the symbionts of invertebrate animal species have advanced our knowledge of the biochemical communication that occurs between the host and its bacterial symbionts. In particular, the ability to manipulate these associations experimentally by introducing genetic variants of the symbionts into naive hosts has allowed the discovery of novel colonization mechanisms and factors. In addition, the role of the symbionts in inducing normal host development has been revealed, and its molecular basis described. In this Review, I discuss many of these developments, focusing on what has been discovered in five well-understood model systems.

  7. Infections Revealing Complement Deficiency in Adults

    PubMed Central

    Audemard-Verger, A.; Descloux, E.; Ponard, D.; Deroux, A.; Fantin, B.; Fieschi, C.; John, M.; Bouldouyre, A.; Karkowsi, L.; Moulis, G.; Auvinet, H.; Valla, F.; Lechiche, C.; Davido, B.; Martinot, M.; Biron, C.; Lucht, F.; Asseray, N.; Froissart, A.; Buzelé, R.; Perlat, A.; Boutboul, D.; Fremeaux-Bacchi, V.; Isnard, S.; Bienvenu, B.

    2016-01-01

    Abstract Complement system is a part of innate immunity, its main function is to protect human from bacterial infection. As genetic disorders, complement deficiencies are often diagnosed in pediatric population. However, complement deficiencies can also be revealed in adults but have been poorly investigated. Herein, we describe a case series of infections revealing complement deficiency in adults to study clinical spectrum and management of complement deficiencies. A nationwide retrospective study was conducted in French university and general hospitals in departments of internal medicine, infectious diseases enrolling patients older than 15 years old who had presented at least one infection leading to a complement deficiency diagnosis. Forty-one patients included between 2002 and 2015 in 19 different departments were enrolled in this study. The male-to-female ratio was 1.3 and the mean age at diagnosis was 28 ± 14 (15–67) years. The main clinical feature was Neisseria meningitidis meningitis 75% (n = 31/41) often involving rare serotype: Y (n = 9) and W 135 (n = 7). The main complement deficiency observed was the common final pathway deficiency 83% (n = 34/41). Half of the cohort displayed severe sepsis or septic shock at diagnosis (n = 22/41) but no patient died. No patient had family history of complement deficiency. The mean follow-up was 1.15 ± 1.95 (0.1–10) years. Half of the patients had already suffered from at least one infection before diagnosis of complement deficiency: meningitis (n = 13), pneumonia (n = 4), fulminans purpura (n = 1), or recurrent otitis (n = 1). Near one-third (n = 10/39) had received prophylactic antibiotics (cotrimoxazole or penicillin) after diagnosis of complement deficiency. The vaccination coverage rate, at the end of the follow-up, for N meningitidis, Streptococcus pneumonia, and Haemophilius influenzae were, respectively, 90% (n = 33/37), 47% (n = 17/36), and 35

  8. Trench Reveals Two Faces of Soils

    NASA Technical Reports Server (NTRS)

    2004-01-01

    This approximate true-color image mosaic from the panoramic camera on the Mars Exploration Rover Opportunity shows a trench dug by the rover in the vicinity of the 'Anatolia' region. Two imprints from the rover's Mossbauer spectrometer instrument were left in the exposed soils. Detailed comparisons between soils exposed at the surface and those found at depth reveal that surface soils have higher levels of hematite while subsurface soils show fine particles derived from basalt. The trench is approximately 11 centimeters deep. This image was taken on sol 81 with the panoramic camera's 430-, 530- and 750-nanometer filters.

  9. Apocalypto: revealing lost text with XMT

    NASA Astrophysics Data System (ADS)

    Mills, David; Davis, Graham R.; Lai, Yu-kun; Rosin, Paul

    2014-09-01

    "Can brute-force high-contrast tomography techniques and image processing techniques retrieve textual content from damaged heritage materials?" The Dental Institute at Queen Mary University of London (QMUL) is the leading centre for very high contrast X-Ray Microtomography imaging. The Apocalypto Project is our collaboration with the heritage community and experts in Computer Vision systems in the Computer Science Department at Cardiff University. This collaboration has developed techniques and a workflow that allows us to reveal textual content from moisture-damaged parchment rolls. This article will also present some initial results from burned and heat shrunken parchment rolls, an insect damaged Mamluk cap and a birch bark roll.

  10. Trench Reveals Two Faces of Soils

    NASA Technical Reports Server (NTRS)

    2004-01-01

    This approximate true-color image mosaic from the panoramic camera on the Mars Exploration Rover Opportunity shows a trench dug by the rover in the vicinity of the 'Anatolia' region. Two imprints from the rover's Mossbauer spectrometer instrument were left in the exposed soils. Detailed comparisons between soils exposed at the surface and those found at depth reveal that surface soils have higher levels of hematite while subsurface soils show fine particles derived from basalt. The trench is approximately 11 centimeters deep. This image was taken on sol 81 with the panoramic camera's 430-, 530- and 750-nanometer filters.

  11. Symbiotic conversations are revealed under genetic interrogation

    PubMed Central

    Ruby, Edward G.

    2013-01-01

    The recent development and application of molecular genetics to the symbionts of invertebrate animal species have advanced our knowledge of the biochemical communication that occurs between the host and its bacterial symbionts. In particular, the ability to manipulate these associations experimentally by introducing genetic variants of the symbionts into naive hosts has allowed the discovery of novel colonization mechanisms and factors. In addition, the role of the symbionts in inducing normal host development has been revealed, and its molecular basis described. In this Review, I discuss many of these developments, focusing on what has been discovered in five well-understood model systems. PMID:18794913

  12. Horseshoe Kidney Incidentally Revealed on Meckel Scintigraphy.

    PubMed

    Bai, Xia; Codreanu, Ion; Yang, Hua; Servaes, Sabah; Zhuang, Hongming

    2015-09-01

    An 8-year-old male patient with history of bloody stools underwent a Meckel diverticulum scintigraphy to evaluate for ectopic gastric mucosa. The static images showed 2 abnormal foci of radiotracer accumulation in the mid-abdomen. Contrary to the renal activity, the foci appeared more prominent on the anterior view and localized anteriorly to the expected kidneys location on the left lateral view. Carefully reviewed dynamic acquisition revealed faint catenary-shaped activity in this region on earlier images, gradually evolving into 2 prominent foci on later images. A horseshoe kidney was suspected, the pathology being confirmed by abdominal ultrasonography.

  13. Elasticity of smectic liquid crystals with in-plane orientational order and dispiration asymmetry

    NASA Astrophysics Data System (ADS)

    Alageshan, Jaya Kumar; Chakrabarti, Buddhapriya; Hatwalne, Yashodhan

    2017-02-01

    The Nelson-Peliti formulation of the elasticity theory of isolated fluid membranes with orientational order emphasizes the interplay between geometry, topology, and thermal fluctuations. Fluid layers of lamellar liquid crystals such as smectic-C , hexatic smectics, and smectic-C* are endowed with in-plane orientational order. We extend the Nelson-Peliti formulation so as to bring these smectics within its ambit. Using the elasticity theory of smectics-C*, we show that positive and negative dispirations (topological defects in Smectic-C* liquid crystals) with strengths of equal magnitude have disparate energies—a result that is amenable to experimental tests.

  14. [Severe pulmonary embolism revealed by status epilepticus].

    PubMed

    Allou, N; Coolen-Allou, N; Delmas, B; Cordier, C; Allyn, J

    2016-12-01

    High-risk pulmonary embolism (PE) is associated with high mortality rate (>50%). In some cases, diagnosis of PE remains a challenge with atypical presentations like in this case report with a PE revealed by status epilepticus. We report the case of a 40-year-old man without prior disease, hospitalized in ICU for status epilepticus. All paraclinical examinations at admission did not show any significant abnormalities (laboratory tests, cardiologic and neurological investigations). On day 1, he presented a sudden circulatory collapse and echocardiography showed right intra-auricular thrombus. He was treated by thrombolysis and arteriovenous extracorporeal membrane oxygenation. After stabilization, computed tomography showed severe bilateral PE. He developed multi-organ failure and died 4days after admission. Pulmonary embolism revealed by status epilepticus has rarely been reported and is associated with poor prognosis. Physicians should be aware and think of the possibility of PE in patients with status epilepticus without any history or risk factors of seizure and normal neurological investigations. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

  15. Revealing Event Saliency in Unconstrained Video Collection.

    PubMed

    Zhang, Dingwen; Han, Junwei; Jiang, Lu; Ye, Senmao; Chang, Xiaojun

    2017-04-01

    Recent progresses in multimedia event detection have enabled us to find videos about a predefined event from a large-scale video collection. Research towards more intrinsic unsupervised video understanding is an interesting but understudied field. Specifically, given a collection of videos sharing a common event of interest, the goal is to discover the salient fragments, i.e., the curt video fragments that can concisely portray the underlying event of interest, from each video. To explore this novel direction, this paper proposes an unsupervised event saliency revealing framework. It first extracts features from multiple modalities to represent each shot in the given video collection. Then, these shots are clustered to build the cluster-level event saliency revealing framework, which explores useful information cues (i.e., the intra-cluster prior, inter-cluster discriminability, and inter-cluster smoothness) by a concise optimization model. Compared with the existing methods, our approach could highlight the intrinsic stimulus of the unseen event within a video in an unsupervised fashion. Thus, it could potentially benefit to a wide range of multimedia tasks like video browsing, understanding, and search. To quantitatively verify the proposed method, we systematically compare the method to a number of baseline methods on the TRECVID benchmarks. Experimental results have demonstrated its effectiveness and efficiency.

  16. Interior Evolution of Ceres Revealed by Dawn

    NASA Astrophysics Data System (ADS)

    Raymond, Carol A.; Park, Ryan S.; Konopliv, Alex S.; Bland, Michael T.; Marchi, Simone; Castillo-Rogez, Julie C.; McCord, Thomas B.; Jaumann, Ralf; Russell, Christopher T.; Prettyman, Thomas H.

    2015-11-01

    Dawn's exploration of Ceres has revealed its geophysical characteristics, informing the processes that have shaped it. Dawn has determined the average diameter of Ceres to be 940 km, smaller than the previously estimated 975 km [1]. This implies a density of 2160 kg/m3, indicating that Ceres is less differentiated than predicted [2]. The low-degree gravity field is consistent with the body being in hydrostatic equilibrium and the magnitude of J2 implies some central condensation. Ceres' entire surface is cratered, implying the lack of a thick (10's of km) water ice layer at the surface. Variability in Ceres' crater morphology indicates that the near-surface layer has variable strength and rheology, likely due to heterogeneity in the near-surface mixture of rock, ice and salt. The lack of a number of expected large impact basins on Ceres can be interpreted to be the result of viscous relaxation, resurfacing or a combination of both. These data provide insights into Ceres' thermal evolution and mechanical properties, which appear to be unique to this warm, icy body.[1] Thomas, P. C., et al., Differentiation of the asteroid Ceres as revealed by its shape, Nature, 437, 224-226, 2005; [2] McCord et al., Ceres: Its Origin, Evolution and Structure and Dawn's Potential Contribution, Space Sci Rev DOI 10.1007/s11214-010-9729-9, 2011.

  17. Resonant X-Ray Diffraction Study of an Unusually Large Phase Coexistance in Smectic Liquid-Crystal Films

    SciTech Connect

    Pan L.; Pindak R.; Barois, P.; Liu, Z.Q.; McCoy, B.K. & Hyang, C.C.

    2012-01-19

    The recent discovery of the new smectic-C{sub d6}* (SmC{sub d6}*) phase [S. Wang et al. Phys. Rev. Lett. 104 027801 (2010)] also revealed the existence of a noisy region in the temperature window between the SmC{sub d6}* phase and the smectic-C{sub d4}* (SmC{sub d4}*) phase. Characterized by multiple resonant peaks spanning a wide region in Q{sub Z}, the corresponding structure of this temperature window has been a mystery. In this Letter, through a careful resonant x-ray diffraction study and simulations of the diffraction spectra, we show that this region is in fact an unusually large coexistence region of the SmC{sub d6}* phase and the SmC{sub d4}* phase. The structure of the noisy region is found to be a heterogeneous mixture of local SmC{sub d6}* and SmC{sub d4}* orders on the sub-{micro}m scale.

  18. Pressure-temperature microscopy of petroleum-derived hydrocarbons

    SciTech Connect

    Perrotta, A.J.; McCullough, J.P.; Beuther, H.

    1983-03-01

    An apparatus allowing microscopy of petroleum derived hydrocarbons at pressures and temperatures comparable to those encountered in the hydroprocessing of coal and oil, and its use in the study of pressure and temperature effects on the crystallization behavior of a decant oil-derived air blown-pitch (DODAB) is described in this paper. Crystallization of the mesophase from aromatic rich precursors can be used as a tracking vehicle whose anisotropy allows easy detection under the polarizing microscope. Mesophase formation pressure dependence using N/sub 2/ and H/sub 2/ reveals that there is a chemical effect associated with H/sub 2/ since N/sub 2/ pressure to 1900 psig had no effect on mesophase formation. In both cases a fine grained anisotropic phase forms initially at the crystallization temperature and 25 psig. In pyrolyzed material mesophase formation under N/sub 2/ is a pressure dependent transformation.

  19. Social patterns revealed through random matrix theory

    NASA Astrophysics Data System (ADS)

    Sarkar, Camellia; Jalan, Sarika

    2014-11-01

    Despite the tremendous advancements in the field of network theory, very few studies have taken weights in the interactions into consideration that emerge naturally in all real-world systems. Using random matrix analysis of a weighted social network, we demonstrate the profound impact of weights in interactions on emerging structural properties. The analysis reveals that randomness existing in particular time frame affects the decisions of individuals rendering them more freedom of choice in situations of financial security. While the structural organization of networks remains the same throughout all datasets, random matrix theory provides insight into the interaction pattern of individuals of the society in situations of crisis. It has also been contemplated that individual accountability in terms of weighted interactions remains as a key to success unless segregation of tasks comes into play.

  20. Revealing the Hidden, High Energy Sun

    NASA Astrophysics Data System (ADS)

    Osten, Rachel A.

    2017-08-01

    Eclipses of the Sun happen when the Moon blocks the Sun's light from our view. It may seem puzzling, then, that solar physicists flock to study the Sun during these special events. Shouldn't there be nothing to see? Yet there is. I will talk about what the tantalizing solar features revealed during solar eclipses tell us about the Sun and its structure, as well as how this relates to what high energy solar satellites routinely discover without the need for eclipses. I will then make a leap into the cosmos to relate this to what astronomers are learning about the nearest stars and their abilities to make good homes for other planets.

  1. Neutron Imaging Reveals Internal Plant Hydraulic Dynamics

    SciTech Connect

    Warren, Jeffrey; Bilheux, Hassina Z; Kang, Misun; Voisin, Sophie; Cheng, Chu-Lin; Horita, Jusuke; Perfect, Edmund

    2013-01-01

    Many terrestrial ecosystem processes are constrained by water availability and transport within the soil. Knowledge of plant water fluxes is thus critical for assessing mechanistic processes linked to biogeochemical cycles, yet resolution of root structure and xylem water transport dynamics has been a particularly daunting task for the ecologist. Through neutron imaging, we demonstrate the ability to non-invasively monitor individual root functionality and water fluxes within Zea mays L. (maize) and Panicum virgatum L. (switchgrass) seedlings growing in a sandy medium. Root structure and growth were readily imaged by neutron radiography and neutron computed tomography. Seedlings were irrigated with water or deuterium oxide and imaged through time as a growth lamp was cycled on to alter leaf demand for water. Sub-millimeter scale resolution reveals timing and magnitudes of root water uptake, redistribution within the roots, and root-shoot hydraulic linkages, relationships not well characterized by other techniques.

  2. Open chromatin reveals the functional maize genome

    PubMed Central

    Rodgers-Melnick, Eli; Vera, Daniel L.; Bass, Hank W.

    2016-01-01

    Cellular processes mediated through nuclear DNA must contend with chromatin. Chromatin structural assays can efficiently integrate information across diverse regulatory elements, revealing the functional noncoding genome. In this study, we use a differential nuclease sensitivity assay based on micrococcal nuclease (MNase) digestion to discover open chromatin regions in the maize genome. We find that maize MNase-hypersensitive (MNase HS) regions localize around active genes and within recombination hotspots, focusing biased gene conversion at their flanks. Although MNase HS regions map to less than 1% of the genome, they consistently explain a remarkably large amount (∼40%) of heritable phenotypic variance in diverse complex traits. MNase HS regions are therefore on par with coding sequences as annotations that demarcate the functional parts of the maize genome. These results imply that less than 3% of the maize genome (coding and MNase HS regions) may give rise to the overwhelming majority of phenotypic variation, greatly narrowing the scope of the functional genome. PMID:27185945

  3. Paraventricular meningioma revealed by mental disorder

    PubMed Central

    Hilmani, Said; Houass, Yassine; El Azhari, Abdessamad

    2016-01-01

    Background: Ventricular meningioma constitutes 2% of intracranial meningioma, representing a challenging disease for neurosurgeons. Although cognitive impairment is one of the major symptoms of ventricular tumors, few studies have reported the details of cognitive impairment before and after their surgical removal. The expected effects on cognitive function should also be considered when choosing a surgical approach. Case Descriptions: We report the case of a large lateral ventricle meningioma revealed by cognitive dysfunction and moderate intellectual disability. The patient underwent subtotal resection of the tumor which had partial improvement in cognitive disorders. It is important to precisely assess neuropsychological function in patients with large brain tumors, and judicious preoperative plan, adequate knowledge of anatomy, and use of correct microsurgical techniques are fundamental in achieving complete resection of paraventricular meningioma with low morbidity. Conclusion: Pre and postoperative precise neuropsychological examinations may identify the potential cognitive impairment and beneficial effects of surgery in patients with large lateral ventricle meningiomas. PMID:28144473

  4. Memory strength and specificity revealed by pupillometry

    PubMed Central

    Papesh, Megan H.; Goldinger, Stephen D.; Hout, Michael C.

    2011-01-01

    Voice-specificity effects in recognition memory were investigated using both behavioral data and pupillometry. Volunteers initially heard spoken words and nonwords in two voices; they later provided confidence-based old/new classifications to items presented in their original voices, changed (but familiar) voices, or entirely new voices. Recognition was more accurate for old-voice items, replicating prior research. Pupillometry was used to gauge cognitive demand during both encoding and testing: Enlarged pupils revealed that participants devoted greater effort to encoding items that were subsequently recognized. Further, pupil responses were sensitive to the cue match between encoding and retrieval voices, as well as memory strength. Strong memories, and those with the closest encoding-retrieval voice matches, resulted in the highest peak pupil diameters. The results are discussed with respect to episodic memory models and Whittlesea’s (1997) SCAPE framework for recognition memory. PMID:22019480

  5. Fracture reveals clustering in cohesive granular matter

    NASA Astrophysics Data System (ADS)

    Tapia, Franco; Santucci, Stéphane; Géminard, Jean-Christophe

    2016-09-01

    We report an experimental study of the morphology of fractures in cohesive granular materials. Cohesion is introduced by equilibrating the grains with a humid atmosphere. The setup allows to produce a controlled crack in a thin layer of a glass beads assembly, and observe with an extremely high resolution the edge of the fracture at the free surface of the layer. The detailed multi-scale analysis of the fracture profile reveals the presence, in the bulk of the material, of clusters of grains whose size increases monotonically with the relative humidity. These results are important because the formation of clusters, resulting in a heterogeneity of the cohesion force, governs the mechanical properties of cohesive granular matter in contact with a humid atmosphere.

  6. Revealing effective classifiers through network comparison

    NASA Astrophysics Data System (ADS)

    Gallos, Lazaros K.; Fefferman, Nina H.

    2014-11-01

    The ability to compare complex systems can provide new insight into the fundamental nature of the processes captured, in ways that are otherwise inaccessible to observation. Here, we introduce the n-tangle method to directly compare two networks for structural similarity, based on the distribution of edge density in network subgraphs. We demonstrate that this method can efficiently introduce comparative analysis into network science and opens the road for many new applications. For example, we show how the construction of a “phylogenetic tree” across animal taxa according to their social structure can reveal commonalities in the behavioral ecology of the populations, or how students create similar networks according to the University size. Our method can be expanded to study many additional properties, such as network classification, changes during time evolution, convergence of growth models, and detection of structural changes during damage.

  7. Protein vivisection reveals elusive intermediates in folding

    PubMed Central

    Zheng, Zhongzhou; Sosnick, Tobin R.

    2010-01-01

    Although most folding intermediates escape detection, their characterization is crucial to the elucidation of folding mechanisms. Here we outline a powerful strategy to populate partially unfolded intermediates: A buried aliphatic residue is substituted with a charged residue (e.g., Leu→Glu−) to destabilize and unfold a specific region of the protein. We apply this strategy to Ubiquitin, reversibly trapping a folding intermediate in which the β5 strand is unfolded. The intermediate refolds to a native-like structure upon charge neutralization under mildly acidic conditions. Characterization of the trapped intermediate using NMR and hydrogen exchange methods identifies a second folding intermediate and reveals the order and free energies of the two major folding events on the native side of the rate-limiting step. This general strategy may be combined with other methods and have broad applications in the study of protein folding and other reactions that require trapping of high energy states. PMID:20144618

  8. Sawfishes stealth revealed using computational fluid dynamics.

    PubMed

    Bradney, D R; Davidson, A; Evans, S P; Wueringer, B E; Morgan, D L; Clausen, P D

    2017-02-27

    Detailed computational fluid dynamics simulations for the rostrum of three species of sawfish (Pristidae) revealed that negligible turbulent flow is generated from all rostra during lateral swipe prey manipulation and swimming. These results suggest that sawfishes are effective stealth hunters that may not be detected by their teleost prey's lateral line sensory system during pursuits. Moreover, during lateral swipes, the rostra were found to induce little velocity into the surrounding fluid. Consistent with previous data of sawfish feeding behaviour, these data indicate that the rostrum is therefore unlikely to be used to stir up the bottom to uncover benthic prey. Whilst swimming with the rostrum inclined at a small angle to the horizontal, the coefficient of drag of the rostrum is relatively low and the coefficient of lift is zero.

  9. Memory strength and specificity revealed by pupillometry.

    PubMed

    Papesh, Megan H; Goldinger, Stephen D; Hout, Michael C

    2012-01-01

    Voice-specificity effects in recognition memory were investigated using both behavioral data and pupillometry. Volunteers initially heard spoken words and nonwords in two voices; they later provided confidence-based old/new classifications to items presented in their original voices, changed (but familiar) voices, or entirely new voices. Recognition was more accurate for old-voice items, replicating prior research. Pupillometry was used to gauge cognitive demand during both encoding and testing: enlarged pupils revealed that participants devoted greater effort to encoding items that were subsequently recognized. Further, pupil responses were sensitive to the cue match between encoding and retrieval voices, as well as memory strength. Strong memories, and those with the closest encoding-retrieval voice matches, resulted in the highest peak pupil diameters. The results are discussed with respect to episodic memory models and Whittlesea's (1997) SCAPE framework for recognition memory.

  10. Metabolomics reveals metabolic biomarkers of Crohn's disease

    SciTech Connect

    Jansson, J.K.; Willing, B.; Lucio, M.; Fekete, A.; Dicksved, J.; Halfvarson, J.; Tysk, C.; Schmitt-Kopplin, P.

    2009-06-01

    The causes and etiology of Crohn's disease (CD) are currently unknown although both host genetics and environmental factors play a role. Here we used non-targeted metabolic profiling to determine the contribution of metabolites produced by the gut microbiota towards disease status of the host. Ion Cyclotron Resonance Fourier Transform Mass Spectrometry (ICR-FT/MS) was used to discern the masses of thousands of metabolites in fecal samples collected from 17 identical twin pairs, including healthy individuals and those with CD. Pathways with differentiating metabolites included those involved in the metabolism and or synthesis of amino acids, fatty acids, bile acids and arachidonic acid. Several metabolites were positively or negatively correlated to the disease phenotype and to specific microbes previously characterized in the same samples. Our data reveal novel differentiating metabolites for CD that may provide diagnostic biomarkers and/or monitoring tools as well as insight into potential targets for disease therapy and prevention.

  11. Licking Microstructure Reveals Rapid Attenuation of Neophobia

    PubMed Central

    Monk, Kevin J.; Rubin, Benjamin D.

    2014-01-01

    Many animals hesitate when initially consuming a novel food and increase their consumption of that food between the first and second sessions of access—a process termed attenuation of neophobia (AN). AN has received attention as a model of learning and memory; it has been suggested that plasticity resulting from an association of the novel tastant with “safe outcome” results in a change in the neural response to the tastant during the second session, such that consumption increases. Most studies have reported that AN emerges only an hour or more after the end of the first exposure to the tastant, consistent with what is known of learning-related plasticity. But these studies have typically measured consumption, rather than real-time behavior, and thus the possibility exists that a more rapidly developing AN remains to be discovered. Here, we tested this possibility, examining both consumption and individual lick times in a novel variant of a brief-access task (BAT). When quantified in terms of consumption, data from the BAT accorded well with the results of a classic one-bottle task—both revealed neophobia/AN specific to higher concentrations (for instance, 28mM) of saccharin. An analysis of licking microstructure, however, additionally revealed a real-time correlate of neophobia—an explicit tendency, similarly specific for 28-mM saccharin, to cut short the initial bout of licks in a single trial (compared with water). This relative hesitancy (i.e., the shortness of the first lick bout to 28-mM saccharin compared with water) that constitutes neophobia not only disappeared between sessions but also gradually declined in magnitude across session 1. These data demonstrate that the BAT accurately measures AN, and that aspects of AN—and the processes underlying familiarization—begin within minutes of the very first taste. PMID:24363269

  12. Ceres Revealed in a Grain of Salt

    NASA Technical Reports Server (NTRS)

    Zolensky, M. E.; Bodnar, R. J.; Fries, M.; Chan, Q. H.-S.; Kebukawa, Y.; Mikouchi, T.; Hagiya, K.; Komatsu, M.; Ohsumi, K.; Steele, A.

    2016-01-01

    Introduction: Zag and Monahans (1998) are H chondrite regolith breccias containing 4.5 giga-year-old halite crystals which contain abundant inclusions of aqueous fluids, solids and organics. These all originated on a cryo-volcanically-active C class asteroid, probably 1 Ceres; the halite was transported to the regolith of the H chondrite parent asteroid, potentially 6 Hebe. Detailed analysis of these solids will thus potentially reveal the mineralogy of Ceres. Mineralogy of solids in the Monahans Halite Solid grains are present in the halites, which were entrained within the mother brines during eruption, including material from the interior and surface of the erupting body. The solids include abundant, widely variable organics that could not have been significantly heated (which would have resulted in the loss of fluids from the halite). Our analyses by Raman microprobe, SEM/EDX, synchrotron X-ray diffraction, UPLC-FD/QToF-MS, C-XANES and TEM reveal that these trapped grains include macromolecular carbon (MMC) similar in structure to CV3 chondrite matrix carbon, aliphatic carbon compounds, olivine (Fo99-59), high- and low-Ca pyroxene, feldspars, phyllosilicates, magnetite, sulfides, metal, lepidocrocite, carbonates, diamond, apatite and zeolites. Conclusions: The halite in Monahans and Zag derive from a water and carbon-rich object that was cryo-volcanically active in the early solar system, probably Ceres. The Dawn spacecraft found that Ceres includes C chondrite materials. Our samples include both protolith and aqueously-altered samples of the body, permitting understanding of alteration conditions. Whatever the halite parent body, it was rich in a wide variety of organics and warm, liquid water at the solar system's dawn.

  13. Speeding Clouds May Reveal Invisible Black Holes

    NASA Astrophysics Data System (ADS)

    Kohler, Susanna

    2017-07-01

    Several small, speeding clouds have been discovered at the center of our galaxy. A new study suggests that these unusual objects may reveal the lurking presence of inactive black holes.Peculiar Cloudsa) Velocity-integrated intensity map showing the location of the two high-velocity compact clouds, HCN0.0090.044 and HCN0.0850.094, in the context of larger molecular clouds. b) and c) Latitude-velocity and longitude-velocity maps for HCN0.0090.044 and HCN0.0850.094, respectively. d) and e) spectra for the two compacts clouds, respectively. Click for a closer look. [Takekawa et al. 2017]Sgr A*, the supermassive black hole marking the center of our galaxy, is surrounded by a region roughly 650 light-years across known as the Central Molecular Zone. This area at the heart of our galaxy is filled with large amounts of warm, dense molecular gas that has a complex distribution and turbulent kinematics.Several peculiar gas clouds have been discovered within the Central Molecular Zone within the past two decades. These clouds, dubbed high-velocity compact clouds, are characterized by their compact sizes and extremely broad velocity widths.What created this mysterious population of energetic clouds? The recent discovery of two new high-velocity compact clouds, reported on in a paper led by Shunya Takekawa (Keio University, Japan), may help us to answer this question.Two More to the CountUsing the James Clerk Maxwell Telescope in Hawaii, Takekawa and collaborators detected the small clouds near the circumnuclear disk at the centermost part of our galaxy. These two clouds have velocity spreads of -80 to -20 km/s and -80 to 0 km/s and compact sizes of just over 1 light-year. The clouds similar appearances and physical properties suggest that they may both have been formed by the same process.Takekawa and collaborators explore and discard several possible origins for these clouds, such as outflows from massive protostars (no massive, luminous stars have been detected affiliated

  14. Neutron Imaging Reveals Internal Plant Hydraulic Dynamics

    NASA Astrophysics Data System (ADS)

    Warren, J.; Bilheux, H.; Kang, M.; Voisin, S.; Cheng, C.; Horita, J.; Perfect, E.

    2011-12-01

    In situ quantification of soil-plant water fluxes have not been fully successful due to a lack of non-destructive techniques capable of revealing roots or water fluxes at relevant spatial scales. Neutron imaging is a unique non-invasive tool that can assess sub-millimeter scale material properties and transport in situ, and which has been successfully applied to characterize soil and plant water status. Here, we have applied neutron radiography and tomography to quantify water transport through individual maize roots in response to internal plant demand. Zea mays seedlings were grown for 10 days in Flint silica sand within 2.6 cm diameter Al chambers. Using a reactor-based neutron source at Oak Ridge National Laboratory (HFIR), water fluxes were tracked through the maize soil-root systems by collecting consecutive neutron radiographs over a 12 h period following irrigation with D2O. D has a much lower neutron attenuation than H, thus D2O displacement of existing H2O within the plant vascular system, or influx of D2O into previously dry tissue or soil is readily tracked by changes in image intensity through time. Plant water release and uptake was regulated by periodically cycling on a high-intensity grow light. From each maize replicate, selected regions of interest (ROI) were delineated around individual roots, root free soil, stem and leaf segments. Changes in ROI were tracked through time to reveal patterns of water flux. The hydration of root and stem tissue cycled in response to illumination; root water content often increased during darkness, then decreased with illumination as water was transported from the root into the stem. Relative root-shoot hydration through time illustrates the balance between demand, storage capacity and uptake, which varies depending on root characteristics and its localized soil environment. The dynamic transport of water between soil, individual roots, stems and leaves was readily visualized and quantified illustrating the value

  15. Revealing the Hot Side of Epsilon Aurigae

    NASA Astrophysics Data System (ADS)

    Hoard, Donald; Stencel, Robert; Howell, Steve

    2012-12-01

    We request a small investment of 24 minutes of Spitzer time, to obtain four IRAC observations of epsilon Aurigae. A naked eye object located near Capella, epsilon Aurigae is the eclipsing binary star with the longest known orbital period, showing a single long duration (~2 yr) eclipse every 27.1 yr. For much of the last 200 years, the nature of the eclipsing object defied explanation. We recently demonstrated that epsilon Aurigae consists of a high luminosity F0 post-AGB star in orbit with a B5 V star surrounded by a solar system sized (~8 AU diameter) disk of cool, dust-dominated material. The eclipse of epsilon Aurigae is a rare event; moreover, it is a unique astrophysical opportunity, since the backlighting of the disk by the high luminosity eclipsed star reveals details that cannot be detected in similar dusty disks around single stars. The current eclipse started in August 2009 and ended in July 2011; we are now in the post-eclipse phase, when the irradiation-heated side of the disk will begin rotating into view. The goals for these observations include: (1) extend our ongoing IRAC monitoring campaign covering the current eclipse to post-eclipse visits; (2) provide a consistent, well-calibrated space-based set of IR photometry for comparison with ongoing ground-based work; and (3) use the composite results to constrain the thermal profile of the disk. A key expectation of these particular observations is to reveal the irradiation-heated portion of the disk, which will be visible on its trailing side following eclipse. Observations of this side of the disk will be crucial to test and constrain new models of disk structure. As part of our overall monitoring campaign with Spitzer, Hubble, Herschel, and numerous ground-based facilities, these proposed observations will make an important contribution to the understanding of stellar evolution in binary stars, including mass transfer and evolution studies, along with new insights into astrophysical disks and post

  16. Theory and Simulation of Extensional Flow-Induced Biaxiality in Discotic Mesophases

    NASA Astrophysics Data System (ADS)

    Singh, Arvinder P.; Rey, Alejandro D.

    1995-09-01

    Flow-induced biaxiality is simulated for a uniaxial discotic nematic liquid crystal subjected to a constant uniaxial, isothermal, incompressible, irrotational, extensional, three dimensional flow, using a previously presented model [Singh A.P. and Rey A.D., J. Phys. II France 4 (1994) 645]. Numerical and analytical solutions of the director triad (n, m, l), and uniaxial (S) and biaxial (P) alignments are given. The unit sphere description of the director triad is used to discuss and analyze the sensitivity of the director triad trajectories and the coupled alignment (uniaxial and biaxial) relaxations to the initial orientation, nematic potential (U), and to the alignment Deborah number (dimensionless extension rate). The evolution of the director triad is given by the rotation of a moving diad (n, l) around a fixed director (m). When the poles of the orientation unit sphere are along the extension axis, and the equator lies in the compression plane of the flow, it is found that the director diad (n, l) dynamics follow geodesic flow and the trajectories belong to the same meridians (great circles through the poles). The space of stable steady state orientation of the uniaxial director n and the biaxial director m is the whole compression plane (the equator of the unit sphere), while that of the biaxial director l is the extension direction (poles). A high degree extension flow-induced biaxiality is found when the uniaxial director is away from the extension axis and when S is relatively low. The scalar order parameter couplings are captured by analyzing the trajectories in the alignment triangle. Computed scientific visualizations of biaxial molecular orientation distributions are used to correlate the director triad dynamics and the alignment's dynamics. The tensor order parameter is used to calculate the main flow-birefringences, thus providing a direct way to verify the theoretical predictions of this paper.

  17. Graphene as a photothermal actuator for control of lipid mesophase structure.

    PubMed

    Quinn, Matthew D J; Wang, Tao; Du, Joanne D; Boyd, Ben J; Hawley, Adrian; Notley, Shannon M

    2017-01-07

    The optical density of pristine graphene is high and broad in the near infrared region of the electromagnetic spectrum positioning this material as a highly efficient photothermal agent for in vivo applications. In this study, surfactant assisted exfoliated graphene was incorporated within bulk lipid samples of varying lipid types: glyceryl monoether, glyceryl monooleate and phytantriol. The pristine graphene sheets did not disrupt the packing of the liquid crystals while being in sufficiently intimate contact to provide localized heating and induce phase transitions. The phase progressions induced through heating using NIR irradiation of the entrained graphene particles within the bulk liquid crystal were studied using SAXS and confirmed using polarized optical microscopy. Increases in apparent temperature experienced by the matrix of up to 50 °C were observed by establishing a SAXS versus bulk temperature calibration curve allowing in situ measurements. The studies demonstrate the potential for use of graphene as a photothermal actuator across a range of lipid based systems of interest in controlled drug delivery.

  18. Nonequilibrium effects in self-assembled mesophase materials: unexpected supercooling effects for cubosomes and hexosomes.

    PubMed

    Dong, Yao-Da; Tilley, Adam J; Larson, Ian; Lawrence, M Jayne; Amenitsch, Heinz; Rappolt, Michael; Hanley, Tracey; Boyd, Ben J

    2010-06-01

    Polar lipids often exhibit equilibrium liquid crystalline structures in excess water, such as the bicontinuous cubic phases (Q(II)) at low temperatures and inverse hexagonal phase (H(II)) at higher temperatures. In this study, the equilibrium and nonequilibrium phase behavior of glyceryl monooleate (GMO) and phytantriol (PHYT) systems in excess water were investigated using both continuous heating and cooling cycles, and rapid temperature changes. Evolution of the phase structure was followed using small-angle X-ray scattering (SAXS). During cooling, not only was supercooling of the liquid crystalline systems by up to 25 degrees C observed, but evidence for nonequilibrium phase structures (not present on heating; such as the gyroid cubic phase only present at low water content in equilibrium) was also apparent. The nonequilibrium phases were surprisingly stable, with return to equilibrium structure for dispersed submicrometer sized particle systems taking more than 13 h in some cases. Inhibition of phase nucleation was the key to greater supercooling effects observed for the dispersed particles compared to the bulk systems. These findings highlight the need for continued study into the nonequilibrium phase structures for these types of systems, as this may influence performance in applications such as drug delivery.

  19. Volume and porosity thermal regulation in lipid mesophases by coupling mobile ligands to soft membranes

    PubMed Central

    Parolini, Lucia; Mognetti, Bortolo M.; Kotar, Jurij; Eiser, Erika; Cicuta, Pietro; Di Michele, Lorenzo

    2015-01-01

    Short DNA linkers are increasingly being exploited for driving-specific self-assembly of Brownian objects. DNA-functionalized colloids can assemble into ordered or amorphous materials with tailored morphology. Recently, the same approach has been applied to compliant units, including emulsion droplets and lipid vesicles. The liquid structure of these substrates introduces new degrees of freedom: the tethers can diffuse and rearrange, radically changing the physics of the interactions. Unlike droplets, vesicles are extremely deformable and DNA-mediated adhesion causes significant shape adjustments. We investigate experimentally the thermal response of pairs and networks of DNA-tethered liposomes and observe two intriguing and possibly useful collective properties: negative thermal expansion and tuneable porosity of the liposome networks. A model providing a thorough understanding of this unexpected phenomenon is developed, explaining the emergent properties out of the interplay between the temperature-dependent deformability of the vesicles and the DNA-mediated adhesive forces. PMID:25565580

  20. Microstructural Studies of In-Situ Mesophase Transformation in the Fabrication of Carbon-Carbon Composites

    DTIC Science & Technology

    2005-03-01

    materials for lithium ion batteries . The principle behind the impregnation with in-situ transformation process is that a wetting molten monomer...catalyst mixture. Naphthalene was the precursor monomer, and aluminum chloride was chosen as the catalyst. Even though AlCl3 was retained in the...Distribution Stmt: Approved for public release; distribution unlimited 3.3.1. Naphthalene and Aluminum Chloride Catalyst The increase in

  1. Nanostructured Monolinolein Miniemulsions as Delivery Systems: Role of the Internal Mesophase on Cytotoxicity and Cell Internalization.

    PubMed

    Guillot, Samuel; Méducin, Fabienne; Poljak, Kristina; Malard, Virginie; Foucault-Collet, Alexandra; Serieye, Sébastien; Pichon, Chantal

    2017-03-08

    Recent advances in nanoparticle systems for improved drug delivery display a great potential for the administration of active molecules. Here, lipid miniemulsions with various internal nanostructures were loaded with the chemotherapeutic agent Paclitaxel. The goal is to assess the impact of internal structures on their efficiency. Previously the structure, the stability and the physico-chemical properties of those carriers were characterized. Modalities of action were addressed by the evaluation of their effects on the tumor cells viability, their cellular uptake by flow cytometry and confocal microscopy detection of fluorescently labeled nanostructured miniemulsions. Nanostructured miniemulsions showed variations in the cell internalization process likely due to differences in the internal structure. All paclitaxel-loaded emulsions were active reservoirs from which Paclitaxel could be released, however bicontinuous cubosomes showed the best efficiency. Considering the fact that these delivery systems can offer a new life to bioactive compounds previously abandoned due to a low aqueous solubility, these data may represent an important step towards the development of new clinical therapeutic strategies against cancers.

  2. Some aspects of the orientational order distribution of flexible chains in a diblock mesophase

    SciTech Connect

    Lorthioir, Cédric Randriamahefa, Solo

    2013-12-14

    The segmental motions of flexible chains in the lamellar structure of a strongly segregated poly(styrene)-poly(dimethylsiloxane) (PS-PDMS) diblock were investigated over a time scale of a few tens of microseconds. {sup 2}H NMR experiments were performed on the PDMS block, selectively perdeuterated. Transverse relaxation measurements show that the main part of the PDMS repeat units display anisotropic reorientational motions within the diblock lamellae and such a segmental ordering essentially results from interchain steric repulsions. {sup 2}H double quantum-based experiments evidenced a non-uniform local stretching of PDMS chains and enabled the underlying distribution of the orientational order parameter to be determined quantitatively. Besides, a fraction of the PDMS chain segments, about 14%, were found to display isotropic – or nearly isotropic – reorientations, which could be assigned to repeat units located within a thin sublayer (about 1–2 nm) at the lamellae midplane, but also deeper in the lamellae, close to folded parts of the chains. These experimental results were confronted to theoretical descriptions of opposing polymer brushes and, in particular, to the strong-stretching theory (SST) including the entropic contribution of free chain ends.

  3. Pyrolysis in the mesophase: a chemist's approach toward preparing carbon nano- and microparticles.

    PubMed

    Gherghel, Lileta; Kübel, Christian; Lieser, Günter; Räder, Hans-Joachim; Müllen, Klaus

    2002-11-06

    A mild pyrolytic method is proposed for the generation of different carbon micro- and nanoparticles that are either unprecedented or have never been reported under the present experimental conditions. A hexa-alkyl-substituted hexa-peri-hexabenzocoronene serves as a graphite-like starting compound that melts into a discotic liquid crystalline phase prior to heat-induced cross-linking and dehydrogenation. An essential feature of the process is that the liquid crystalline order persists even above 400 degrees C, i.e., during alkyl chain cleavage. The present approach bears a resemblance to carbomesophase formation during graphitization starting from pitch. The pyrolysis products are characterized by matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry, optical microscopy, selected area electron diffraction (SAED), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HRTEM).

  4. Detailed analyses of FCC decant oil as a starting feedstock for mesophase pitch

    SciTech Connect

    Mochida, I.; Korai, Y.; Hieida, T. ); Azuma, A.; Kitajima, E. )

    1991-01-01

    Four typical DOs supplied from Japanese refineries were analyzed in detail by GC, FD-MS {sup 1}H and {sup 13}C-NMR after the fractionations by column chromatography. A DO carries 30% saturate and 70% aromatic fractions. The saturate consisted principally of the straight paraffins. The aromatic fraction was separated into five substractions (AR1 - AR5) of which contents distributed rather evenly, the middle fraction (AR 3) occupying the largest of 30%. The aromatic components had consisted of aromatic rings from 2(AR1) to 4(AR4+5), of some aryl-aryl linkages and naphthenic rings being included. The lighter aromatic fraction carried more alkyl groups, enhance its solubility and elution in the column. B DO appeared heaviest among the DOs in the present study. The oils carried only 10% of the saturate and 75% of AR3-AR5 aromatic subfractions. Its saturate was of carried rather short chains and more isoparaffins. Its aromatic components had very similar aromatic units to those of A DO in the same subfraction, although the heaviest fraction of the former once contained also a small portion of 6 aromatic rings.

  5. Volume and porosity thermal regulation in lipid mesophases by coupling mobile ligands to soft membranes

    NASA Astrophysics Data System (ADS)

    Parolini, Lucia; Mognetti, Bortolo M.; Kotar, Jurij; Eiser, Erika; Cicuta, Pietro; di Michele, Lorenzo

    2015-01-01

    Short DNA linkers are increasingly being exploited for driving-specific self-assembly of Brownian objects. DNA-functionalized colloids can assemble into ordered or amorphous materials with tailored morphology. Recently, the same approach has been applied to compliant units, including emulsion droplets and lipid vesicles. The liquid structure of these substrates introduces new degrees of freedom: the tethers can diffuse and rearrange, radically changing the physics of the interactions. Unlike droplets, vesicles are extremely deformable and DNA-mediated adhesion causes significant shape adjustments. We investigate experimentally the thermal response of pairs and networks of DNA-tethered liposomes and observe two intriguing and possibly useful collective properties: negative thermal expansion and tuneable porosity of the liposome networks. A model providing a thorough understanding of this unexpected phenomenon is developed, explaining the emergent properties out of the interplay between the temperature-dependent deformability of the vesicles and the DNA-mediated adhesive forces.

  6. Probing influence of mesophasic transformation on performance of self-emulsifying system: effect of ion.

    PubMed

    Patil, Sharvil S; Venugopal, Edakkal; Bhat, Suresh; Mahadik, Kakasaheb R; Paradkar, Anant R

    2012-02-06

    Self-emulsifying systems are mixtures of oils and surfactants, ideally isotropic, sometimes including cosolvents, which emulsify under conditions of gentle agitation, similar to those which would be encountered in the gastrointestinal tract. The process of self-emulsification has remained the center of attraction for most researchers. Controlled hydration of self-emulsifying systems shows formation of an intermediate gel phase which upon rupture forms an emulsion. Current work was undertaken to understand and explore the microstructural properties of intermediate gel phase which are believed to influence the performance (droplet size) of the final formulation. The effect of additives on microstructural properties of intermediate gel phase has also been investigated. Microstructural elucidation of hydrated samples of intermediate regimes was done by using techniques such as small angle X-ray scattering, differential scanning calorimetry and rheology. Samples from intermediate regimes showed formation of local lamellar structure which swelled with hydration. In the present work, the effect of addition of salt form of naproxen (sodium and potassium) and naproxen (base) on microstructural properties of intermediate regimes was investigated. Systems containing naproxen salts formed larger droplets whereas naproxen base formed smaller ones. Microstructural properties of intermediate lamellar structures were well correlated with performance of the final formulation. The current studies indicate that by controlling the properties of intermediate regimes optimized formulations with desired performance can be tailor-made.

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

    PubMed

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

    2016-08-28

    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.

  8. Overcoming merohedral twinning in crystals of bacteriorhodopsin grown in lipidic mesophase.

    PubMed

    Borshchevskiy, Valentin; Efremov, Rouslan; Moiseeva, Ekaterina; Büldt, Georg; Gordeliy, Valentin

    2010-01-01

    Twinning is one of the most common crystal-growth defects in protein crystallography. There are neither efficient rational approaches for the growth of nontwinned protein crystals nor are there examples of systematic studies of the dependence of the twinning-ratio distribution on crystallization conditions. The description of the twinning phenomenon has been covered even less for membrane-protein crystals and is non-existent for crystals grown using lipidic phases (in meso). In the present work, possibilities for overcoming merohedral twinning are investigated for crystals of the membrane protein bacteriorhodopsin (bR) grown in meso. It is shown that traditional crystallization additives are not effective in the case of the in meso crystallization of bR. The twinning ratio was determined for 310 crystals grown under different crystallization conditions. A correlation of the twinning ratio with the growth rate of the crystals was observed. Slow growth indicated that crystals had a noticeable chance of avoiding twinning. Model calculations were performed in order to rationalize this observation. The calculations confirmed the experimental observation that most crystals consist of two twin domains and showed that under this condition small changes in the probability of twin-domain formation lead to dramatic changes in the number of nontwinned crystals, which explains why slow crystal growth results in a considerable number of nontwinned crystals.

  9. Tetrahedratic mesophases, chiral order, and helical domains induced by quadrupolar and octupolar interactions

    NASA Astrophysics Data System (ADS)

    Trojanowski, Karol; Pająk, Grzegorz; Longa, Lech; Wydro, Thomas

    2012-07-01

    We present an exhaustive account of phases and phase transitions that can be stabilized in the recently introduced generalized Lebwohl-Lasher model with quadrupolar and octupolar microscopic interactions [L. Longa, G. Pająk, and T. Wydro, Phys. Rev. EPLEEE81539-375510.1103/PhysRevE.79.040701 79, 040701(R) (2009)]. A complete mean-field analysis of the model, along with Monte Carlo simulations allows us to identify four distinct classes of the phase diagrams with a number of multicritical points where, in addition to the standard uniaxial and biaxial nematic phases, the other nematic like phases are stabilized. These involve, among the others, tetrahedratic (T), nematic tetrahedratic (NT), and chiral nematic tetrahedratic (NT*) phases of global Td, D2d, and D2 symmetry, respectively. Molecular order parameters and correlation functions in these phases are determined. We conclude with generalizations of the model that give a simple molecular interpretation of macroscopic regions with opposite optical activity (ambidextrous chirality), observed, e.g., in bent-core systems. An estimate of the helical pitch in the NT* phase is also given.

  10. Characterization of a Biomimetic Mesophase Composed of Nonionic Surfactants and an Aqueous Solvent.

    PubMed

    Adrien, V; Rayan, G; Reffay, M; Porcar, L; Maldonado, A; Ducruix, A; Urbach, W; Taulier, N

    2016-10-11

    We have investigated the physical and biomimetic properties of a sponge (L3) phase composed of pentaethylene glycol monododecyl ether (C12E5), a nonionic surfactant, an aqueous solvent, and a cosurfactant. The following cosurfactants, commonly used for solubilizing membrane proteins, were incorporated: n-octyl-β-d-glucopyranoside (β-OG), n-dodecyl-β-d-maltopyranoside (DDM), 4-cyclohexyl-1-butyl-β-d-maltoside (CYMAL-4), and 5-cyclohexyl-1-pentyl-β-d-maltoside (CYMAL-5). Partial phase diagrams of these systems were created. The L3 phase was characterized using crossed polarizers, diffusion of a fluorescent probe by fluorescence recovery after pattern photobleaching (FRAPP), and freeze fracture electron microscopy (FFEM). By varying the hydration of the phase, we were able to tune the distance between adjacent bilayers. The characteristic distance (db) of the phase was obtained from small angle scattering (SAXS/SANS) as well as from FFEM, which yielded complementary db values. These db values were neither affected by the nature of the cosurfactant nor by the addition of membrane proteins. These findings illustrate that a biomimetic surfactant sponge phase can be created in the presence of several common membrane protein-solubilizing detergents, thus making it a versatile medium for membrane protein studies.

  11. Diffusion, molecular separation, and drug delivery from lipid mesophases with tunable water channels.

    PubMed

    Negrini, Renata; Mezzenga, Raffaele

    2012-11-27

    Lyotropic liquid crystals characterized by a bicontinuous cubic phase (BCP) have a structure characterized by interpenetrated water channels following triply periodic minimal surfaces, which can be stable in excess water conditions and thus suitable in a multitude of applications. The control of the water channels size in these systems has a direct impact on their use for drug delivery, crystallization, and membrane separation processes. In this work we carry out systematic diffusion studies to show how the control on the water channel dimensions directly correlates with the release and separation performance of bicontinuous cubic phases. Specifically, we tune the water channels diameter of the monolinolein/water system by adding different amounts of sucrose stearate, which, having hydration-enhancing properties, can shift the boundaries of the phase diagram. We then design a model bicontinuous cubic phase lipidic membrane of the Im3m space group, having a sugar ester to monolinolein ratio of 20%, and we follow the diffusion within its water channels, by using molecules that differ systematically in size and molecular conformation, and we demonstrate, for each class of molecules, a diffusion-enhanced process upon increase of the water channel diameter. Finally, we also show the ability of the bicontinuous cubic phase to efficiently and selectively separate nanoparticles of a target size, by choosing an amount of sucrose stearate for which the water channel diameter and the nanoparticle dimensions match, demonstrating the possible use of these systems as filtering membranes of tunable molecular cutoff.

  12. Observation of an unprecedented body centered cubic micellar mesophase from rod-coil molecules.

    PubMed

    Lee, Eunji; Ryu, Ja-Hyoung; Park, Myoung-Hwan; Lee, Myongsoo; Han, Kyung-Hee; Chung, Yeon-Wook; Cho, Byoung-Ki

    2007-07-28

    We have demonstrated that rod-coil molecules based on a tetra-p-phenylene rod and a poly(propylene oxide) coil self-assemble into an unprecedented body centered cubic micellar structure in the melt, through detailed morphological analysis by X-ray scattering and transmission electron microscopy experiments.

  13. Biosignatures as revealed by spectropolarimetry of Earthshine.

    PubMed

    Sterzik, Michael F; Bagnulo, Stefano; Palle, Enric

    2012-02-29

    Low-resolution intensity spectra of Earth's atmosphere obtained from space reveal strong signatures of life ('biosignatures'), such as molecular oxygen and methane with abundances far from chemical equilibrium, as well as the presence of a 'red edge' (a sharp increase of albedo for wavelengths longer than 700 nm) caused by surface vegetation. Light passing through the atmosphere is strongly linearly polarized by scattering (from air molecules, aerosols and cloud particles) and by reflection (from oceans and land). Spectropolarimetric observations of local patches of Earth's sky light from the ground contain signatures of oxygen, ozone and water, and are used to characterize the properties of clouds and aerosols. When applied to exoplanets, ground-based spectropolarimetry can better constrain properties of atmospheres and surfaces than can standard intensity spectroscopy. Here we report disk-integrated linear polarization spectra of Earthshine, which is sunlight that has been first reflected by Earth and then reflected back to Earth by the Moon. The observations allow us to determine the fractional contribution of clouds and ocean surface, and are sensitive to visible areas of vegetation as small as 10 per cent. They represent a benchmark for the diagnostics of the atmospheric composition, mean cloud height and surfaces of exoplanets.

  14. The IC 342-Maffei 1 Group Revealed

    NASA Astrophysics Data System (ADS)

    McCall, M. L.; Buta, R.

    1996-12-01

    Deep wide-field CCD images of thirteen members of the IC 342-Maffei 1 Group in the Northern Milky Way have been acquired in the Johnson V and Cousins I photometric systems. The observations were obtained with the Kitt Peak Burrell-Schmidt telescope in Arizona during six nights in November 1995. Almost none of these galaxies was effectively studied in the past because of the heavy foreground extinction and significant foreground star contamination in the direction of the group. The tens of thousands of foreground stars included on the Schmidt images have been successfully subtracted using DAOPHOT, revealing the true extent and total brightness of most of the galaxies for the first time. In the absence of galactic extinction, Maffei 1, Maffei 2, and IC 342 would be among the five brightest galaxies in the northern sky, and both Maffei 1 and IC 342 would subtend angles as large as the full Moon. The results are critical for assessing the degree to which the group influenced the dynamical evolution of the Local Group. In this poster, we will present deep photographs, total magnitudes and color indices, luminosity profiles, and distance estimates for the member galaxies.

  15. Balance Trees Reveal Microbial Niche Differentiation.

    PubMed

    Morton, James T; Sanders, Jon; Quinn, Robert A; McDonald, Daniel; Gonzalez, Antonio; Vázquez-Baeza, Yoshiki; Navas-Molina, Jose A; Song, Se Jin; Metcalf, Jessica L; Hyde, Embriette R; Lladser, Manuel; Dorrestein, Pieter C; Knight, Rob

    2017-01-01

    Advances in sequencing technologies have enabled novel insights into microbial niche differentiation, from analyzing environmental samples to understanding human diseases and informing dietary studies. However, identifying the microbial taxa that differentiate these samples can be challenging. These issues stem from the compositional nature of 16S rRNA gene data (or, more generally, taxon or functional gene data); the changes in the relative abundance of one taxon influence the apparent abundances of the others. Here we acknowledge that inferring properties of individual bacteria is a difficult problem and instead introduce the concept of balances to infer meaningful properties of subcommunities, rather than properties of individual species. We show that balances can yield insights about niche differentiation across multiple microbial environments, including soil environments and lung sputum. These techniques have the potential to reshape how we carry out future ecological analyses aimed at revealing differences in relative taxonomic abundances across different samples. IMPORTANCE By explicitly accounting for the compositional nature of 16S rRNA gene data through the concept of balances, balance trees yield novel biological insights into niche differentiation. The software to perform this analysis is available under an open-source license and can be obtained at https://github.com/biocore/gneiss. Author Video: An author video summary of this article is available.

  16. Revealing the quantum regime in tunnelling plasmonics.

    PubMed

    Savage, Kevin J; Hawkeye, Matthew M; Esteban, Rubén; Borisov, Andrei G; Aizpurua, Javier; Baumberg, Jeremy J

    2012-11-22

    When two metal nanostructures are placed nanometres apart, their optically driven free electrons couple electrically across the gap. The resulting plasmons have enhanced optical fields of a specific colour tightly confined inside the gap. Many emerging nanophotonic technologies depend on the careful control of this plasmonic coupling, including optical nanoantennas for high-sensitivity chemical and biological sensors, nanoscale control of active devices, and improved photovoltaic devices. But for subnanometre gaps, coherent quantum tunnelling becomes possible and the system enters a regime of extreme non-locality in which previous classical treatments fail. Electron correlations across the gap that are driven by quantum tunnelling require a new description of non-local transport, which is crucial in nanoscale optoelectronics and single-molecule electronics. Here, by simultaneously measuring both the electrical and optical properties of two gold nanostructures with controllable subnanometre separation, we reveal the quantum regime of tunnelling plasmonics in unprecedented detail. All observed phenomena are in good agreement with recent quantum-based models of plasmonic systems, which eliminate the singularities predicted by classical theories. These findings imply that tunnelling establishes a quantum limit for plasmonic field confinement of about 10(-8)λ(3) for visible light (of wavelength λ). Our work thus prompts new theoretical and experimental investigations into quantum-domain plasmonic systems, and will affect the future of nanoplasmonic device engineering and nanoscale photochemistry.

  17. Revealing the values behind convenience food consumption.

    PubMed

    Botonaki, Anna; Mattas, Konstadinos

    2010-12-01

    The increasing importance of convenience in consumer food choices has attracted researchers' interest. In the effort to understand how convenience affects consumers' food preferences, values are believed to play an important role. The present study attempts to examine the way personal values suggested by Schwartz (1992) are associated with behaviour and attitudes regarding convenience food. A number of constructs describing food related attitudes and behaviours were developed and their relationship with personal values was analyzed following the methodology proposed by Brunsø, Scholderer, and Grunert (2004). Data were collected through a questionnaire survey from a random sample of consumers in Thessaloniki city, Greece. The results reveal that convenience food consumption and convenience orientation in the food domain are mainly connected with values that motivate people to seek new experiences, act independently and enhance their own personal interests, while are in conflict with values of conservation and self-transcendence. The opposite holds for other food related attitudes and behaviours like involvement with cooking and variety in diet. The findings seem to be of particular interest not only for marketers of food products, but also for food policy makers.

  18. VISTA Reveals the Secret of the Unicorn

    NASA Astrophysics Data System (ADS)

    2010-10-01

    A new infrared image from ESO's VISTA survey telescope reveals an extraordinary landscape of glowing tendrils of gas, dark clouds and young stars within the constellation of Monoceros (the Unicorn). This star-forming region, known as Monoceros R2, is embedded within a huge dark cloud. The region is almost completely obscured by interstellar dust when viewed in visible light, but is spectacular in the infrared. An active stellar nursery lies hidden inside a massive dark cloud rich in molecules and dust in the constellation of Monoceros. Although it appears close in the sky to the more familiar Orion Nebula it is actually almost twice as far from Earth, at a distance of about 2700 light-years. In visible light a grouping of massive hot stars creates a beautiful collection of reflection nebulae where the bluish starlight is scattered from parts of the dark, foggy outer layers of the molecular cloud. However, most of the new-born massive stars remain hidden as the thick interstellar dust strongly absorbs their ultraviolet and visible light. In this gorgeous infrared image taken from ESO's Paranal Observatory in northern Chile, the Visible and Infrared Survey Telescope for Astronomy (VISTA [1], eso0949) penetrates the dark curtain of cosmic dust and reveals in astonishing detail the folds, loops and filaments sculpted from the dusty interstellar matter by intense particle winds and the radiation emitted by hot young stars. "When I first saw this image I just said 'Wow!' I was amazed to see all the dust streamers so clearly around the Monoceros R2 cluster, as well as the jets from highly embedded young stellar objects. There is such a great wealth of exciting detail revealed in these VISTA images," says Jim Emerson, of Queen Mary, University of London and leader of the VISTA consortium. With its huge field of view, large mirror and sensitive camera, VISTA is ideal for obtaining deep, high quality infrared images of large areas of the sky, such as the Monoceros R2 region

  19. Phylogenetic proximity revealed by neurodevelopmental event timings.

    PubMed

    Nagarajan, Radhakrishnan; Clancy, Barbara

    2008-01-01

    Statistical properties such as distribution and correlation signatures were investigated using a temporal database of common neurodevelopmental events in the three species most frequently used in experimental studies, rat, mouse, and macaque. There was a fine nexus between phylogenetic proximity and empirically derived dates of the occurrences of 40 common events including the neurogenesis of cortical layers and outgrowth milestones of developing axonal projections. Exponential and power-law approximations to the distribution of the events reveal strikingly similar decay patterns in rats and mice when compared to macaques. Subsequent hierarchical clustering of the common event timings also captures phylogenetic proximity, an association further supported by multivariate linear regression data. These preliminary results suggest that statistical analyses of the timing of developmental milestones may offer a novel measure of phylogenetic classifications. This may have added pragmatic value in the specific support it offers for the reliability of rat/mouse comparative modeling, as well as in the broader implications for the potential of meta-analyses using databases assembled from the extensive empirical literature.

  20. Revealing Invisible Photonic Inscriptions: Images from Strain

    PubMed Central

    2015-01-01

    Photonic structural materials have received intensive interest and have been strongly developed over the past few years for image displays, sensing, and anticounterfeit materials. Their “smartness” arises from their color responsivity to changes of environment, strain, or external fields. Here, we introduce a novel invisible photonic system that reveals encrypted images or characters by simply stretching, or immersing in solvents. This type of intriguing photonic material is composed of regularly arranged core–shell particles that are selectively cross-linked by UV irradiation, giving different strain response compared to un-cross-linked regions. The images reversibly appear and disappear when cycling the strain and releasing it. The unique advantages of this soft polymer opal system compared with other types of photonic gels are that it can be produced in roll to roll quantities, can be vigorously deformed to achieve strong color changes, and has no solvent evaporation issues because it is a photonic rubber system. We demonstrate potential applications together with a fabrication procedure which is straightforward and scalable, vital for user take-up. Our work deepens understanding of this rubbery photonic system based on core–shell nanospheres. PMID:26039279

  1. Revealing Open Quantum Systems with Subsystem DFT

    NASA Astrophysics Data System (ADS)

    Krishtal, Alisa; Pavanello, Michele

    The traditional quantum chemical methods, wave function or density based, are designed to solve for a closed system, where the Hamiltonian contains all relevant interactions. The closed system is, however, not realistic, as in real life the system is embedded in an environment with which it interacts to some degree. Including the description of the environment at the full quantum mechanical level leads to the Open Quantum Systems (OQS) theory: the only theory which can describe non-Markovian dynamics between the system and the environment. By allowing the flow of information in both directions phenomena such as quantum entanglement, relevant for the design of quantum computers, become available. While most OQS theories rely on the density matrix to describe the system-bath interaction, time-dependent subsystem DFT allows to approach the problem using the electron density. Through Dyson-like equations connecting the density-density response kernels of the OQS and its environment, the extent to which non-Markovian dynamics is present can be revealed. We illustrate this for the process of excitation energy transfer in coupled chromophores embedded in explicit solvent.

  2. Caged Naloxone Reveals Opioid Signaling Deactivation Kinetics

    PubMed Central

    Banghart, Matthew R.; Shah, Ruchir C.; Lavis, Luke D.

    2013-01-01

    The spatiotemporal dynamics of opioid signaling in the brain remain poorly defined. Photoactivatable opioid ligands provide a means to quantitatively measure these dynamics and their underlying mechanisms in brain tissue. Although activation kinetics can be assessed using caged agonists, deactivation kinetics are obscured by slow clearance of agonist in tissue. To reveal deactivation kinetics of opioid signaling we developed a caged competitive antagonist that can be quickly photoreleased in sufficient concentrations to render agonist dissociation effectively irreversible. Carboxynitroveratryl-naloxone (CNV-NLX), a caged analog of the competitive opioid antagonist NLX, was readily synthesized from commercially available NLX in good yield and found to be devoid of antagonist activity at heterologously expressed opioid receptors. Photolysis in slices of rat locus coeruleus produced a rapid inhibition of the ionic currents evoked by multiple agonists of the μ-opioid receptor (MOR), but not of α-adrenergic receptors, which activate the same pool of ion channels. Using the high-affinity peptide agonist dermorphin, we established conditions under which light-driven deactivation rates are independent of agonist concentration and thus intrinsic to the agonist-receptor complex. Under these conditions, some MOR agonists yielded deactivation rates that are limited by G protein signaling, whereas others appeared limited by agonist dissociation. Therefore, the choice of agonist determines which feature of receptor signaling is unmasked by CNV-NLX photolysis. PMID:23960100

  3. Community structure revealed by phase locking.

    PubMed

    Zhou, Ming-Yang; Zhuo, Zhao; Cai, Shi-min; Fu, Zhongqian

    2014-09-01

    Community structure can naturally emerge in paths to synchronization, and scratching it from the paths is a tough issue that accounts for the diverse dynamics of synchronization. In this paper, with assumption that the synchronization on complex networks is made up of local and collective processes, we proposed a scheme to lock the local synchronization (phase locking) at a stable state, meanwhile, suppress the collective synchronization based on Kuramoto model. Through this scheme, the network dynamics only contains the local synchronization, which suggests that the nodes in the same community synchronize together and these synchronization clusters well reveal the community structure of network. Furthermore, by analyzing the paths to synchronization, the relations or overlaps among different communities are also obtained. Thus, the community detection based on the scheme is performed on five real networks and the observed community structures are much more apparent than modularity-based fast algorithm. Our results not only provide a deep insight to understand the synchronization dynamics on complex network but also enlarge the research scope of community detection.

  4. Sequence tagging reveals unexpected modifications in toxicoproteomics.

    PubMed

    Dasari, Surendra; Chambers, Matthew C; Codreanu, Simona G; Liebler, Daniel C; Collins, Ben C; Pennington, Stephen R; Gallagher, William M; Tabb, David L

    2011-02-18

    Toxicoproteomic samples are rich in posttranslational modifications (PTMs) of proteins. Identifying these modifications via standard database searching can incur significant performance penalties. Here, we describe the latest developments in TagRecon, an algorithm that leverages inferred sequence tags to identify modified peptides in toxicoproteomic data sets. TagRecon identifies known modifications more effectively than the MyriMatch database search engine. TagRecon outperformed state of the art software in recognizing unanticipated modifications from LTQ, Orbitrap, and QTOF data sets. We developed user-friendly software for detecting persistent mass shifts from samples. We follow a three-step strategy for detecting unanticipated PTMs in samples. First, we identify the proteins present in the sample with a standard database search. Next, identified proteins are interrogated for unexpected PTMs with a sequence tag-based search. Finally, additional evidence is gathered for the detected mass shifts with a refinement search. Application of this technology on toxicoproteomic data sets revealed unintended cross-reactions between proteins and sample processing reagents. Twenty-five proteins in rat liver showed signs of oxidative stress when exposed to potentially toxic drugs. These results demonstrate the value of mining toxicoproteomic data sets for modifications.

  5. Revealing global regulatory perturbations across human cancers

    PubMed Central

    Goodarzi, Hani; Elemento, Olivier; Tavazoie, Saeed

    2010-01-01

    Summary The discovery of pathways and regulatory networks whose perturbation contributes to neoplastic transformation remains a fundamental challenge for cancer biology. We show that such pathway perturbations, and the cis-regulatory elements through which they operate, can be efficiently extracted from global gene-expression profiles. Our approach utilizes information-theoretic analysis of expression levels, pathways, and genomic sequences. Analysis across a diverse set of human cancers reveals the majority of previously known cancer pathways. Through de novo motif discovery we associate these pathways with transcription-factor binding sites and miRNA targets, including those of E2F, NF-Y, p53, and let-7. Follow-up experiments confirmed that these predictions correspond to functional in vivo regulatory interactions. Strikingly, the majority of the perturbations, associated with putative cis-regulatory elements, fall outside of known cancer pathways. Our study provides a systems-level dissection of regulatory perturbations in cancer—an essential component of a rational strategy for therapeutic intervention and drug-target discovery. PMID:20005852

  6. Overnight lexical consolidation revealed by speech segmentation.

    PubMed

    Dumay, Nicolas; Gareth Gaskell, M

    2012-04-01

    Two experiments explored the consolidation of spoken words, and assessed whether post-sleep novel competitor effects truly reflect engagement of these novel words in competition for lexical segmentation. Two types of competitor relationships were contrasted: the onset-aligned case (such as "frenzylk"), where the novel word is a close variant of the existing word: they start at the same time point and overlap on most of their segments; and the fully embedding case (such as "lirmucktoze"), where the existing word corresponds to a smaller embedded portion of its novel competitor and is thus less noticeable. Experiment 1 (pause detection) revealed a similar performance for both cases, with no competitor effect immediately after exposure, but significant inhibition after 24 h and seven days. Experiment 2 (word spotting) produced exactly the same pattern; however, as is the case with existing word carriers (cf. McQueen, Norris, & Cutler, 1994), the inhibition was much stronger for fully embedded than for onset-aligned targets (e.g., "lirmuckt" vs. "frenzyl"). Meanwhile, explicit measures of learning, i.e., free recall and recognition, improved over time. These results cannot be explained by either consolidation of episodic traces or acquisition of new phonological/dialectal variants. We argue instead that they reflect a general trait of vocabulary learning and consolidation.

  7. Niche engineering reveals complementary resource use.

    PubMed

    Gable, Jacob T; Crowder, David W; Northfield, Tobin D; Steffan, Shawn A; Snyder, William E

    2012-09-01

    Greater resource use by diverse communities might result from species occupying complementary niches. Demonstrating niche complementarity among species is challenging, however, due to the difficulty in relating differences between species in particular traits to their use of complementary resources. Here, we overcame this obstacle by exploiting plastic foraging behavior in a community of predatory insects common on Brassica oleracea plants in Washington, USA. These predators complemented one another by partitioning foraging space, with some species foraging primarily along leaf edges and others at leaf centers. We hypothesized that emergent biodiversity effects would occur when predators partitioned foraging space on leaves, but not when spatial complementarity was dampened. Indeed, on intact leaves, edge- and center-foraging predators combined to kill more prey than any single predator species could by itself. These emergent diversity effects, however, disappeared on plants damaged by the caterpillar Plutella xylostella. Caterpillar chew-holes brought edge habitats to the center of leaves, so that all predator species could attack aphids anywhere on plants. With spatial niche differences diminished, there were no benefits of predator diversity; the most voracious single predator species killed the most aphids. Thus, caterpillar herbivory determined whether multi-predator-species effects reflected complementarity or species' individual impacts. Our study provides direct evidence for a causative relationship between niche differentiation and increased resource consumption by diverse communities, as revealed by ecological engineers that homogenize the foraging environment.

  8. Revealing the dual streams of speech processing

    PubMed Central

    Fridriksson, Julius; Yourganov, Grigori; Bonilha, Leonardo; Basilakos, Alexandra; Rorden, Christopher

    2016-01-01

    Several dual route models of human speech processing have been proposed suggesting a large-scale anatomical division between cortical regions that support motor–phonological aspects vs. lexical–semantic aspects of speech processing. However, to date, there is no complete agreement on what areas subserve each route or the nature of interactions across these routes that enables human speech processing. Relying on an extensive behavioral and neuroimaging assessment of a large sample of stroke survivors, we used a data-driven approach using principal components analysis of lesion-symptom mapping to identify brain regions crucial for performance on clusters of behavioral tasks without a priori separation into task types. Distinct anatomical boundaries were revealed between a dorsal frontoparietal stream and a ventral temporal–frontal stream associated with separate components. Collapsing over the tasks primarily supported by these streams, we characterize the dorsal stream as a form-to-articulation pathway and the ventral stream as a form-to-meaning pathway. This characterization of the division in the data reflects both the overlap between tasks supported by the two streams as well as the observation that there is a bias for phonological production tasks supported by the dorsal stream and lexical–semantic comprehension tasks supported by the ventral stream. As such, our findings show a division between two processing routes that underlie human speech processing and provide an empirical foundation for studying potential computational differences that distinguish between the two routes. PMID:27956600

  9. Feather corticosterone reveals developmental stress in seabirds.

    PubMed

    Will, Alexis P; Suzuki, Yuya; Elliott, Kyle H; Hatch, Scott A; Watanuki, Yutaka; Kitaysky, Alexander S

    2014-07-01

    In nest-bound avian offspring, food shortages typically trigger a release of the stress hormone corticosterone (CORT). Recent studies indicate that CORT is passively deposited in the tissue of growing feathers and thus may provide an integrated measure of stress incurred during development in the nest. The current hypothesis predicts that, assuming a constant rate of feather growth, elevated CORT circulating in the blood corresponds to higher levels of CORT in feather tissue, but experimental evidence for nutritionally stressed chicks is lacking. Here, we examined how food limitation affects feather CORT content in the rhinoceros auklet (Cerorhinca moncerata). We (i) used captive chicks reared on control versus restricted diets, and (ii) applied this technique to free-living chicks with unknown nutritional histories that fledged at three separate colonies. We found that (i) feather growth was not affected by experimentally induced nutritional stress; (ii) captive chicks raised on a restricted diet had higher levels of CORT in their primary feathers; (iii) feather CORT deposition is a sensitive method of detecting nutritional stress; and (iv) free-living fledglings from the colony with poor reproductive performance had higher CORT in their primary feathers. We conclude that feather CORT is a sensitive integrated measure revealing the temporal dynamics of food limitations experienced by rhinoceros auklet nestlings. The use of feather CORT may be a powerful endocrine tool in ecological and evolutionary studies of bird species with similar preferential allocation of limited resources to feather development.

  10. Balance Trees Reveal Microbial Niche Differentiation

    PubMed Central

    Morton, James T.; Sanders, Jon; Quinn, Robert A.; McDonald, Daniel; Gonzalez, Antonio; Vázquez-Baeza, Yoshiki; Navas-Molina, Jose A.; Metcalf, Jessica L.; Hyde, Embriette R.; Lladser, Manuel; Dorrestein, Pieter C.

    2017-01-01

    ABSTRACT Advances in sequencing technologies have enabled novel insights into microbial niche differentiation, from analyzing environmental samples to understanding human diseases and informing dietary studies. However, identifying the microbial taxa that differentiate these samples can be challenging. These issues stem from the compositional nature of 16S rRNA gene data (or, more generally, taxon or functional gene data); the changes in the relative abundance of one taxon influence the apparent abundances of the others. Here we acknowledge that inferring properties of individual bacteria is a difficult problem and instead introduce the concept of balances to infer meaningful properties of subcommunities, rather than properties of individual species. We show that balances can yield insights about niche differentiation across multiple microbial environments, including soil environments and lung sputum. These techniques have the potential to reshape how we carry out future ecological analyses aimed at revealing differences in relative taxonomic abundances across different samples. IMPORTANCE By explicitly accounting for the compositional nature of 16S rRNA gene data through the concept of balances, balance trees yield novel biological insights into niche differentiation. The software to perform this analysis is available under an open-source license and can be obtained at https://github.com/biocore/gneiss. Author Video: An author video summary of this article is available. PMID:28144630

  11. Radio Telescopes Reveal Unseen Galactic Cannibalism

    NASA Astrophysics Data System (ADS)

    2008-06-01

    Radio-telescope images have revealed previously-unseen galactic cannibalism -- a triggering event that leads to feeding frenzies by gigantic black holes at the cores of galaxies. Astronomers have long suspected that the extra-bright cores of spiral galaxies called Seyfert galaxies are powered by supermassive black holes consuming material. However, they could not see how the material is started on its journey toward the black hole. Optical/Radio Comparison Visible-light (left) and radio (right) image of galaxy pair: Radio image shows gas streaming between galaxies. CREDIT: Kuo et al., NRAO/AUI/NSF Click on image for more graphics. One leading theory said that Seyfert galaxies have been disturbed by close encounters with neighboring galaxies, thus stirring up their gas and bringing more of it within the gravitational reach of the black hole. However, when astronomers looked at Seyferts with visible-light telescopes, only a small fraction showed any evidence of such an encounter. Now, new images of hydrogen gas in Seyferts made using the National Science Foundation's Very Large Array (VLA) radio telescope show the majority of them are, in fact, disturbed by ongoing encounters with neighbor galaxies. "The VLA lifted the veil on what's really happening with these galaxies," said Cheng-Yu Kuo, a graduate student at the University of Virginia. "Looking at the gas in these galaxies clearly showed that they are snacking on their neighbors. This is a dramatic contrast with their appearance in visible starlight," he added. The effect of the galactic encounters is to send gas and dust toward the black hole and produce energy as the material ultimately is consumed. Black holes, concentrations of matter so dense that not even light can escape their gravitational pull, reside at the cores of many galaxies. Depending on how rapidly the black hole is eating, the galaxy can show a wide range of energetic activity. Seyfert galaxies have the mildest version of this activity, while

  12. Saturn Probe: Revealing Solar System Origins

    NASA Astrophysics Data System (ADS)

    Spilker, T. R.

    2015-12-01

    Comparative studies of the gas giant and ice giant planets are needed to reliably discriminate among competing theories of the origin and evolution of giant planets and the solar system, but we lack critical measurements. A Saturn atmospheric entry probe mission would fill a vital part of that gap, allowing comparative studies of Jupiter and Saturn, providing the basis for later comparisons with the ice giants Uranus and Neptune, and informing studies of extrasolar planetary systems now being characterized. The Galileo Probe mission provided the first in situ studies of Jupiter's atmosphere. Similar measurements at Saturn, Uranus and Neptune would provide an important comparative planetology context for the Galileo results. Cassini's "Proximal Orbits" in 2017 will reveal Saturn's internal structure to complement the Juno mission's similar measurements at Jupiter. A Saturn entry probe, complementing the Galileo Probe investigations at Jupiter, would complete a solid basis for improved understanding of both Jupiter and Saturn, an important stepping stone to understanding Uranus and Neptune and solar system formation and evolution. The 2012 Decadal Survey ("DS") added Saturn Probe science objectives to NASA's New Frontiers Program: highest-priority Tier 1 objectives any New Frontiers implementation must achieve, and Tier 2, high priority but lower than Tier 1. A DS mission concept study using extremely conservative assumptions concluded that a Saturn Probe project could fit within New Frontiers resource constraints, giving a PI confidence that they could pursue some Tier 2 objectives, customizing for the proper balance of science return, science team composition, procured or contributed instruments, etc. Contributed instruments could significantly enhance the payload and the science team for greater science return. They also provide international collaboration opportunities, with science benefits well demonstrated by missions such as Cassini-Huygens and Rosetta.

  13. Revealing atropisomer axial chirality in drug discovery.

    PubMed

    LaPlante, Steven R; Edwards, Paul J; Fader, Lee D; Jakalian, Araz; Hucke, Oliver

    2011-03-07

    An often overlooked source of chirality is atropisomerism, which results from slow rotation along a bond axis due to steric hindrance and/or electronic factors. If undetected or not managed properly, this time-dependent chirality has the potential to lead to serious consequences, because atropisomers can be present as distinct enantiomers or diastereoisomers with their attendant different properties. Herein we introduce a strategy to reveal and classify compounds that have atropisomeric chirality. Energy barriers to axial rotation were calculated using quantum mechanics, from which predicted high barriers could be experimentally validated. A calculated rotational energy barrier of 20 kcal mol(-1) was established as a suitable threshold to distinguish between atropisomers and non-atropisomers with a prediction accuracy of 86%. This methodology was applied to subsets of drug databases in the course of which atropisomeric drugs were identified. In addition, some drugs were exposed that were not yet known to have this chiral attribute. The most valuable utility of this tool will be to predict atropisomerism along the drug discovery pathway. When used in concert with our compound classification scheme, decisions can be made during early discovery stages such as "hit-to-lead" and "lead optimization," to foresee and validate the presence of atropisomers and to exercise options of removing, further stabilizing, or rendering the chiral axis of interest more freely rotatable via SAR design, thereby decreasing this potential liability within a compound series. The strategy can also improve drug development plans, such as determining whether a drug or series should be developed as a racemic mixture or as an isolated single compound. Moreover, the work described herein can be extended to other chemical fields that require the assessment of potential chiral axes.

  14. NASA's Hyperwall Revealing the Big Picture

    NASA Technical Reports Server (NTRS)

    Sellers, Piers

    2011-01-01

    NASA:s hyperwall is a sophisticated visualization tool used to display large datasets. The hyperwall, or video wall, is capable of displaying multiple high-definition data visualizations and/or images simultaneously across an arrangement of screens. Functioning as a key component at many NASA exhibits, the hyperwall is used to help explain phenomena, ideas, or examples of world change. The traveling version of the hyperwall is typically comprised of nine 42-50" flat-screen monitors arranged in a 3x3 array (as depicted below). However, it is not limited to monitor size or number; screen sizes can be as large as 52" and the arrangement of screens can include more than nine monitors. Generally, NASA satellite and model data are used to highlight particular themes in atmospheric, land, and ocean science. Many of the existing hyperwall stories reveal change across space and time, while others display large-scale still-images accompanied by descriptive, story-telling captions. Hyperwall content on a variety of Earth Science topics already exists and is made available to the public at: eospso.gsfc.nasa.gov/hyperwall. Keynote and PowerPoint presentations as well as Summary of Story files are available for download on each existing topic. New hyperwall content and accompanying files will continue being developed to promote scientific literacy across a diverse group of audience members. NASA invites the use of content accessible through this website but requests the user to acknowledge any and all data sources referenced in the content being used.

  15. Quadrupole transitions revealed by Borrmann spectroscopy.

    PubMed

    Pettifer, Robert F; Collins, Stephen P; Laundy, David

    2008-07-10

    The Borrmann effect-a dramatic increase in transparency to X-ray beams-is observed when X-rays satisfying Bragg's law diffract through a perfect crystal. The minimization of absorption seen in the Borrmann effect has been explained by noting that the electric field of the X-ray beam approaches zero amplitude at the crystal planes, thus avoiding the atoms. Here we show experimentally that under conditions of absorption suppression, the weaker electric quadrupole absorption transitions are effectively enhanced to such a degree that they can dominate the absorption spectrum. This effect can be exploited as an atomic spectroscopy technique; we show that quadrupole transitions give rise to additional structure at the L(1), L(2) and L(3) absorption edges of gadolinium in gadolinium gallium garnet, which mark the onset of excitations from 2s, 2p(1/2) and 2p(3/2) atomic core levels, respectively. Although the Borrmann effect served to underpin the development of the theory of X-ray diffraction, this is potentially the most important experimental application of the phenomenon since its first observation seven decades ago. Identifying quadrupole features in X-ray absorption spectroscopy is central to the interpretation of 'pre-edge' spectra, which are often taken to be indicators of local symmetry, valence and atomic environment. Quadrupolar absorption isolates states of different symmetries to that of the dominant dipole spectrum, and typically reveals orbitals that dominate the electronic ground-state properties of lanthanides and 3d transition metals, including magnetism. Results from our Borrmann spectroscopy technique feed into contemporary discussions regarding resonant X-ray diffraction and the nature of pre-edge lines identified by inelastic X-ray scattering. Furthermore, because the Borrmann effect has been observed in photonic materials, it seems likely that the quadrupole enhancement reported here will play an important role in modern optics.

  16. Passive seismology reveals biannual calving periodicity

    NASA Astrophysics Data System (ADS)

    Bartholomaus, T. C.; Larsen, C. F.; West, M. E.; Oneel, S.

    2013-12-01

    Iceberg calving is a large and variable component of the total mass loss from marine-terminating glaciers worldwide. However, the processes that control the size and variability of calving fluxes are poorly understood. Even more basic descriptions of iceberg calving, such as its seasonality, are uncertain. Here, we present nearly two years of automatically-estimated calving fluxes at Yahtse Glacier, a tidewater glacier whose terminus flows at ~7 km/yr towards the Gulf of Alaska. At the terminus, ice losses to calving and submarine melt total approximately 1.5 km^3/yr. In order to identify temporal variability in this mean rate, we develop a statistical model of calving size based on characteristics of calving-generated icequakes. These characteristics include 4 amplitude-based variables and 5 variables related to the shape of the icequake envelope. We build our model by combining automatically-detected icequakes (O'Neel et al., 2007) located at the terminus of Yahtse Glacier (Jones et al., 2013) with a training set of 1400 icequakes produced by visually-observed calving events (Bartholomaus et al., 2012). In each of the models tested (regression trees, multinomial logistic regression and multiple linear regession), icequake duration emerges as the single best predictor of iceberg size, consistent with past studies (Qamar, 1988; O'Neel et al., 2007). Additional predictors, such as the mean icequake amplitude and the kurtosis of the icequake envelope improve the predictive capability of the model and reduce the mean squared error to well-within the error of the in-person classification. Once validated, we apply our model to ~ 400,000 icequakes produced by calving events at Yahtse Glacier between June 2009 and September 2011. These results reveal fluctuations in calving rate at a range of timescales, including twice per year. We suggest that the roughly 50%, biannual variation in calving rate is the result of the trade-off between two competing processes at the

  17. Dramatic Outburst Reveals Nearest Black Hole

    NASA Astrophysics Data System (ADS)

    2000-01-01

    Sgr. The radio observations revealed the presence of a jet escaping from the system at mind-boggling speeds. Only three other galactic X-ray stellar systems have been found to eject material at such speeds. They have been dubbed "microquasars" because, on a smaller scale, they resemble quasars, which lie at the hearts of distant galaxies and also spew out high-velocity jets of particles. In galaxy-core quasars, the black holes are millions of times more massive than the Sun; in the more nearby microquasars the black holes are roughly three to twenty times more massive than the Sun. The extremely high velocity of the jets suggests that their origin lies close to the event horizon of a black hole. Microquasar activity is thought to arise when the black hole in the binary system draws material away from its companion star. The material surrounding the black hole forms a rapidly spinning disk called an accretion disk. This disk is heated by friction to millions of degrees, causing it to emit X-rays. As spiralling gas moves into the gravity well of the black hole, it moves faster and faster. Magnetic fields in the disk are believed to expel the charged subatomic particles at speeds close to that of light. As the charged particles interact with the magnetic fields, they emit radio waves. If some of the material escapes by being magnetically expelled into space, the matter may continue moving at the tremendous speed it had attained near the black hole. After their ejection, the jets of particles expand and cool, fading from astronomers' view. V4641 Sgr excites astronomers because it is close and because it acted so differently from other microquasars. In other microquasars, outbursts have dimmed more slowly over weeks or months rather than hours. "There's something fundamentally different about this one; it's more extreme than any other example," Hjellming said. "And because this system happens to be so close to us, `it is very likely that there are more objects like V4641

  18. Planetary Interior Structure Revealed by Spin Dynamics

    NASA Astrophysics Data System (ADS)

    Margot, J.; Peale, S. J.; Jurgens, R. F.; Slade, M. A.; Holin, I. V.

    2002-12-01

    The spin state of a planet depends on the distribution of mass within the interior, gradual and discrete changes in its moments of inertia, dissipation mechanisms at the surface and below, and external torques. Detailed measurements of the spin dynamics can therefore reveal much about planetary interior structure, interactions at the core-mantle and atmosphere-surface boundaries, and mass redistribution events. Studies of the spin precession, polar wobble, and length of day variations have been used to determine Earth's moments of inertia and rigidity and to study the effects of atmospheric angular momentum changes, post-glacial rebound, and large earthquakes. In planetary investigations the spin measurements are particularly important because other means of constraining interior properties require in-situ or orbiting sensors (e.g. seismometers, magnetometers, and Doppler tracking of spacecraft). Here we describe the successful implementation of a new Earth-based radar technique (Holin, 1992) that provides spin state measurements with unprecedented accuracy. Our first observations were designed to characterize Mercury's core. Peale (1976) showed that the measurement of four quantities (the obliquity of the planet, the amplitude of its longitude librations, and the second-degree gravitational harmonics) are sufficient to determine the size and state of Mercury's core. The existence of a molten core would place strong constraints on the thermal and rotational histories of the planet, with profound implications for the composition and rotation state of the planet at the time of formation. A solid core would have a fundamental impact on theories of planetary magnetic field generation. We observed Mercury with the Goldstone radar and the Green Bank Telescope in May-June 2002. We illuminated the planet with a monochromatic signal, recorded the scattered power at the two antennas, and cross-correlated the echoes in the time domain. We obtained strong correlations which

  19. Chemical provinces reveal Elysium Volcano's compositional evolution

    NASA Astrophysics Data System (ADS)

    Susko, D. A.; Karunatillake, S.; Wray, J. J.; Skok, J. R.; Hurowitz, J.; Ojha, L.; Judice, T.; Bently, R. O. J.

    2014-12-01

    Chemical provinces of Mars became definable[1-3] with the maps of elemental mass fractions generated with Mars Odyssey Gamma Ray Spectrometer (GRS) data[4,5]. Previous work highlighted the Elysium lava flow province as anomalous, with a depletion in K and Th relative to the average crust in the rest of Mars (ROM).[3] We characterize the elemental composition, geology, and geomorphology of the region to constrain the processes that have contributed to its evolution. We compare SE Elysium with its North West lava fields, advancing prior work on thermal evolution of the martian mantle.[6] Lava fields at both sites probably source from Elysium eruptions. Both show similar Si content, as well as a Ca-enrichment compared to ROM, consistent with prior models.[6,7] Nevertheless, the two fields are compositionally distinct from each other, with NW Elysium decisively depleted in Ca and Fe, but enriched in K and Th. Such distinctness, in elements that reflect magmatic fractionation, reveals the possibility that a single volcanic complex on Mars may evolve rapidly during the Amazonian era, causing variable flow compositions. Interestingly, a chemical province containing volcanics that is contemporaneous with Elysium, overlaps the Tharsis region.[3] Unlike Elysium, the K and Th distributions within Tharsis are indistinguishable from ROM. Meanwhile, the mass fraction signature in Tharsis is enriched in Cl and depleted in Si. Such contrast, in chemical anomalies between volcanic constructs of similar age, may indicate that the depletion of K and Th in SE Elysium did not arise from temporal evolution of the mantle. [1] Taylor, G. et al. Geology 38, 183-186, 2010 [2] Gasnault, O. et al. 207, 226-247, 2010 [3] Karunatillake, S. et al. J. Geophys. Res. 114, E12001, 2009 [4] Boynton, W. V. et al. J. Geophys. Res. 112, E12S99, 2007 [5] Feldman, W. C. et al. J. Geophys. Res. 109, E09006, 2004 [6] Baratoux, D. et al. Nature 472, 338-41, 2011 [7] Balta, J. et al. Geology 41, 1115

  20. Microradiometers Reveal Ocean Health, Climate Change

    NASA Technical Reports Server (NTRS)

    2013-01-01

    When NASA researcher Stanford Hooker is in the field, he pays close attention to color. For Hooker, being in the field means being at sea. On one such research trip to the frigid waters of the Arctic, with a Coast Guard icebreaker looming nearby and the snow-crusted ice shelf a few feet away, Hooker leaned over the edge of his small boat and lowered a tethered device into the bright turquoise water, a new product devised by a NASA partner and enabled by a promising technology for oceanographers and atmospheric scientists alike. Color is a function of light. Pure water is clear, but the variation in color observed during a visit to the beach or a flight along a coastline depends on the water s depth and the constituents in it, how far down the light penetrates and how it is absorbed and scattered by dissolved and suspended material. Hooker cares about ocean color because of what it can reveal about the health of the ocean, and in turn, the health of our planet. "The main thing we are interested in is the productivity of the water," Hooker says. The seawater contains phytoplankton, microscopic plants, which are the food base for the ocean s ecosystems. Changes in the water s properties, whether due to natural seasonal effects or human influence, can lead to problems for delicate ecosystems such as coral reefs. Ocean color can inform researchers about the quantities and distribution of phytoplankton and other materials, providing clues as to how the world ocean is changing. NASA s Coastal Zone Color Scanner, launched in 1978, was the first ocean color instrument flown on a spacecraft. Since then, the Agency s ocean color research capabilities have become increasingly sophisticated with the launch of the SeaWiFS instrument in 1997 and the twin MODIS instruments carried into orbit on NASA s Terra (1999) and Aqua (2002) satellites. The technology provides sweeping, global information on ocean color on a scale unattainable by any other means. One issue that arises from

  1. Natural history of chronic hepatitis B: what exactly has REVEAL revealed?

    PubMed

    Iloeje, Uchenna H; Yang, Hwai-I; Chen, Chien-Jen

    2012-10-01

    Chronic hepatitis B virus (HBV) infection is a serious public health problem because of its worldwide prevalence and potential to cause adverse consequences. The Risk Evaluation of Viral Load Elevation and Associated Liver Disease/Cancer-Hepatitis B Virus (REVEAL-HBV) study carried out in Taiwan was used to investigate the natural history of chronic hepatitis B. The REVEAL-HBV study has established an HBV viral load paradigm in the natural history of chronic hepatitis B (CHB). Serum HBV DNA level has been shown to be significantly and independently associated with incidence of hepatocellular carcinoma (HCC) and cirrhosis and liver-related mortality across a biological gradient. It is also a major predictor of HBsAg seroclearance. Genetic features including HBV genotype and basal core promoter A1762T/G1764A mutant, and precore G1896A mutant were documented as predictors of HCC risk. Inactive HBV carriers still had an increased risk on HCC development and liver-related mortality compared with HBsAg -seronegatives. Nomograms focusing on facilitating risk communication between patients and clinicians were developed incorporating non-invasive clinical parameters to predict long-term HCC risk. These will hopefully contribute to evidence-based decisions in the clinical management of CHB patients. A somewhat provocative and novel finding from the REVEAL-HBV study is the association of chronic HBV infection in active replication with an increased pancreatic cancer risk especially in women less than 50 years old. This finding will hopefully spur further research in this area seeking confirmatory evidence. Finally, we hope that the REVEAL-HBV study will continue to be a source of data to answer other important questions in chronic hepatitis B research going forward. © 2012 John Wiley & Sons A/S.

  2. Shocking Detail of Superstar's Activity Revealed

    NASA Astrophysics Data System (ADS)

    1999-10-01

    NASA's Chandra X-ray Observatory has imaged Eta Carinae and revealed a hot inner core around this mysterious superstar. The new X-ray observation shows three distinct structures: an outer, horseshoe shaped ring about two light years in diameter, a hot inner core about 3 light months in diameter, and a hot central source less than a light month in diameter which may contain the superstar. All three structures are thought to represent shock waves produced by matter rushing away from the superstar at supersonic speeds. The temperature of the shock-heated gas ranges from 60 million degrees Celsius in the central regions to 3 million degrees Celsius on the outer structure. An earlier image of Eta Carinae by the Hubble Space Telescope revealed two spectacular bubbles of gas expanding in opposite directions away from a central bright region at speeds in excess of a million miles per hour. The inner region visible in the Chandra image has never been resolved before, and appears to be associated with a central disk of high velocity gas rushing out at much higher speeds perpendicular to the bipolar optical nebula. "It is not what I expected," said Dr. Fred Seward of the Harvard-Smithsonian Center for Astrophysics. "I expected to see a strong point source with a little diffuse emission cloud around it. Instead, we see just the opposite- a bright cloud of diffuse emission, and much less radiation from the center." "The Chandra image contains some puzzles for existing ideas of how a star can produce such hot and intense X-rays," agreed Prof. Kris Davidson of the University of Minnesota. "In the most popular theory, X-rays are made by colliding gas streams from two stars so close together that they'd look like a point source to us. But what happens to gas streams that escape to farther distances? The extended hot stuff in the middle of the new image gives demanding new conditions for any theory to meet." Eta Carinae is one of the most enigmatic and intriguing objects in our

  3. Hubble reveals heart of Lagoon Nebula

    NASA Image and Video Library

    2017-09-27

    Image release date September 22, 2010 To view a video of this image go here: www.flickr.com/photos/gsfc/5014452203 Caption: A spectacular new NASA/ESA Hubble Space Telescope image reveals the heart of the Lagoon Nebula. Seen as a massive cloud of glowing dust and gas, bombarded by the energetic radiation of new stars, this placid name hides a dramatic reality. The Advanced Camera for Surveys (ACS) on the NASA/ESA Hubble Space Telescope has captured a dramatic view of gas and dust sculpted by intense radiation from hot young stars deep in the heart of the Lagoon Nebula (Messier 8). This spectacular object is named after the wide, lagoon-shaped dust lane that crosses the glowing gas of the nebula. This structure is prominent in wide-field images, but cannot be seen in this close-up. However the strange billowing shapes and sandy texture visible in this image make the Lagoon Nebula’s watery name eerily appropriate from this viewpoint too. Located four to five thousand light-years away, in the constellation of Sagittarius (the Archer), Messier 8 is a huge region of star birth that stretches across one hundred light-years. Clouds of hydrogen gas are slowly collapsing to form new stars, whose bright ultraviolet rays then light up the surrounding gas in a distinctive shade of red. The wispy tendrils and beach-like features of the nebula are not caused by the ebb and flow of tides, but rather by ultraviolet radiation’s ability to erode and disperse the gas and dust into the distinctive shapes that we see. In recent years astronomers probing the secrets of the Lagoon Nebula have found the first unambiguous proof that star formation by accretion of matter from the gas cloud is ongoing in this region. Young stars that are still surrounded by an accretion disc occasionally shoot out long tendrils of matter from their poles. Several examples of these jets, known as Herbig-Haro objects, have been found in this nebula in the last five years, providing strong support for

  4. Sharp Vision Reveals Intimacy of Stars

    NASA Astrophysics Data System (ADS)

    2005-11-01

    Sharp Vision Reveals Intimacy of Stars AMBER instrument on VLTI Probes Environment of Stars Using the newly installed AMBER instrument on ESO's Very Large Telescope Interferometer, which combines the light from two or three 8.2-m Unit Telescopes thereby amounting to observe with a telescope of 40 to 90 metres in diameter, two international teams of astronomers observed with unprecedented detail the environment of two stars. One is a young, still-forming star and the new results provide useful information on the conditions leading to the creation of planets. The other is on the contrary a star entering the latest stages of its life. The astronomers found, in both cases, evidence for a surrounding disc. ESO PR Photo 36a/05 ESO PR Photo 36a/05 The Young Stellar Object MWC 297 (Artist's View) [Preview - JPEG: 400 x 502 pix - 50k] [Normal - JPEG: 800 x 1004 pix - 330k] A first group of astronomers [1], led by Fabien Malbet from the Laboratoire d'Astrophysique de Grenoble, France, studied the young 10-solar mass stellar object MWC 297, which is still in the very early stage of its life [2]. "This scientific breakthrough opens the doors to an especially detailed scrutiny of the very close environment of young stars and will bring us invaluable knowledge on how planets form", says Malbet. It is amazing to see the amount of details the astronomers could achieve while observing an object located more than 800 light-years away and hidden by a large amount of gas and dust. They found the object to be surrounded by a proto-planetary disc extending to about the size of our Solar System, but truncated in his inner part until about half the distance between the Earth and the Sun. Moreover, the scientists found the object to be surrounded by an outflowing wind, the velocity of which increased by a factor 9, from about 70 km/s near the disc to 600 km/s in the polar regions [3]. "The reason why the inner part of the disc should be truncated is not clear", adds Malbet. "This raises

  5. The lower atmosphere of Pluto revealed

    NASA Astrophysics Data System (ADS)

    2009-03-01

    ), attached to ESO's Very Large Telescope, have now revealed that the atmosphere as a whole, not just the upper atmosphere, has a mean temperature of minus 180 degrees Celsius, and so it is indeed "much hotter" than the surface. In contrast to the Earth's atmosphere [2], most, if not all, of Pluto's atmosphere is thus undergoing a temperature inversion: the temperature is higher, the higher in the atmosphere you look. The change is about 3 to 15 degrees per kilometre. On Earth, under normal circumstances, the temperature decreases through the atmosphere by about 6 degrees per kilometre. "It is fascinating to think that with CRIRES we are able to precisely measure traces of a gas in an atmosphere 100 000 times more tenuous than the Earth's, on an object five times smaller than our planet and located at the edge of the Solar System," says co-author Hans-Ulrich Käufl. "The combination of CRIRES and the VLT is almost like having an advanced atmospheric research satellite orbiting Pluto." The reason why Pluto's surface is so cold is linked to the existence of Pluto's atmosphere, and is due to the sublimation of the surface ice; much like sweat cools the body as it evaporates from the surface of the skin, this sublimation has a cooling effect on the surface of Pluto. In this respect, Pluto shares some properties with comets, whose coma and tails arise from sublimating ice as they approach the Sun. The CRIRES observations also indicate that methane is the second most common gas in Pluto's atmosphere, representing half a percent of the molecules. "We were able to show that these quantities of methane play a crucial role in the heating processes in the atmosphere and can explain the elevated atmospheric temperature," says Lellouch. Two different models can explain the properties of Pluto's atmosphere. In the first, the astronomers assume that Pluto's surface is covered with a thin layer of methane, which will inhibit the sublimation of the nitrogen frost. The second scenario invokes

  6. 21 CFR 1.21 - Failure to reveal material facts.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Failure to reveal material facts. 1.21 Section 1... GENERAL ENFORCEMENT REGULATIONS General Labeling Requirements § 1.21 Failure to reveal material facts. (a) Labeling of a food, drug, device, or cosmetic shall be deemed to be misleading if it fails to reveal...

  7. 21 CFR 1.21 - Failure to reveal material facts.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Failure to reveal material facts. 1.21 Section 1... GENERAL ENFORCEMENT REGULATIONS General Labeling Requirements § 1.21 Failure to reveal material facts. (a) Labeling of a food, drug, device, or cosmetic shall be deemed to be misleading if it fails to reveal...

  8. What Facial Appearance Reveals Over Time: When Perceived Expressions in Neutral Faces Reveal Stable Emotion Dispositions

    PubMed Central

    Adams, Reginald B.; Garrido, Carlos O.; Albohn, Daniel N.; Hess, Ursula; Kleck, Robert E.

    2016-01-01

    It might seem a reasonable assumption that when we are not actively using our faces to express ourselves (i.e., when we display nonexpressive, or neutral faces), those around us will not be able to read our emotions. Herein, using a variety of expression-related ratings, we examined whether age-related changes in the face can accurately reveal one’s innermost affective dispositions. In each study, we found that expressive ratings of neutral facial displays predicted self-reported positive/negative dispositional affect, but only for elderly women, and only for positive affect. These findings meaningfully replicate and extend earlier work examining age-related emotion cues in the face of elderly women (Malatesta et al., 1987a). We discuss these findings in light of evidence that women are expected to, and do, smile more than men, and that the quality of their smiles predicts their life satisfaction. Although ratings of old male faces did not significantly predict self-reported affective dispositions, the trend was similar to that found for old female faces. A plausible explanation for this gender difference is that in the process of attenuating emotional expressions over their lifetimes, old men reveal less evidence of their total emotional experiences in their faces than do old women. PMID:27445944

  9. 21 CFR 1.21 - Failure to reveal material facts.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... to reveal facts that are: (1) Material in light of other representations made or suggested by... differences of opinion with respect to warnings (including contraindications, precautions, adverse reactions...

  10. 21 CFR 1.21 - Failure to reveal material facts.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... to reveal facts that are: (1) Material in light of other representations made or suggested by... differences of opinion with respect to warnings (including contraindications, precautions, adverse reactions...

  11. [Implantable loop recorders of the Reveal family (Medtronic)].

    PubMed

    Voss, Frederik

    2016-12-01

    This review explains the implantable loop recorders Medtronic Reveal XT and Medtronic Reveal LINQ. Technical specifications of the two devices are described in great detail. Additional tips for implantation as well as device programming are given including specific considerations of follow-up.

  12. On the correlation between the structure of lyotropic carriers and the delivery profiles of two common NSAIDs.

    PubMed

    Cohen-Avrahami, Marganit; Shames, Alexander I; Ottaviani, M Francesca; Aserin, Abraham; Garti, Nissim

    2014-10-01

    Two non-steroidal anti-inflammatory drugs (NSAIDs), sodium diclofenac (Na-DFC) and celecoxib (CLXB) were solubilized within cubic and lamellar mesophases as carriers for transdermal drug delivery. SD-NMR, SAXS, ATR-FTIR, and EPR measurements were performed to examine the systems' characteristics and the interactions between the drugs and their hosting mesophases. The amphiphilic drug Na-DFC was found to incorporate at the interfaces of the cubic and lamellar mesophases and thus to act as a cosurfactant and a "structure stabilizer". It increased the order degree and the interactions between the GMO molecules and led the systems toward denser packing. CLXB exhibits an opposite effect on the mesophases. Its solubilization within both systems is accompanied with significant channel swelling and decrease in the order degree. The hydrophobic, rigid and bulky CLXB behaves as a "structure breaker", incorporated between the GMO tails, disturbing the mesophase packing and enhancing the repulsion at the tails region, limiting their close binding. Release experiments from Franz cells revealed that Na-DFC release is dependent on the quantity of water within the hosting mesophase as the water-rich formulation exhibits 1.5-fold enhancement in the release of the drug, compared to the lamellar phase. In contrast, CLXB release was not influenced by the water quantity, hinting that the release mechanisms of the drugs are different while Na-DFC diffuses from the water channels to the external phase, CLXB diffusion occurs through the continuous lipophilic region. The difference in the solubilization sites and interactions of each drug with the mesophases affect their release profiles and determine the preferred formulations for each drug's delivery vehicle.

  13. How Costly is Hospital Quality? A Revealed-Preference Approach*

    PubMed Central

    Romley, John A.; Goldman, Dana P.

    2013-01-01

    We analyze the cost of quality improvement in hospitals, dealing with two challenges. Hospital quality is multidimensional and hard to measure, while unobserved productivity may influence quality supply. We infer the quality of hospitals in Los Angeles from patient choices. We then incorporate ‘revealed quality’ into a cost function, instrumenting with hospital demand. We find that revealed quality differentiates hospitals, but is not strongly correlated with clinical quality. Revealed quality is quite costly, and tends to increase with hospital productivity. Thus, non-clinical aspects of the hospital experience (perhaps including patient amenities) play important roles in hospital demand, competition, and costs. PMID:22299199

  14. Facial cellulitis revealing choreo-acanthocytosis: a case report.

    PubMed

    Samia, Younes; Yosra, Cherif; Foued, Bellazreg; Mouna, Aissi; Olfa, Berriche; Jihed, Souissi; Hammadi, Braham; Mahbouba, Frih-Ayed; Amel, Letaief; Habib, Sfar Mohamed

    2014-01-01

    We report a 62 year-old-man with facial cellulitis revealing choreo-acanthocytosis (ChAc). He showed chorea that started 20 years ago. The orofacial dyskinisia with tongue and cheek biting resulted in facial cellulitis. The peripheral blood smear revealed acanthocytosis of 25%. The overall of chorea, orofacial dyskinetic disorder, peripheral neuropathy, disturbed behavior, acanthocytosis and the atrophy of caudate nuclei was suggestive of a diagnosis of ChAc. To our knowledge no similar cases of facial cellulitis revealing choreo-acanthocytosis (ChAc) were found in a review of the literature.

  15. 14. DETAIL VIEW, FLUTED PILASTER AND PANELLED REVEAL IN DOORWAY ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    14. DETAIL VIEW, FLUTED PILASTER AND PANELLED REVEAL IN DOORWAY BETWEEN VESTIBULE AND STAIRHALL (NOTE WOOD GRAINING), WITH SCALE - Bowieville, 522 Church Road South, Leeland, Prince George's County, MD

  16. General view of the archaeological site showing excavation and revealing ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    General view of the archaeological site showing excavation and revealing the steps leading down into the eighteenth-century burial vault - Harry Buck House, North of Main Street (14800 Governor Oden Bowie Drive), Upper Marlboro, Prince George's County, MD

  17. Many Ignore Fire Safety at Home, Survey Reveals

    MedlinePlus

    ... medlineplus.gov/news/fullstory_162699.html Many Ignore Fire Safety at Home, Survey Reveals Holiday activities can ... dangerous time of year, but many families ignore fire and burn safety tips, a new survey finds. ...

  18. Direct sequencing of the human microbiome readily reveals community differences

    PubMed Central

    2010-01-01

    Culture-independent studies of human microbiota by direct genomic sequencing reveal quite distinct differences among communities, indicating that improved sequencing capacity can be most wisely utilized to study more samples, rather than more sequences per sample. PMID:20441597

  19. Revealing the molecular signatures of host-pathogen interactions

    PubMed Central

    2011-01-01

    Advances in sequencing technology and genome-wide association studies are now revealing the complex interactions between hosts and pathogen through genomic variation signatures, which arise from evolutionary co-existence. PMID:22011345

  20. [Deep vein thrombosis revealing myeloproliferative syndrome in two adolescents].

    PubMed

    Bertrand, A; Heissat, S; Caron, N; Viremouneix, L; Pracros, J-P; Javouhey, E; Lachaux, A; Mialou, V

    2014-05-01

    Deep vein thrombosis occurs in 30% of patients with essential thrombocythemia, but rarely at initial diagnosis. We report two pediatric patients with essential thrombocythemia revealed by atypical deep vein thrombosis. First, a 16-year-old girl presented Budd-Chiari syndrome revealed by a hemorrhagic shock. Clinical exam revealed isolated splenomegaly. A search for thrombophilia found a factor V Leiden homozygous mutation and a Jak2 mutation. Bone marrow biopsy confirmed the diagnosis of a myeloproliferative disorder. The second case, a 17-year-old girl, had a routine examination by her physician that revealed splenomegaly. Ultrasonography displayed thrombus in the splenic and portal vein. An isolated Jak2 mutation was found and a myeloproliferative disorder was confirmed by bone marrow biopsy. The diagnosis of myeloproliferative disorder was made in both patients presenting atypical venous thrombosis with a Jak2 mutation and confirmed by bone marrow biopsy. These initial presentations of myeloproliferative disorders are rare in childhood and possibly underdiagnosed.

  1. Everett Weinreb, Photographer, April 1989 FOUNDATION DETAIL REVEALED AS RESULT ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    Everett Weinreb, Photographer, April 1989 FOUNDATION DETAIL REVEALED AS RESULT OF HOUSE DEMOLITION - Irvine Ranch Agricultural Headquarters, Boyd Tenant House, Southeast of Intersection of San Diego & Santa Ana Freeways, Irvine, Orange County, CA

  2. [Eosinophilic pneumonia revealing B-cell non-Hodgkin lymphoma].

    PubMed

    Fikal, Siham; Sajiai, Hafsa; Serhane, Hind; Aitbatahar, Salma; Amro, Lamyae

    2016-01-01

    The diagnosis of eosinophilic pneumonia is rare and malignant etiology remains exceptional. Eosinophilic pneumonia etiology varies and is mainly dominated by allergic and drug causes. We report the case of a 61-year-old patient with B-cell non-Hodgkin lymphoma revealed by eosinophilic pneumonia. The diagnosis of eosinophilic pneumonia was confirmed by eosinophil count of 56% in bronchoalveolar lavage. Immunohistochemical examination of bone marrow biopsy revealed malignant Small B cells non-Hodgkin lymphoma.

  3. Revealing of HII-regions in Galaxies with Panoramic Spectroscopy

    NASA Astrophysics Data System (ADS)

    Hakopian, S. A.; Balayan, S. K.

    2016-06-01

    Observations intended to investigation and revealing of nodes of processes of nuclear and starforming activity in galaxies were performed via panoramic spectroscopy. Data obtained on Mrk 1050 revealed evidence of starforming activity also outside the central engine of high surface brightness. Two small HII-regions, being likely a part of the chain, are located in the part of the spiral branch coming from the nucleus part.

  4. Collective Molecular Motion during V-Shaped Switching in a Smectic Liquid Crystal

    NASA Astrophysics Data System (ADS)

    Park, Byoungchoo; Seomun, San-seong; Nakata, Michi; Takahashi, Masayoshi; Takanishi, Yoichi; Ishikawa, Ken; Takezoe, Hideo

    1999-03-01

    The molecular motion during V-shaped switching in a homogeneously aligned smectic C*-like liquid crystal (LC) cell has been investigated by measuring the effective optical anisotropy Δneff, apparent tilt angle θapp, switching current, and second-harmonic generation and comparing them with the simulated results based on two extreme models, i.e., random model and collective model, where molecules switch randomly and collectively, respectively. The comparison revealed that the collective switching motion of LC molecules is more reasonable than the random motion. Moreover, it was also confirmed that the observed infrared absorption anisotropy of the phenyl stretching mode due to LC molecular distributions strongly supports the collective model. From these results, it was demonstrated that LC molecules do not switch randomly but all the LC molecules rotate collectively on a cone under the driving field.

  5. Supermolecular bent configuration composed of achiral flexible liquid crystal trimers exhibiting chiral domains with opposite handedness.

    PubMed

    Sasaki, Haruna; Takanishi, Yoichi; Yamamoto, Jun; Yoshizawa, Atsushi

    2015-03-26

    Chirality's effects on physical properties of materials and how chirality arises have persisted as attractive issues in chemistry. We prepared a homologous series of achiral liquid crystal trimers in which three phenylpyrimidine units are connected via flexible heptamethylene spacers. An equimolecular mixture of a trimer with a nematic (N) phase and that with smectic A (SmA), smectic C (SmC), and smectic B phases was found to exhibit an N phase, a SmC phase, and a B4 phase composed of chiral domains with opposite handedness. The chiral characteristics of the B4 phase were confirmed by uncrossing the polarizers in opposite directions. XRD measurements reveal that both SmC and B4 phases have an interdigitated layer structure. That molecular interdigitation might form a supermolecular bent configuration that can produce saddle splay curvature to drive the B4 phase.

  6. Camelid genomes reveal evolution and adaptation to desert environments.

    PubMed

    Wu, Huiguang; Guang, Xuanmin; Al-Fageeh, Mohamed B; Cao, Junwei; Pan, Shengkai; Zhou, Huanmin; Zhang, Li; Abutarboush, Mohammed H; Xing, Yanping; Xie, Zhiyuan; Alshanqeeti, Ali S; Zhang, Yanru; Yao, Qiulin; Al-Shomrani, Badr M; Zhang, Dong; Li, Jiang; Manee, Manee M; Yang, Zili; Yang, Linfeng; Liu, Yiyi; Zhang, Jilin; Altammami, Musaad A; Wang, Shenyuan; Yu, Lili; Zhang, Wenbin; Liu, Sanyang; Ba, La; Liu, Chunxia; Yang, Xukui; Meng, Fanhua; Wang, Shaowei; Li, Lu; Li, Erli; Li, Xueqiong; Wu, Kaifeng; Zhang, Shu; Wang, Junyi; Yin, Ye; Yang, Huanming; Al-Swailem, Abdulaziz M; Wang, Jun

    2014-10-21

    Bactrian camel (Camelus bactrianus), dromedary (Camelus dromedarius) and alpaca (Vicugna pacos) are economically important livestock. Although the Bactrian camel and dromedary are large, typically arid-desert-adapted mammals, alpacas are adapted to plateaus. Here we present high-quality genome sequences of these three species. Our analysis reveals the demographic history of these species since the Tortonian Stage of the Miocene and uncovers a striking correlation between large fluctuations in population size and geological time boundaries. Comparative genomic analysis reveals complex features related to desert adaptations, including fat and water metabolism, stress responses to heat, aridity, intense ultraviolet radiation and choking dust. Transcriptomic analysis of Bactrian camels further reveals unique osmoregulation, osmoprotection and compensatory mechanisms for water reservation underpinned by high blood glucose levels. We hypothesize that these physiological mechanisms represent kidney evolutionary adaptations to the desert environment. This study advances our understanding of camelid evolution and the adaptation of camels to arid-desert environments.

  7. Revealing physical interaction networks from statistics of collective dynamics.

    PubMed

    Nitzan, Mor; Casadiego, Jose; Timme, Marc

    2017-02-01

    Revealing physical interactions in complex systems from observed collective dynamics constitutes a fundamental inverse problem in science. Current reconstruction methods require access to a system's model or dynamical data at a level of detail often not available. We exploit changes in invariant measures, in particular distributions of sampled states of the system in response to driving signals, and use compressed sensing to reveal physical interaction networks. Dynamical observations following driving suffice to infer physical connectivity even if they are temporally disordered, are acquired at large sampling intervals, and stem from different experiments. Testing various nonlinear dynamic processes emerging on artificial and real network topologies indicates high reconstruction quality for existence as well as type of interactions. These results advance our ability to reveal physical interaction networks in complex synthetic and natural systems.

  8. Activity screening of environmental metagenomic libraries reveals novel carboxylesterase families

    PubMed Central

    Popovic, Ana; Hai, Tran; Tchigvintsev, Anatoly; Hajighasemi, Mahbod; Nocek, Boguslaw; Khusnutdinova, Anna N.; Brown, Greg; Glinos, Julia; Flick, Robert; Skarina, Tatiana; Chernikova, Tatyana N.; Yim, Veronica; Brüls, Thomas; Paslier, Denis Le; Yakimov, Michail M.; Joachimiak, Andrzej; Ferrer, Manuel; Golyshina, Olga V.; Savchenko, Alexei; Golyshin, Peter N.; Yakunin, Alexander F.

    2017-01-01

    Metagenomics has made accessible an enormous reserve of global biochemical diversity. To tap into this vast resource of novel enzymes, we have screened over one million clones from metagenome DNA libraries derived from sixteen different environments for carboxylesterase activity and identified 714 positive hits. We have validated the esterase activity of 80 selected genes, which belong to 17 different protein families including unknown and cyclase-like proteins. Three metagenomic enzymes exhibited lipase activity, and seven proteins showed polyester depolymerization activity against polylactic acid and polycaprolactone. Detailed biochemical characterization of four new enzymes revealed their substrate preference, whereas their catalytic residues were identified using site-directed mutagenesis. The crystal structure of the metal-ion dependent esterase MGS0169 from the amidohydrolase superfamily revealed a novel active site with a bound unknown ligand. Thus, activity-centered metagenomics has revealed diverse enzymes and novel families of microbial carboxylesterases, whose activity could not have been predicted using bioinformatics tools. PMID:28272521

  9. Revealing physical interaction networks from statistics of collective dynamics

    PubMed Central

    Nitzan, Mor; Casadiego, Jose; Timme, Marc

    2017-01-01

    Revealing physical interactions in complex systems from observed collective dynamics constitutes a fundamental inverse problem in science. Current reconstruction methods require access to a system’s model or dynamical data at a level of detail often not available. We exploit changes in invariant measures, in particular distributions of sampled states of the system in response to driving signals, and use compressed sensing to reveal physical interaction networks. Dynamical observations following driving suffice to infer physical connectivity even if they are temporally disordered, are acquired at large sampling intervals, and stem from different experiments. Testing various nonlinear dynamic processes emerging on artificial and real network topologies indicates high reconstruction quality for existence as well as type of interactions. These results advance our ability to reveal physical interaction networks in complex synthetic and natural systems. PMID:28246630

  10. Wigner flow reveals topological order in quantum phase space dynamics.

    PubMed

    Steuernagel, Ole; Kakofengitis, Dimitris; Ritter, Georg

    2013-01-18

    The behavior of classical mechanical systems is characterized by their phase portraits, the collections of their trajectories. Heisenberg's uncertainty principle precludes the existence of sharply defined trajectories, which is why traditionally only the time evolution of wave functions is studied in quantum dynamics. These studies are quite insensitive to the underlying structure of quantum phase space dynamics. We identify the flow that is the quantum analog of classical particle flow along phase portrait lines. It reveals hidden features of quantum dynamics and extra complexity. Being constrained by conserved flow winding numbers, it also reveals fundamental topological order in quantum dynamics that has so far gone unnoticed.

  11. Primary Splenic Angiosarcoma Revealed by Bone Marrow Metastasis

    PubMed Central

    Anoun, Soumaya; Marouane, Sofia; Quessar, Asmae; Benchekroun, Said

    2014-01-01

    Primary splenic angiosarcomas are the most common malignant non-hematopoietic tumors of the spleen. Metastatic diseases were found in 69% of patients in a reported series but the incidence of bone marrow involvement is unclear. We report a rare case of a 25-years-old Moroccan woman with unsuspected primary splenic angiosarcoma revealed by bone marrow metastasis. She presented with serious anemia and splenomegaly. Bone marrow biopsy revealed proliferating spindle cells. Computed tomography scanning showed an enlarged spleen with heterogeneous lesions. Splenectomy was performed and retrospective histological study of the spleen confirmed the diagnosis. She died 1 year after splenectomy. PMID:25541659

  12. Primary splenic angiosarcoma revealed by bone marrow metastasis.

    PubMed

    Anoun, Soumaya; Marouane, Sofia; Quessar, Asmae; Benchekroun, Said

    2014-12-05

    Primary splenic angiosarcomas are the most common malignant non-hematopoietic tumors of the spleen. Metastatic diseases were found in 69% of patients in a reported series but the incidence of bone marrow involvement is unclear. We report a rare case of a 25-years-old Moroccan woman with unsuspected primary splenic angiosarcoma revealed by bone marrow metastasis. She presented with serious anemia and splenomegaly. Bone marrow biopsy revealed proliferating spindle cells. Computed tomography scanning showed an enlarged spleen with heterogeneous lesions. Splenectomy was performed and retrospective histological study of the spleen confirmed the diagnosis. She died 1 year after splenectomy.

  13. Natural Disasters that Reveal Cracks in Our Social Foundation

    ERIC Educational Resources Information Center

    Langer, Nieli

    2004-01-01

    The recent deaths of more than 13,000 French elderly in the European heat wave of 2003 revealed cracks in the social foundation of urban communities, here and abroad. The breakdown occurred in community services, neighborhood networks, and governmental agencies that were responsible for warning of impending dangers to at-risk elderly. This paper…

  14. Adaptation to High Ethanol Reveals Complex Evolutionary Pathways

    PubMed Central

    Das, Anupam; Espinosa-Cantú, Adriana; De Maeyer, Dries; Arslan, Ahmed; Van Pee, Michiel; van der Zande, Elisa; Meert, Wim; Yang, Yudi; Zhu, Bo; Marchal, Kathleen; DeLuna, Alexander; Van Noort, Vera; Jelier, Rob; Verstrepen, Kevin J.

    2015-01-01

    Tolerance to high levels of ethanol is an ecologically and industrially relevant phenotype of microbes, but the molecular mechanisms underlying this complex trait remain largely unknown. Here, we use long-term experimental evolution of isogenic yeast populations of different initial ploidy to study adaptation to increasing levels of ethanol. Whole-genome sequencing of more than 30 evolved populations and over 100 adapted clones isolated throughout this two-year evolution experiment revealed how a complex interplay of de novo single nucleotide mutations, copy number variation, ploidy changes, mutator phenotypes, and clonal interference led to a significant increase in ethanol tolerance. Although the specific mutations differ between different evolved lineages, application of a novel computational pipeline, PheNetic, revealed that many mutations target functional modules involved in stress response, cell cycle regulation, DNA repair and respiration. Measuring the fitness effects of selected mutations introduced in non-evolved ethanol-sensitive cells revealed several adaptive mutations that had previously not been implicated in ethanol tolerance, including mutations in PRT1, VPS70 and MEX67. Interestingly, variation in VPS70 was recently identified as a QTL for ethanol tolerance in an industrial bio-ethanol strain. Taken together, our results show how, in contrast to adaptation to some other stresses, adaptation to a continuous complex and severe stress involves interplay of different evolutionary mechanisms. In addition, our study reveals functional modules involved in ethanol resistance and identifies several mutations that could help to improve the ethanol tolerance of industrial yeasts. PMID:26545090

  15. Thrombotic Microangiopathy Revealing Bone Metastases from an Ethmoid Sinus Carcinoma

    PubMed Central

    Morisse, Mony Chenda; Kontar, Loay; Bihan, Céline; Boone, Mathieu; Lachaier, Emma; Titeca-Beauport, Dimitri; Maizel, Julien; Chauffert, Bruno

    2016-01-01

    Cancer-related thrombotic microangiopathy (TMA) is a rare entity whose clinical and biological characteristics have been described in various tumors. Here we describe the first case of cancer-related TMA revealing diffuse bone metastases from an ethmoid sinus carcinoma. PMID:27721770

  16. Stroke and pituitary apoplexy revealing an internal carotid artery dissection.

    PubMed

    Cho, Tae-Hee; Rheims, Sylvain; Ritzenthaler, Thomas; Berthezene, Yves; Nighoghossian, Norbert

    2014-01-01

    A 40-year-old hypertensive woman experienced a left hemispheric stroke revealing an acute pituitary apoplexy and a dissection limited to the lacerum segment of the left internal carotid artery. The relationship between pituitary apoplexy and arterial dissection is discussed. Copyright © 2014 National Stroke Association. Published by Elsevier Inc. All rights reserved.

  17. Fundamental Patterns Underlying Neurotoxicity Revealed by DNA Microarray Expression Profiling

    DTIC Science & Technology

    2004-09-01

    microarray analysis of the dopaminergic cell line, SN4741 , revealed induction of stress indices following MPP* treatment (Chun et al., 2001). To...response to a wide range of cellular stresses including oxidative insult of the nigral dopaminergic cell line SN4741 with hydrogen peroxide or MPP* (Salinas

  18. Long-term satellite record reveals likely recent aerosol trend.

    PubMed

    Mishchenko, Michael I; Geogdzhayev, Igor V; Rossow, William B; Cairns, Brian; Carlson, Barbara E; Lacis, Andrew A; Liu, Li; Travis, Larry D

    2007-03-16

    Analysis of the long-term Global Aerosol Climatology Project data set reveals a likely decrease of the global optical thickness of tropospheric aerosols by as much as 0.03 during the period from 1991 to 2005. This recent trend mirrors the concurrent global increase in solar radiation fluxes at Earth's surface and may have contributed to recent changes in surface climate.

  19. Integrated genomics of Mucorales reveals novel therapeutic targets

    USDA-ARS?s Scientific Manuscript database

    Mucormycosis is a life-threatening infection caused by Mucorales fungi. We sequenced 30 fungal genomes and performed transcriptomics with three representative Rhizopus and Mucor strains with human airway epithelial cells during fungal invasion to reveal key host and fungal determinants contributing ...

  20. [Two cases of severe pruritus revealing Hodgkin's disease in children].

    PubMed

    Amy de la Bretèque, M; Bilan, P; Galesowski, A; Chevallier, B; Drouot, D; Sigal, M-L; Mahé, E

    2014-12-01

    Pruritus in children is a frequent reason for consultation, most often related to a common dermatosis. Where dermatological investigation fails to reveal a dermatological cause, a general cause may be suspected. We report three cases of pruritus revealing Hodgkin's lymphoma in children. Case 1: a 14-year-old girl presented pruritus with diffuse scratching lesions present for 6 months, associated with right cervical lymph nodes occurring after the onset of pruritus. Tomodensitometry revealed involvement of the supra- and sub-diaphragmatic lymph nodes as well as pulmonary involvement. Lymph node biopsy confirmed nodular sclerosing Hodgkin's lymphoma. Case 2: a 14-year-old boy was hospitalized for suspected psychogenic pruritus. He presented intense itching, predominantly in the lower extremities and at night, occurring over the previous 6 months as well as night sweats. Examination showed that the patient had lost 5kg in 1 month and had a low-grade fever of 38°C; he presented linear striated scratching lesions on both legs. Cervical and inguinal lymphadenopathy was seen. The chest scan also revealed supra-diaphragmatic adenomegalies. The biopsy confirmed Hodgkin's lymphoma. Systemic causes of pruritus in children are poorly described in the literature. In these two cases, pruritus allowed a diagnosis of Hodgkin's lymphoma to be made, emphasizing the important role of dermatologists in the early diagnosis of haematological malignancy. Copyright © 2014. Published by Elsevier Masson SAS.

  1. When Values and Behaviors Conflict: Immigrant BSW Students' Experiences Revealed

    ERIC Educational Resources Information Center

    Calderwood, Kimberly; Harper, Kim; Ball, Kellie; Liang, David

    2009-01-01

    This qualitative study reveals the discomfort seven immigrant bachelor of social work students reported experiencing when the behaviors expected of them as Canadian social workers conflicted with their fundamental family values. Behaviorally, participants had assimilated to Canadian and to social work cultures; however, the values they held from…

  2. Experimentally implementable criteria revealing substructures of genuine multipartite entanglement

    SciTech Connect

    Huber, Marcus; Schimpf, Hans; Gabriel, Andreas; Spengler, Christoph; Bruss, Dagmar; Hiesmayr, Beatrix C.

    2011-02-15

    We present a general framework that reveals substructures of genuine multipartite entanglement. Via simple inequalities it is possible to discriminate different sets of multipartite qubit states. These inequalities are beneficial regarding experimental examinations as only local measurements are required. Furthermore, the number of observables scales favorably with system size. In exemplary cases we demonstrate the noise resistance and discuss implementations.

  3. Puzzles in modern biology. I. Male sterility, failure reveals design

    PubMed Central

    Frank, Steven A.

    2016-01-01

    Many human males produce dysfunctional sperm. Various plants frequently abort pollen. Hybrid matings often produce sterile males. Widespread male sterility is puzzling. Natural selection prunes reproductive failure. Puzzling failure implies something that we do not understand about how organisms are designed. Solving the puzzle reveals the hidden processes of design. PMID:28004842

  4. Chemical milling solution reveals stress corrosion cracks in titanium alloy

    NASA Technical Reports Server (NTRS)

    Braski, D. N.

    1967-01-01

    Solution of hydrogen flouride, hydrogen peroxide, and water reveals hot salt stress corrosion cracks in various titanium alloys. After the surface is rinsed in water, dried, and swabbed with the solution, it can be observed by the naked eye or at low magnification.

  5. Paraneoplastic opsoclonus-myoclonus-ataxia syndrome revealing dual malignancy.

    PubMed

    Nasri, A; Kacem, I; Jerdak, F; Djebara, M Ben; Mejri, N; Sidhom, Y; Gargouri, A; Gouider, Riadh

    2016-10-01

    Dual malignancy has been rarely associated to paraneoplastic syndromes. We describe an unusual case of metachronous small cell lung carcinoma revealed by opsoclonus-myoclonus ataxia syndrome in a 69-year-old patient with known prostate adenocarcinoma, with positive anti-Hu and anti-Yo antibodies and good responsiveness to corticosteroids and chemotherapy.

  6. [Elbow abscess revealing cat-scratch disease: about a case].

    PubMed

    Nkaoui, Mustafa; El Bardouni, Ahmed; Lazrek, Omar; Ibo, Nasser; Zouaidia, Fouad; Kharmaz, Mohamed; Elouadghiri, Mohamed; Lamrani, Omar; Mahfoud, Mustapha; Berrada, Mohamed Saleh

    2017-01-01

    Cat-scratch disease (CSD) is a common cause of chronic benign lymphadenopathy in the child and the young adult. Bartonella henselae is the agent responsible for this disease. Common symptoms include regional lymphadenopathy associated with fever. We report a clinically atypical and potentially misleading case of a 18-year old girl with CSD revealed by elbow abscess.

  7. Puzzles in modern biology. I. Male sterility, failure reveals design.

    PubMed

    Frank, Steven A

    2016-01-01

    Many human males produce dysfunctional sperm. Various plants frequently abort pollen. Hybrid matings often produce sterile males. Widespread male sterility is puzzling. Natural selection prunes reproductive failure. Puzzling failure implies something that we do not understand about how organisms are designed. Solving the puzzle reveals the hidden processes of design.

  8. Nilaja Sun's "No Child"...: Revealing Teaching and Learning through Theater

    ERIC Educational Resources Information Center

    Hetland, Lois

    2009-01-01

    This article presents an analysis of Nilaja Sun's one-woman play, "No Child" . . ., that applies the Studio Habits of Mind framework to reveal essential features of great teaching artistry and great teaching. The play conveys much about twenty-first century schools and the policies that control them; about respect, equity, justice, and the lack of…

  9. 24. Demolitin of Pier G reveals the center bays at ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    24. Demolitin of Pier G reveals the center bays at the track well in transverse section. Note structural system of first, second, and third floors, as well as the monitor roof. - Lehigh Valley Railroad, Pier G, Jersey City, Hudson County, NJ

  10. Perspective view. Fivestory reinforced concrete factory building reveals the structural ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    Perspective view. Five-story reinforced concrete factory building reveals the structural frame on the exterior of the facade. Twelve bay facade facing onto Clay Avenue (north facade) has first floor openings bricked up. Mix of typical factory windows and glass block windows fill the majority of the openings on the rest of building - Russell Industrial Center, 1600 Clay Avenue, Detroit, MI

  11. The Basics of How to Reveal Epilepsy--Part Two

    ERIC Educational Resources Information Center

    Mittan, Robert J.

    2009-01-01

    In the April 2009 edition of "Exceptional Parent," Part One of this series explored why, for their own emotional well-being, it is so important for parents to tell others about their or their child's epilepsy. This month's installment will discuss the basics of how to reveal epilepsy to others, including some additional advantages one receives in…

  12. Detail of south granite pier revealing riveted truss ends and ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    Detail of south granite pier revealing riveted truss ends and iron footing plates on top of granite cap stones. View north - New York, New Haven & Hartford Railroad, Fort Point Channel Rolling Lift Bridge, Spanning Fort Point Channel, Boston, Suffolk County, MA

  13. Carbohydrate active enzymes revealed in Coptotermes formosanus transcriptome

    USDA-ARS?s Scientific Manuscript database

    A normalized cDNA library of Coptotermes formosanus was constructed using mixed RNA isolated from workers, soldiers, nymphs and alates of both sexes. Sequencing of this library generated 131,637 EST and 25,939 unigenes were assembled. Carbohydrate active enzymes (CAZymes) revealed in this library we...

  14. Revealing the Effects of Cognitive Education Programmes through Dynamic Assessment

    ERIC Educational Resources Information Center

    Tzuriel, David

    2011-01-01

    The major objective of this paper is to demonstrate the effectiveness of dynamic assessment (DA) in revealing outcomes of cognitive education programmes. Three programmes based on "mediated learning experience" theory are reviewed: "Feuerstein's Instrumental Enrichment", "Bright Start", and "Peer Mediation with…

  15. When Values and Behaviors Conflict: Immigrant BSW Students' Experiences Revealed

    ERIC Educational Resources Information Center

    Calderwood, Kimberly; Harper, Kim; Ball, Kellie; Liang, David

    2009-01-01

    This qualitative study reveals the discomfort seven immigrant bachelor of social work students reported experiencing when the behaviors expected of them as Canadian social workers conflicted with their fundamental family values. Behaviorally, participants had assimilated to Canadian and to social work cultures; however, the values they held from…

  16. The Basics of How to Reveal Epilepsy--Part Two

    ERIC Educational Resources Information Center

    Mittan, Robert J.

    2009-01-01

    In the April 2009 edition of "Exceptional Parent," Part One of this series explored why, for their own emotional well-being, it is so important for parents to tell others about their or their child's epilepsy. This month's installment will discuss the basics of how to reveal epilepsy to others, including some additional advantages one receives in…

  17. Natural Disasters that Reveal Cracks in Our Social Foundation

    ERIC Educational Resources Information Center

    Langer, Nieli

    2004-01-01

    The recent deaths of more than 13,000 French elderly in the European heat wave of 2003 revealed cracks in the social foundation of urban communities, here and abroad. The breakdown occurred in community services, neighborhood networks, and governmental agencies that were responsible for warning of impending dangers to at-risk elderly. This paper…

  18. Cassini Flybys Reveal Details About Titan Seas and Lakes

    NASA Astrophysics Data System (ADS)

    Showstack, Randy

    2013-12-01

    The Cassini spacecraft's flybys of Saturn's moon Titan reveal new details about the sizes, depths, and locations of the seas and lakes, whose liquid is mostly methane, that dot the moon's northern hemisphere, according to findings presented by scientists at a 12 December news briefing at the AGU Fall Meeting in San Francisco, Calif.

  19. Effect of processing pressure on the properties of graphite foam

    NASA Astrophysics Data System (ADS)

    Shah, Raviraj; Soni, Neha; Shrivastava, R.

    2013-06-01

    Graphite foam samples were prepared by heating mesophase pitch at different processing pressures followed by carbonization and graphitization under inert atmosphere. These samples were characterized for density, surface morphology and thermal conductivity. Microstructure of the samples indicate that processing pressure controls the evolution of volatiles from mesophase pitch to create a structure having optimum pore size, ligament thickness and junctions, which all are responsible for physical and thermal properties of resultant graphite foam. The study reveals that there is a relationship between processing pressure and the final density & thermal conductivity.

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

    PubMed

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

    2014-03-26

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

  1. Direct visualization reveals kinetics of meiotic chromosome synapsis

    SciTech Connect

    Rog, Ofer; Dernburg, Abby  F.

    2015-03-17

    The synaptonemal complex (SC) is a conserved protein complex that stabilizes interactions along homologous chromosomes (homologs) during meiosis. The SC regulates genetic exchanges between homologs, thereby enabling reductional division and the production of haploid gametes. Here, we directly observe SC assembly (synapsis) by optimizing methods for long-term fluorescence recording in C. elegans. We report that synapsis initiates independently on each chromosome pair at or near pairing centers—specialized regions required for homolog associations. Once initiated, the SC extends rapidly and mostly irreversibly to chromosome ends. Quantitation of SC initiation frequencies and extension rates reveals that initiation is a rate-limiting step in homolog interactions. Eliminating the dynein-driven chromosome movements that accompany synapsis severely retards SC extension, revealing a new role for these conserved motions. This work provides the first opportunity to directly observe and quantify key aspects of meiotic chromosome interactions and will enable future in vivo analysis of germline processes.

  2. Maps of random walks on complex networks reveal community structure.

    PubMed

    Rosvall, Martin; Bergstrom, Carl T

    2008-01-29

    To comprehend the multipartite organization of large-scale biological and social systems, we introduce an information theoretic approach that reveals community structure in weighted and directed networks. We use the probability flow of random walks on a network as a proxy for information flows in the real system and decompose the network into modules by compressing a description of the probability flow. The result is a map that both simplifies and highlights the regularities in the structure and their relationships. We illustrate the method by making a map of scientific communication as captured in the citation patterns of >6,000 journals. We discover a multicentric organization with fields that vary dramatically in size and degree of integration into the network of science. Along the backbone of the network-including physics, chemistry, molecular biology, and medicine-information flows bidirectionally, but the map reveals a directional pattern of citation from the applied fields to the basic sciences.

  3. Sequencing of Seven Haloarchaeal Genomes Reveals Patterns of Genomic Flux

    PubMed Central

    Lynch, Erin A.; Langille, Morgan G. I.; Darling, Aaron; Wilbanks, Elizabeth G.; Haltiner, Caitlin; Shao, Katie S. Y.; Starr, Michael O.; Teiling, Clotilde; Harkins, Timothy T.; Edwards, Robert A.; Eisen, Jonathan A.; Facciotti, Marc T.

    2012-01-01

    We report the sequencing of seven genomes from two haloarchaeal genera, Haloferax and Haloarcula. Ease of cultivation and the existence of well-developed genetic and biochemical tools for several diverse haloarchaeal species make haloarchaea a model group for the study of archaeal biology. The unique physiological properties of these organisms also make them good candidates for novel enzyme discovery for biotechnological applications. Seven genomes were sequenced to ∼20×coverage and assembled to an average of 50 contigs (range 5 scaffolds - 168 contigs). Comparisons of protein-coding gene compliments revealed large-scale differences in COG functional group enrichment between these genera. Analysis of genes encoding machinery for DNA metabolism reveals genera-specific expansions of the general transcription factor TATA binding protein as well as a history of extensive duplication and horizontal transfer of the proliferating cell nuclear antigen. Insights gained from this study emphasize the importance of haloarchaea for investigation of archaeal biology. PMID:22848480

  4. Revealing how network structure affects accuracy of link prediction

    NASA Astrophysics Data System (ADS)

    Yang, Jin-Xuan; Zhang, Xiao-Dong

    2017-08-01

    Link prediction plays an important role in network reconstruction and network evolution. The network structure affects the accuracy of link prediction, which is an interesting problem. In this paper we use common neighbors and the Gini coefficient to reveal the relation between them, which can provide a good reference for the choice of a suitable link prediction algorithm according to the network structure. Moreover, the statistical analysis reveals correlation between the common neighbors index, Gini coefficient index and other indices to describe the network structure, such as Laplacian eigenvalues, clustering coefficient, degree heterogeneity, and assortativity of network. Furthermore, a new method to predict missing links is proposed. The experimental results show that the proposed algorithm yields better prediction accuracy and robustness to the network structure than existing currently used methods for a variety of real-world networks.

  5. Drosophila models reveal novel insights into mechanisms underlying neurodegeneration

    PubMed Central

    Mohan, Ryan D; Workman, Jerry L; Abmayr, Susan M

    2014-01-01

    The SAGA chromatin modifying complex functions as a transcriptional coactivator for a large number of genes, and SAGA dysfunction has been linked to carcinogenesis and neurodegenerative disease. The protein complex is comprised of approximately 20 subunits, arranged in a modular fashion, and includes 2 enzymatic subunits: the Gcn5 acetyltransferase and the Non-stop deubiquitinase. As we learn more about SAGA, it becomes evident that this complex functions through sophisticated mechanisms that support very precise regulation of gene expression. Here we describe recent findings in which a Drosophila loss-of-function model revealed novel mechanisms for regulation of SAGA-mediated histone H2B deubiquitination. This model also yielded novel and surprising insights into mechanisms that underlie progressive neurodegenerative disease. Lastly, we comment on the utility of Drosophila as a model for neurodegenerative disease through which crucial and conserved mechanisms may be revealed. PMID:25483136

  6. Obscure pulmonary masses: bronchial impaction revealed by CT

    SciTech Connect

    Pugatch, R.D.; Gale, M.E.

    1983-11-01

    Dilated bronchi impacted with mucus or tumor are recognized on standard chest radiographs because they are surrounded by aerated pulmonary parenchyma. When imaged in different projections, these lesions produce a variety of appearances that are generally familiar. This report characterizes less familiar computed tomographic (CT) findings in eight patients with pathologic bronchial distension of congenital, neoplastic, or infectious etiologies and correlates them with chest films. In seven patients, CT readily revealed dilated bronchi and/or regional lung hypodensity. In four of these cases, CT led to the initial suspicion of dilated bronchi. CT should be used early in the evaluation of atypical pulmonary mass lesions or to confirm suspected bronchial impaction because of the high probability it will reveal diagnostic features.

  7. Mitogenome revealed multiple postdomestication genetic mixtures of West African sheep.

    PubMed

    Brahi, O H D; Xiang, H; Chen, X; Farougou, S; Zhao, X

    2015-10-01

    Notable diversity observed within African ovine breeds makes them of great interests, but limited studies on genetic origins and domestications remain poorly understood. Here, we investigate the evolutionary status of West African native breeds, Djallonke and Sahelian sheep using mitogenome sequencing. Compared with other ovine mitogenome sequences, West African sheep were revealed a Eurasian origin, and the initially tamed sheep breeds in West Africa have been genetically mixed with each other and mixed with European breeds. Worldwide domestic sheep is deemed the Eurasian origin and migrated west to Europe and Africa and east to the Far East, in which dispersed and received selection for acclimation to autochthonic environment independently and ultimately evolved into different native breeds, respectively. Our results contribute to the comprehensive understanding of the domestic sheep origin and reveal multiple postdomestication genetic amelioration processes.

  8. Intracranial hemorrhage revealing pseudohypoparathyroidism as a cause of fahr syndrome.

    PubMed

    Swami, Abhijit; Kar, Giridhari

    2011-01-01

    Pseudohypoparathyroidism is an infrequently encountered disease. It is one of the causes of Fahr syndrome which also is a rare clinical entity caused by multiple diseases. A 4-year-old man hospitalized for sudden onset left hemiparesis and hypertension was diagnosed to have right thalamic and midbrain hemorrhage on plain CT scan of the head which also revealed co-existent extensive intracranial calcifications involving the basal ganglia and cerebellum bilaterally. General physical examination revealed features of Albright hereditary osteodystrophy, goitre, hypertension, left hemiparesis, and signs of cerebellar dysfunction. Laboratory findings suggested hypocalcemia, hyperphosphatemia along with high TSH, low FT(4), low FT(3), and high anti-TPO antibody. Though bilateral intracranial calcifications are usually encountered as an incidental radiological finding in the CT scan of brain, in this case, the patient admitted for thalamic and midbrain hemorrhage was on investigation for associated intracranial calcification, and goitre was also found to have coexisting pseudohypoparathyroidism and autoimmune hypothyroidism.

  9. Intracranial Hemorrhage Revealing Pseudohypoparathyroidism as a Cause of Fahr Syndrome

    PubMed Central

    Swami, Abhijit; Kar, Giridhari

    2011-01-01

    Pseudohypoparathyroidism is an infrequently encountered disease. It is one of the causes of Fahr syndrome which also is a rare clinical entity caused by multiple diseases. A 4-year-old man hospitalized for sudden onset left hemiparesis and hypertension was diagnosed to have right thalamic and midbrain hemorrhage on plain CT scan of the head which also revealed co-existent extensive intracranial calcifications involving the basal ganglia and cerebellum bilaterally. General physical examination revealed features of Albright hereditary osteodystrophy, goitre, hypertension, left hemiparesis, and signs of cerebellar dysfunction. Laboratory findings suggested hypocalcemia, hyperphosphatemia along with high TSH, low FT4, low FT3, and high anti-TPO antibody. Though bilateral intracranial calcifications are usually encountered as an incidental radiological finding in the CT scan of brain, in this case, the patient admitted for thalamic and midbrain hemorrhage was on investigation for associated intracranial calcification, and goitre was also found to have coexisting pseudohypoparathyroidism and autoimmune hypothyroidism. PMID:22937338

  10. Acting without seeing: eye movements reveal visual processing without awareness.

    PubMed

    Spering, Miriam; Carrasco, Marisa

    2015-04-01

    Visual perception and eye movements are considered to be tightly linked. Diverse fields, ranging from developmental psychology to computer science, utilize eye tracking to measure visual perception. However, this prevailing view has been challenged by recent behavioral studies. Here, we review converging evidence revealing dissociations between the contents of perceptual awareness and different types of eye movement. Such dissociations reveal situations in which eye movements are sensitive to particular visual features that fail to modulate perceptual reports. We also discuss neurophysiological, neuroimaging, and clinical studies supporting the role of subcortical pathways for visual processing without awareness. Our review links awareness to perceptual-eye movement dissociations and furthers our understanding of the brain pathways underlying vision and movement with and without awareness.

  11. Benign Cystic Peritoneal Mesothelioma Revealed by Small Bowel Obstruction

    PubMed Central

    Bray Madoué, Kaimba; Boniface, Moifo; Annick Laure, Edzimbi; Pierre, Herve

    2016-01-01

    Benign cystic peritoneal mesothelioma is a rare tumor which frequently occurs in women of reproductive age. Abdominal pain associated with pelvic or abdominal mass is the common clinical presentation. We report the case of a 22-year-old woman with a pathological proved benign cystic mesothelioma of the peritoneum revealed by a small bowel obstruction and a painful left-sided pelvic mass with signs of psoitis. Contrast enhanced abdominal CT-scan demonstrated a large pelvic cystic mass with mass effect on rectosigmoid and pelvic organs. The patient underwent surgical removal of the tumor. Pathological examination revealed the diagnosis of benign cystic mesothelioma of the peritoneum. The outcome was excellent with a 12-month recoil. PMID:27066288

  12. Revealing topological superconductivity in extended quantum spin Hall Josephson junctions.

    PubMed

    Lee, Shu-Ping; Michaeli, Karen; Alicea, Jason; Yacoby, Amir

    2014-11-07

    Quantum spin Hall-superconductor hybrids are promising sources of topological superconductivity and Majorana modes, particularly given recent progress on HgTe and InAs/GaSb. We propose a new method of revealing topological superconductivity in extended quantum spin Hall Josephson junctions supporting "fractional Josephson currents." Specifically, we show that as one threads magnetic flux between the superconductors, the critical current traces an interference pattern featuring sharp fingerprints of topological superconductivity-even when noise spoils parity conservation.

  13. [Late pneumomediastinum revealed by acute pulmonary edema in hemodialysis].

    PubMed

    El Amrani, Mohamed; El Kabbaj, Driss; Benyahia, Mohammed

    2014-04-01

    Central venous catheterization occupies an important place in the treatment of end stage renal disease pending the creation of an arteriovenous fistula. However, this procedure is not devoid of complications. We report a case of late pneumomediastinum revealed by an acute pulmonary edema in a young patient on hemodialysis, and we discuss its characteristics. Copyright © 2014 Association Société de néphrologie. Published by Elsevier SAS. All rights reserved.

  14. Dermatomyositis revealing breast cancer: report of a case.

    PubMed

    Lamquami, Safae; Errarhay, Sanae; Mamouni, Nisrine; Bouchikhi, Chahrazad; Banani, Abdelaziz

    2015-01-01

    Dermatomyositis (DM) is a rare connective corresponding to an inflammatory disease of skeletal muscles. Paraneoplastic origin must always be sought, primarily gynecological tumor in women, but the investigations are often made difficult by the fact that a primary tumor is often not detectable at the time of the cutaneous manifestations. This approach includes in addition to the monitoring report at regular intervals of 6 to 12 months for two years after diagnosis. We report a case of Dermatomyositis revealing breast cancer.

  15. Placental Abruption Revealed by Hemoperitoneum: A Case Report

    PubMed Central

    Bertholdt, C.; Vincent-Rohfritsch, A.; Tsatsaris, V.; Goffinet, F.

    2016-01-01

    Background Hemoperitoneum is a life-threatening surgical emergency. Diagnosis of the cause is often difficult, in particular, during pregnancy when it may be either obstetric or nonobstetric. Case We report the case of a hemoperitoneum caused by the backflow of blood through a uterine tube, due to placental abruption. Conclusion Hemoperitoneum in pregnant women with no other signs can reveal placental abruption. The difficulty in identifying the cause may delay appropriate management. PMID:27994944

  16. [Neonatal adrenal hemorrhage revealed by jaundice: a case report].

    PubMed

    Oulmaati, A; Hays, S; Mory-Thomas, N; Bretones, P; Bensaid, M; Jordan, I; Bonfils, M; Godbert, I; Picaud, J-C

    2012-04-01

    The clinical presentation of adrenal hemorrhage varies, depending on the extent of hemorrhage as well as the amount of adrenal cortex involved by the hemorrhage. We report here a case of neonatal adrenal hemorrhage revealed by late onset of neonatal jaundice. This adrenal hemorrhage most probably resulted from shoulder dystocia. The aim of this work was to focus on the fact that jaundice can be caused by adrenal hemorrhage and to emphasize the crucial importance of abdominal ultrasound in cases of persistent jaundice.

  17. Diabetic acido-ketosis revealing thiamine-responsive megaloblastic anemia.

    PubMed

    Bouyahia, O; Ouderni, M; Ben Mansour, F; Matoussi, N; Khaldi, F

    2009-12-01

    Thiamine-responsive megaloblastic anemia (TRMA) is a rare autosomal recessive disorder characterized by megaloblastic anemia, diabetes mellitus and progressive sensorineural deafness. We report the cases of two infants, aged 4 and 5 months, hospitalized for diabetic ketoacidosis requiring insulin therapy. Laboratory tests revealed megaloblasic anemia, thrombocytopenia and normal thiamine level. Neurosensorial investigations showed bilateral deafness and ophthalmic involvement. Treatment with oral thiamine normalized hematological disorders and controlled diabetes; however, thiamine therapy had no impact on neurosensorial disorders.

  18. Revealing bismuth oxide hollow nanoparticle formation by the Kirkendall effect.

    PubMed

    Niu, Kai-Yang; Park, Jungwon; Zheng, Haimei; Alivisatos, A Paul

    2013-01-01

    We study the formation of bismuth oxide hollow nanoparticles by the Kirkendall effect using liquid cell transmission electron microscopy (TEM). Rich dynamics of bismuth diffusion through the bismuth oxide shell have been captured in situ. The diffusion coefficient of bismuth through bismuth oxide shell is 3-4 orders of magnitude higher than that of bulk. Observation reveals that defects, temperature, sizes of the particles, and so forth can affect the diffusion of reactive species and modify the kinetics of the hollowing process.

  19. [Chicken pox recurrence revealing a renal adenocarcinoma in an adult].

    PubMed

    Thieulent, N; Grezard, P; Wolf, F; Barrut, D; Perrot, H

    2000-09-01

    A new episode of chicken pox in adults who had a well documented infection previously is usually observed in immunocompromised individuals. The principal immunodeficiency factors are hematology diseases, acquired immunodeficiency disease and old age. We report here the case of a young woman who after a contaminating contact presented a recurrence of typical chicken pox. Morphological investigations evidenced a right kidney tumor which pathology revealed to be a renal adenocarcinoma. We discuss this pathological association and review cases reported in the literature.

  20. Revealing the secrets of composite helmets of ancient Japanese tradition

    NASA Astrophysics Data System (ADS)

    Salvemini, F.; Grazzi, F.; Fedrigo, A.; Williams, A.; Civita, F.; Scherillo, A.; Vontobel, P.; Hartmann, S.; Lehmann, E.; Zoppi, M.

    2013-08-01

    We present novel results from a non-invasive examination of two kabuto (helmets), made in Japan in the 17th century. Neutron-imaging experiments (radiography and tomography), carried out at the ICON and NEUTRA beamlines, operating at the neutron source SINQ (CH), have allowed to determine the inner metal structure and manufacturing techniques of these beautiful examples of past technology, revealing some otherwise invisible details.

  1. Water Bubble revealing a refracted image of ESA Andre Kuipers

    NASA Image and Video Library

    2012-02-28

    ISS030-E-108804 (28 Feb. 2012) -- A close look at this four-inch polished metal sphere onboard the International Space Station reveals a reflected image of NASA astronaut Don Pettit, Expedition 30 flight engineer. Using a 105-mm lens, Pettit took a series of pictures of the sphere. Also visible is hardware from the Capillary Flow Experiment-2 (CFE-2) Vane Gap 1 Experiment, in the U.S. Laboratory Destiny.

  2. Proposal for revealing quantum nonlocality via local contextuality.

    PubMed

    Cabello, Adán

    2010-06-04

    Two distant systems can exhibit quantum nonlocality even though the correlations between them admit a local model. This nonlocality can be revealed by testing extra correlations between successive measurements on one of the systems which do not admit a noncontextual model whatever the reduced state of this system is. This shows that quantum contextuality plays a fundamental role in quantum nonlocality, and allows an experimental test of the Kochen-Specker with locality theorem.

  3. Active medulloblastoma enhancers reveal subgroup-specific cellular origins

    PubMed Central

    Lin, Charles Y.; Erkek, Serap; Tong, Yiai; Yin, Linlin; Federation, Alexander J.; Zapatka, Marc; Haldipur, Parthiv; Kawauchi, Daisuke; Risch, Thomas; Warnatz, Hans-Jörg; Worst, Barbara C.; Ju, Bensheng; Orr, Brent A.; Zeid, Rhamy; Polaski, Donald R.; Segura-Wang, Maia; Waszak, Sebastian M.; Jones, David T.W.; Kool, Marcel; Hovestadt, Volker; Buchhalter, Ivo; Sieber, Laura; Johann, Pascal; Chavez, Lukas; Gröschel, Stefan; Ryzhova, Marina; Korshunov, Andrey; Chen, Wenbiao; Chizhikov, Victor V.; Millen, Kathleen J.; Amstislavskiy, Vyacheslav; Lehrach, Hans; Yaspo, Marie-Laure; Eils, Roland; Lichter, Peter; Korbel, Jan O.; Pfister, Stefan M.; Bradner, James E.; Northcott, Paul A.

    2016-01-01

    Summary Medulloblastoma is a highly malignant paediatric brain tumour, often inflicting devastating consequences on the developing child. Genomic studies have revealed four distinct molecular subgroups with divergent biology and clinical behaviour. An understanding of the regulatory circuitry governing the transcriptional landscapes of medulloblastoma subgroups, and how this relates to their respective developmental origins, is lacking. Using H3K27ac and BRD4 ChIP-Seq, coupled with tissue-matched DNA methylation and transcriptome data, we describe the active cis-regulatory landscape across 28 primary medulloblastoma specimens. Analysis of differentially regulated enhancers and super-enhancers reinforced inter-subgroup heterogeneity and revealed novel, clinically relevant insights into medulloblastoma biology. Computational reconstruction of core regulatory circuitry identified a master set of transcription factors, validated by ChIP-Seq, that are responsible for subgroup divergence and implicate candidate cells-of-origin for Group 4. Our integrated analysis of enhancer elements in a large series of primary tumour samples reveals insights into cis-regulatory architecture, unrecognized dependencies, and cellular origins. PMID:26814967

  4. Using metabarcoding to reveal and quantify plant-pollinator interactions

    PubMed Central

    Pornon, André; Escaravage, Nathalie; Burrus, Monique; Holota, Hélène; Khimoun, Aurélie; Mariette, Jérome; Pellizzari, Charlène; Iribar, Amaia; Etienne, Roselyne; Taberlet, Pierre; Vidal, Marie; Winterton, Peter; Zinger, Lucie; Andalo, Christophe

    2016-01-01

    Given the ongoing decline of both pollinators and plants, it is crucial to implement effective methods to describe complex pollination networks across time and space in a comprehensive and high-throughput way. Here we tested if metabarcoding may circumvent the limits of conventional methodologies in detecting and quantifying plant-pollinator interactions. Metabarcoding experiments on pollen DNA mixtures described a positive relationship between the amounts of DNA from focal species and the number of trnL and ITS1 sequences yielded. The study of pollen loads of insects captured in plant communities revealed that as compared to the observation of visits, metabarcoding revealed 2.5 times more plant species involved in plant-pollinator interactions. We further observed a tight positive relationship between the pollen-carrying capacities of insect taxa and the number of trnL and ITS1 sequences. The number of visits received per plant species also positively correlated to the number of their ITS1 and trnL sequences in insect pollen loads. By revealing interactions hard to observe otherwise, metabarcoding significantly enlarges the spatiotemporal observation window of pollination interactions. By providing new qualitative and quantitative information, metabarcoding holds great promise for investigating diverse facets of interactions and will provide a new perception of pollination networks as a whole. PMID:27255732

  5. Activity screening of environmental metagenomic libraries reveals novel carboxylesterase families

    DOE PAGES

    Popovic, Ana; Hai, Tran; Tchigvintsev, Anatoly; ...

    2017-03-08

    Metagenomics has made accessible an enormous reserve of global biochemical diversity. In order to tap into this vast resource of novel enzymes, we have screened over one million clones from metagenome DNA libraries derived from sixteen different environments for carboxylesterase activity and identified 714 positive hits. Here, we validated the esterase activity of 80 selected genes, which belong to 17 different protein families including unknown and cyclase-like proteins. Three metagenomic enzymes exhibited lipase activity, and seven proteins showed polyester depolymerization activity against polylactic acid and polycaprolactone. Detailed biochemical characterization of four new enzymes revealed their substrate preference, whereas their catalyticmore » residues were identified using site-directed mutagenesis. The crystal structure of the metal-ion dependent esterase MGS0169 from the amidohydrolase superfamily revealed a novel active site with a bound unknown ligand. Thus, activity-centered metagenomics has revealed diverse enzymes and novel families of microbial carboxylesterases, whose activity could not have been predicted using bioinformatics tools.« less

  6. Tal1 transgenic expression reveals absence of B lymphocytes.

    PubMed

    Palamarchuk, Alexey; Zanesi, Nicola; Aqeilan, Rami I; Efanov, Alexey; Maximov, Vadim; Santanam, Urmila; Hagan, John P; Croce, Carlo M; Pekarsky, Yuri

    2006-06-15

    TAL1 oncogene encodes a helix-loop-helix transcription factor, Tal1, which is required for blood cell development, and its activation is a frequent event in T-cell acute lymphoblastic leukemia. Tal1 interacts and inhibits other helix-loop-helix factors such as E47 and HEB. To investigate the function of Tal1 in B cells, we generated Emu-TAL1 transgenic mouse line, expressing Tal1 in mouse B-cell lineage. Fluorescence-activated cell sorting (FACS) analysis of lymphocytes isolated from spleens of five out of five founders reveals complete absence of IgM- or CD19-expressing cells. Only 2% to 3% of these cells were B220+ and 100% of B220+ cells were CD43+, indicating that these mice were able to make pro-B cells. Similarly, FACS analysis of bone marrow cells in Emu-TAL1 mice revealed complete absence of B220+IgM+ and B220+CD19+ cells. Analysis of the recombination status of IgH genes revealed the presence of D-J but absence or drastic reduction of V-D-J rearrangements. Our results suggest that Tal1 overexpression in B cells results in a phenotype similar to that of B cells of E47/E2A knockout animals. This represents first in vivo evidence that Tal1 can completely inhibit E47/E2A function.

  7. Active medulloblastoma enhancers reveal subgroup-specific cellular origins.

    PubMed

    Lin, Charles Y; Erkek, Serap; Tong, Yiai; Yin, Linlin; Federation, Alexander J; Zapatka, Marc; Haldipur, Parthiv; Kawauchi, Daisuke; Risch, Thomas; Warnatz, Hans-Jörg; Worst, Barbara C; Ju, Bensheng; Orr, Brent A; Zeid, Rhamy; Polaski, Donald R; Segura-Wang, Maia; Waszak, Sebastian M; Jones, David T W; Kool, Marcel; Hovestadt, Volker; Buchhalter, Ivo; Sieber, Laura; Johann, Pascal; Chavez, Lukas; Gröschel, Stefan; Ryzhova, Marina; Korshunov, Andrey; Chen, Wenbiao; Chizhikov, Victor V; Millen, Kathleen J; Amstislavskiy, Vyacheslav; Lehrach, Hans; Yaspo, Marie-Laure; Eils, Roland; Lichter, Peter; Korbel, Jan O; Pfister, Stefan M; Bradner, James E; Northcott, Paul A

    2016-02-04

    Medulloblastoma is a highly malignant paediatric brain tumour, often inflicting devastating consequences on the developing child. Genomic studies have revealed four distinct molecular subgroups with divergent biology and clinical behaviour. An understanding of the regulatory circuitry governing the transcriptional landscapes of medulloblastoma subgroups, and how this relates to their respective developmental origins, is lacking. Here, using H3K27ac and BRD4 chromatin immunoprecipitation followed by sequencing (ChIP-seq) coupled with tissue-matched DNA methylation and transcriptome data, we describe the active cis-regulatory landscape across 28 primary medulloblastoma specimens. Analysis of differentially regulated enhancers and super-enhancers reinforced inter-subgroup heterogeneity and revealed novel, clinically relevant insights into medulloblastoma biology. Computational reconstruction of core regulatory circuitry identified a master set of transcription factors, validated by ChIP-seq, that is responsible for subgroup divergence, and implicates candidate cells of origin for Group 4. Our integrated analysis of enhancer elements in a large series of primary tumour samples reveals insights into cis-regulatory architecture, unrecognized dependencies, and cellular origins.

  8. Traumatic extradural haematoma revealed after contralateral decompressive craniectomy.

    PubMed

    Nadig, Adarsh S; King, Andrew T

    2012-12-01

    Traumatic extradural haematoma following a severe head injury is well documented in neurosurgical literature. We report a case of traumatic extradural haematoma which initially was concealed by the high intracranial pressure (ICP) and revealed after the contralateral decompressive craniectomy. A 21-year-old roofer sustained severe head injury from a fall. The CT brain showed right sided fronto-temporal contusions with small acute subdural haematoma and left orbital roof fracture extending into the temporal bone. ICP was above 45 mmHg even after maximal medical therapy. Decompressive craniectomy was performed on the right side along with contusionectomy. Within an hour, ICP spiked and the CT brain showed left side extradural haematoma. The second surgery demonstrated a bleeding middle meningeal artery associated with the left temporal bone fracture. The clinical sequence of events, radiological and operative findings revealed this to be a traumatic extradural haematoma sustained at the initial trauma. This was revealed after the tamponade effect was released from the initial decompressive craniectomy on the contralateral side.

  9. Transient light-induced intracellular oxidation revealed by redox biosensor

    SciTech Connect

    Kolossov, Vladimir L.; Beaudoin, Jessica N.; Hanafin, William P.; DiLiberto, Stephen J.; Kenis, Paul J.A.; Rex Gaskins, H.

    2013-10-04

    Highlights: •Time-resolved live cell imaging revealed light-induced oxidation. •Only the roGFP probe fused with glutaredoxin reveals photooxidation. •The transient oxidation is rapidly reduced by the cytosolic antioxidant system. •Intracellular photooxidation is media-dependent. •Oxidation is triggered exclusively by exposure to short wavelength excitation. -- Abstract: We have implemented a ratiometric, genetically encoded redox-sensitive green fluorescent protein fused to human glutaredoxin (Grx1-roGFP2) to monitor real time intracellular glutathione redox potentials of mammalian cells. This probe enabled detection of media-dependent oxidation of the cytosol triggered by short wavelength excitation. The transient nature of light-induced oxidation was revealed by time-lapse live cell imaging when time intervals of less than 30 s were implemented. In contrast, transient ROS generation was not observed with the parental roGFP2 probe without Grx1, which exhibits slower thiol-disulfide exchange. These data demonstrate that the enhanced sensitivity of the Grx1-roGFP2 fusion protein enables the detection of short-lived ROS in living cells. The superior sensitivity of Grx1-roGFP2, however, also enhances responsiveness to environmental cues introducing a greater likelihood of false positive results during image acquisition.

  10. Using metabarcoding to reveal and quantify plant-pollinator interactions.

    PubMed

    Pornon, André; Escaravage, Nathalie; Burrus, Monique; Holota, Hélène; Khimoun, Aurélie; Mariette, Jérome; Pellizzari, Charlène; Iribar, Amaia; Etienne, Roselyne; Taberlet, Pierre; Vidal, Marie; Winterton, Peter; Zinger, Lucie; Andalo, Christophe

    2016-06-03

    Given the ongoing decline of both pollinators and plants, it is crucial to implement effective methods to describe complex pollination networks across time and space in a comprehensive and high-throughput way. Here we tested if metabarcoding may circumvent the limits of conventional methodologies in detecting and quantifying plant-pollinator interactions. Metabarcoding experiments on pollen DNA mixtures described a positive relationship between the amounts of DNA from focal species and the number of trnL and ITS1 sequences yielded. The study of pollen loads of insects captured in plant communities revealed that as compared to the observation of visits, metabarcoding revealed 2.5 times more plant species involved in plant-pollinator interactions. We further observed a tight positive relationship between the pollen-carrying capacities of insect taxa and the number of trnL and ITS1 sequences. The number of visits received per plant species also positively correlated to the number of their ITS1 and trnL sequences in insect pollen loads. By revealing interactions hard to observe otherwise, metabarcoding significantly enlarges the spatiotemporal observation window of pollination interactions. By providing new qualitative and quantitative information, metabarcoding holds great promise for investigating diverse facets of interactions and will provide a new perception of pollination networks as a whole.

  11. 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.

  12. Phospholipid mesophases at solid interfaces: in-situ X-ray diffraction and spin-label studies.

    PubMed

    Rappolt, Michael; Amenitsch, Heinz; Strancar, Janez; Teixeira, Cilaine V; Kriechbaum, Manfred; Pabst, Georg; Majerowicz, Monika; Laggner, Peter

    2004-11-29

    In this work, we report on recent investigations, both on the global and on the local molecular architecture of supported phospholipid model membranes. A brief theoretical introduction explains how global structural information on supramolecular lipid ensembles can be retrieved from surface X-ray diffraction measurements as well as how spin-label electron paramagnetic resonance spectroscopy (EPR) provides complementary information on the local environment of probe molecules. The combination of especially designed X-ray cells with the technique of small- and wide-angle X-ray surface scattering makes it possible to explore various fields of lipid research and its applications. Examples for different physico-chemical conditions are presented: (i) in situ chemistry under excess of water conditions demonstrating how solid-supported lipid films sense salinity, (ii) the 3D electron density reconstruction of a vesicle-fusion intermediate under controlled humidity, and (iii) complementary temperature and pressure effects on oriented phospholipid samples. Further, special attention has been given to the influence of different film preparation techniques with respect to quality and the defect structure manifestation. To resolve the proportions and local properties of defects in a hydrated lipid-deposited surface, spin-label EPR was applied. The results from 9.6 GHz EPR as well as from 1.2 GHz EPR suggest the alignment to be in the range between 30% and 80%. In addition, slow time-dependent EPR measurements point to nano-structural rearrangements due to water flow and reduction of alignment quality.

  13. ZnS quantum dot induced phase transitional changes and enhanced ferroelectric mesophase in QDs/FLC composites

    NASA Astrophysics Data System (ADS)

    Vimal, T.; Pandey, S.; Singh, D. P.; Gupta, S. K.; Agrahari, K.; Kumbhakar, P.; Kole, A. K.; Manohar, R.

    2017-01-01

    In the present study, we report the dielectric and electro - optical (E - O) study of ZnS quantum dots (QDs) dispersed ferroelectric liquid crystal (FLC) material. Change in the SmC*- SmA phase transition temperature has been investigated by the thermal study. Width of SmC* phase is found to be slightly increased due to the dispersion of ZnS QDs, which has also been observed in the dielectric and E - O study of composites. Fitting of spontaneous polarization curves on the temperature scale has been done theoretically to obtain the change in SmC*- SmA phase transition temperature. A significant modification in the FLC material parameters (like spontaneous polarization, optical response time, tilt angle and rotational viscosity) has been observed after the dispersion of QDs. These modifications are the consequences of the strong dipolar interaction between the FLC molecule and QDs. Significant fastening of the optical response time for low conc. of QDs dispersed FLC composite shows its utilization in advanced display devices.

  14. Molecular and crystal structures of p-heptyloxyphenyl p-hexyloxybenzoate and p-butyloxyphenyl p-heptyloxybenzoate: Mesophase design

    SciTech Connect

    Kuz'mina, L. G. Gunina, M. A.; Churakov, A. V.; Pestov, S. M.

    2013-03-15

    Two aromatic esters with the formulas C{sub 6}H{sub 13}-O-C{sub 6}H{sub 4}-C(O)O-C{sub 6}H{sub 4}-O-C{sub 7}H{sub 15} (1) and C{sub 7}H{sub 15}-O-C{sub 6}H{sub 4}-C(O)O-C{sub 6}H{sub 4}-O-C{sub 4}H{sub 9} (2) belonging to nematic liquid-crystal compounds were studied by X-ray diffraction. Compound 1 crystallizes in two modifications: monoclinic (1-m) and triclinic (1-tr). The crystal packing of 1 and 2 is built from alternating loosely packed aliphatic regions and closely packed aromatic regions. In crystal structures 1-m and 2, the aromatic regions are linked into chains by hydrogen bonds with the participation of the carbonyl oxygen atom of the ester group and the C-H fragment of the benzene ring, but these hydrogen bonds in 1-m are much weaker than in 2. In 1-m there are {pi}-stacking interactions between the molecules, resulting in the formation of centrosymmetric dimers with an interplanar distance of 3.45 A. In 1-tr, the aromatic fragments form a herringbone packing motif favorable for a two-dimensional network of directional C-H...{pi}-system interactions.

  15. Liquid crystal engineering--new complex mesophase structures and their relations to polymer morphologies, nanoscale patterning and crystal engineering.

    PubMed

    Tschierske, Carsten

    2007-12-01

    This critical review focuses on recent progress in the field of T-shaped ternary amphiphiles. These molecules can self-assemble into a series of new liquid crystalline (LC) phases with polygonal cylinder structures, new lamellar phases and LC phases combining columns and layers. These structures are analyzed on the basis of symmetry, net topology and tiling pattern (Laves and Archimedean tilings) and discussed in relation to morphologies of multiblock copolymers, self organized DNA super-lattices, metal-organic frameworks, crystal-engineering and self-assembled periodic superstructures on surfaces (210 references).

  16. Interior Evolution of Ceres and Vesta Revealed by Dawn

    NASA Astrophysics Data System (ADS)

    Raymond, C. A.; Russell, C. T.; Bland, M. T.; Castillo, J. C.; De Sanctis, M. C.; Ermakov, A.; Jaumann, R.; Konopliv, A. S.; Marchi, S.; McCord, T. B.; McSween, H. Y., Jr.; Nathues, A.; Park, R. S.; Prettyman, T. H.; Toplis, M. J.; Zuber, M. T.

    2015-12-01

    Dawn's exploration of Vesta and Ceres has revealed their geophysical characteristics, informing the processes that shaped the bodies. Dawn has determined the average diameter of Ceres to be 940 km, smaller than the previously estimated 975 km [1]. This implies a density of 2160 kg/m3, indicating that Ceres is less differentiated than predicted [2]. Ceres' entire surface is cratered, implying the lack of a thick (10's of km) water ice layer at the surface. Variability in Ceres' crater morphology indicates that the near-surface layer has variable strength and rheology, likely due to heterogeneity in the near-surface mixture of rock, ice and salt. These observations may indicate that Ceres lost a significant amount of an original surface ice layer due to impact erosion. The lack of large impact basins on Ceres can be interpreted to be the result of viscous relaxation. These data provide insights into Ceres' thermal evolution and mechanical properties, which appear to be unique to this warm, icy body. In contrast to Ceres, Vesta formed very early and hot, resulting in a fully differentiated body. Dawn's exploration revealed geophysical and geochemical evidence for an iron-rich core and basaltic crust. However, unlike the pre-Dawn paradigm of Vesta's evolution, Dawn found that the crust and mantle of Vesta are less distinct than predicted by classical differentiation models. [1] Thomas, P. C., et al., Differentiation of the asteroid Ceres as revealed by its shape, Nature, 437, 224-226, 2005; [2] McCord et al., Ceres: Its Origin, Evolution and Structure and Dawn's Potential Contribution, Space Sci Rev
DOI 10.1007/s11214-010-9729-9, 2011.

  17. Genes but Not Genomes Reveal Bacterial Domestication of Lactococcus Lactis

    PubMed Central

    Passerini, Delphine; Beltramo, Charlotte; Coddeville, Michele; Quentin, Yves; Ritzenthaler, Paul

    2010-01-01

    Background The population structure and diversity of Lactococcus lactis subsp. lactis, a major industrial bacterium involved in milk fermentation, was determined at both gene and genome level. Seventy-six lactococcal isolates of various origins were studied by different genotyping methods and thirty-six strains displaying unique macrorestriction fingerprints were analyzed by a new multilocus sequence typing (MLST) scheme. This gene-based analysis was compared to genomic characteristics determined by pulsed-field gel electrophoresis (PFGE). Methodology/Principal Findings The MLST analysis revealed that L. lactis subsp. lactis is essentially clonal with infrequent intra- and intergenic recombination; also, despite its taxonomical classification as a subspecies, it displays a genetic diversity as substantial as that within several other bacterial species. Genome-based analysis revealed a genome size variability of 20%, a value typical of bacteria inhabiting different ecological niches, and that suggests a large pan-genome for this subspecies. However, the genomic characteristics (macrorestriction pattern, genome or chromosome size, plasmid content) did not correlate to the MLST-based phylogeny, with strains from the same sequence type (ST) differing by up to 230 kb in genome size. Conclusion/Significance The gene-based phylogeny was not fully consistent with the traditional classification into dairy and non-dairy strains but supported a new classification based on ecological separation between “environmental” strains, the main contributors to the genetic diversity within the subspecies, and “domesticated” strains, subject to recent genetic bottlenecks. Comparison between gene- and genome-based analyses revealed little relationship between core and dispensable genome phylogenies, indicating that clonal diversification and phenotypic variability of the “domesticated” strains essentially arose through substantial genomic flux within the dispensable genome

  18. Tributaries of West Antarctic Ice Streams Revealed by RADARSAT Interferometry.

    PubMed

    Joughin; Gray; Bindschadler; Price; Morse; Hulbe; Mattar; Werner

    1999-10-08

    Interferometric RADARSAT data are used to map ice motion in the source areas of four West Antarctic ice streams. The data reveal that tributaries, coincident with subglacial valleys, provide a spatially extensive transition between slow inland flow and rapid ice stream flow and that adjacent ice streams draw from shared source regions. Two tributaries flow into the stagnant ice stream C, creating an extensive region that is thickening at an average rate of 0.49 meters per year. This is one of the largest rates of thickening ever reported in Antarctica.

  19. Electronic properties of nanoentities revealed by electrically driven rotation

    PubMed Central

    Fan, D. L.; Zhu, Frank Q.; Xu, Xiaobin; Cammarata, Robert C.; Chien, C. L.

    2012-01-01

    Direct electric measurement via small contacting pads on individual quasi-one-dimensional nanoentities, such as nanowires and carbon nanotubes, are usually required to access its electronic properties. We show in this work that 1D nanoentities in suspension can be driven to rotation by AC electric fields. The chirality of the resultantrotation unambiguously reveals whether the nanoentities are metal, semiconductor, or insulator due to the dependence of the Clausius–Mossotti factor on the material conductivity and frequency. This contactless method provides rapid and parallel identification of the electrical characteristics of 1D nanoentities. PMID:22645373

  20. Protein tagging reveals new insights into signaling in flagella.

    PubMed

    Ishikawa, Takashi

    2014-03-03

    In this issue, Oda et al. (2014. J. Cell Biol. http://dx.doi.org/10.1083/jcb.201312014) use mutant analysis, protein tagging, and cryoelectron tomography to determine the detailed location of components in flagellar radial spokes-a complex of proteins that connect the peripheral microtubule doublets to the central pair. Remarkably, this approach revealed an interaction between radial spokes and the central pair based on geometry rather than a specific signaling mechanism, highlighting the importance of studying a system in three dimensions.

  1. Estimating the probability of failure when testing reveals no failures

    NASA Technical Reports Server (NTRS)

    Miller, Keith W.; Morell, Larry J.; Noonan, Robert E.; Park, Stephen K.; Nicol, David M.; Murrill, Branson W.; Voas, Jeffrey M.

    1992-01-01

    Formulas for estimating the probability of failure when testing reveals no errors are introduced. These formulas incorporate random testing results, information about the input distribution, and prior assumptions about the probability of failure of the software. The formulas are not restricted to equally likely input distributions, and the probability of failure estimate can be adjusted when assumptions about the input distribution change. The formulas are based on a discrete sample space statistical model of software and include Bayesian prior assumptions. Reusable software and software in life-critical applications are particularly appropriate candidates for this type of analysis.

  2. How the ``Blues'' reveals the intimacy of music and physics

    NASA Astrophysics Data System (ADS)

    Gibson, J. Murray

    2013-03-01

    Little do most people know when they hear blues piano - and you'll hear some live in this talk - that physics permeates the style, as it does all of music. Why should you care? By deconstructing blues piano the intimacy of physics, mathematics and music will be revealed in its glory.[1] The exercise says something about how the brains of the music composer and of the listener must be intimately linked to the physical principles of acoustics. And it provides a great vehicle to explain physical phenomena to non-scientists - everything from quantum mechanics to protein structure.

  3. [Tracheobronchopathia osteochondrodysplasias. About one case revealed by haemoptysis].

    PubMed

    Abid, Leïla; Ayadi-Kaddour, Aïda; Braham, Emna; Ismail, Olfa; Tritar, Fatma; Meraï, Samira; El Mezni, Faouzi

    2006-11-01

    Tracheobronchopathia osteochondrodysplasias is a benign and rare chronic disease, whose etiology remains obscure. It is characterized by the presence of subepithelial osteocartilaginous focal lesions without any relation to tracheal rings, essentially localized in the lower two thirds of the trachea and the major bronchi. We report a new case of tracheobronchopathia osteochondrodysplasias in a 47-year-old man, localized at the lower half of the trachea, revealed by haemoptysis. The lesion was suspected by bronchoscopy and the diagnosis was made histologically, showing heterotopic bone formation. The evolution of this affection was marked by a good clinical tolerance with only a symptomatic treatment.

  4. Estimating the probability of failure when testing reveals no failures

    NASA Technical Reports Server (NTRS)

    Miller, Keith W.; Morell, Larry J.; Noonan, Robert E.; Park, Stephen K.; Nicol, David M.; Murrill, Branson W.; Voas, Jeffrey M.

    1992-01-01

    Formulas for estimating the probability of failure when testing reveals no errors are introduced. These formulas incorporate random testing results, information about the input distribution, and prior assumptions about the probability of failure of the software. The formulas are not restricted to equally likely input distributions, and the probability of failure estimate can be adjusted when assumptions about the input distribution change. The formulas are based on a discrete sample space statistical model of software and include Bayesian prior assumptions. Reusable software and software in life-critical applications are particularly appropriate candidates for this type of analysis.

  5. Circumstellar Environments of MYSOs Revealed by IFU Spectroscopy

    NASA Astrophysics Data System (ADS)

    Navarete, F.; Damineli, A.; Barbosa, C. L.; Blum, R. D.

    2015-01-01

    Formation of massive stars (M > 8 M ⊙) is still not well understood and lacks of observational constraints. We observed 7 MYSO candidates using the NIFS spectrometer at Gemini North Telescope to study the accretion process at high angular resolution (~ 50 mas) and very closer to the central star. Preliminary results for 2 sources have revealed circumstellar structures traced by Brackett-Gamma, CO lines and extended H2 emission. Both sources present kinematics in the CO absorption lines, suggesting rotating structures. The next step will derive the central mass of each source by applying a keplerian model for these CO features.

  6. Mediated amperometry reveals different modes of yeast responses to sugars.

    PubMed

    Garjonyte, Rasa; Melvydas, Vytautas; Malinauskas, Albertas

    2016-02-01

    Menadione-mediated amperometry at carbon paste electrodes modified with various yeasts (Saccharomyces cerevisiae, Candida pulcherrima, Pichia guilliermondii and Debaryomyces hansenii) was employed to monitor redox activity inside the yeast cells induced by glucose, fructose, sucrose, maltose or galactose. Continuous measurements revealed distinct modes (transient or gradually increasing) of the current development during the first 2 to 3 min after subjection to glucose, fructose and sucrose at electrodes containing S. cerevisiae and non-Saccharomyces strains. Different modes (increasing or decreasing) of the current development after yeast subjection to galactose at electrodes with S. cerevisiae or D. hansenii and at electrodes with C. pulcherrima and P. guilliermondii suggested different mechanisms of galactose assimilation.

  7. Cutaneous metastasis revealing a relapse of gastric linitis: Another case

    PubMed Central

    Kairouani, Mouna; Perrin, Julie; Dietemann-Barabinot, Anne; Diab, Rafiq; Ruck, Stephane

    2012-01-01

    INTRODUCTION Cutaneous metastasis from gastric cancer is a rare occurrence. The linitis gastric carcinoma accounts only 8.7% of all gastric cancers. PRESENTATION OF CASE We report a case of female patient who was followed for linits cancer with peritoneal metastasis treated by six cycles of chemotherapy. After seventeen months of control, the relapse of the disease revealed by occurrence of cutaneous metastatsis. DISCUSSION Cutaneous metastasis from linit gastric is rare and the prognostic remains poor. The treatment is palliative. CONCLUSION This rare presentation should encourage the practitioners to biopsy any suspicion skin lesion. PMID:23276763

  8. Cutaneous metastasis revealing a relapse of gastric linitis: Another case.

    PubMed

    Kairouani, Mouna; Perrin, Julie; Dietemann-Barabinot, Anne; Diab, Rafiq; Ruck, Stephane

    2013-01-01

    Cutaneous metastasis from gastric cancer is a rare occurrence. The linitis gastric carcinoma accounts only 8.7% of all gastric cancers. We report a case of female patient who was followed for linits cancer with peritoneal metastasis treated by six cycles of chemotherapy. After seventeen months of control, the relapse of the disease revealed by occurrence of cutaneous metastatsis. Cutaneous metastasis from linit gastric is rare and the prognostic remains poor. The treatment is palliative. This rare presentation should encourage the practitioners to biopsy any suspicion skin lesion. Copyright © 2012 Surgical Associates Ltd. Published by Elsevier Ltd. All rights reserved.

  9. [Tetraparesis revealing Conn adenoma in a pregnant woman].

    PubMed

    Assoufi, Naoufal; Bahadi, Nessrine; Omri, Nawal El; Sekkach, Youssef; Ameziane, Taoufiq; Ghafir, Driss

    2016-01-01

    We report the case of Conn adenoma revealed by tetraparesis in a 33-year old pregnant woman at the 16(th)week of amenorrhea. The patient had a blood pressure of 147/87 mmHg, which was considered high-normal, hypokalemia at 1.1 mmol/l. The diagnosis was confirmed by hormone dosage which showed elevated plasma aldosterone levels and decreased plasma renin activity. MRI showed a left adrenal nodule, 1.5 cm in diameter, compatible with adrenal adenoma. Left adrenalectomy was performed with simple postoperative course and normalization of kalemia and blood pressure.

  10. Memory in motion: movement dynamics reveal memory strength.

    PubMed

    Papesh, Megan H; Goldinger, Stephen D

    2012-10-01

    Recognition memory is typically examined as a discrete end-state, describable by static variables, such as accuracy, response time, and confidence. In the present study, we combined real-time mouse-tracking with subsequent, overt confidence estimates to examine the dynamic nature of memory decisions. By examining participants' streaming x-, y- mouse coordinates during recognition decisions, we observed that movement trajectories revealed underlying response confidence. More confident decisions were associated with shorter decision times and more linear response trajectories. Less confident decisions were made slowly, with increased trajectory curvature. Statistical indices of curvature and decision times, including area-under-the-curve and time to maximum deviation, suggested that memory strength relates to response dynamics. Whether participants were correct or incorrect, old responses showed a stronger correspondence between mouse trajectories and confidence, relative to new responses. We suggest that people subjectively experience a correspondence between feelings of memory and feelings of confidence; that subjective experience reveals itself in real-time decision processes, as suggested by sequential sampling models of recognition decisions.

  11. Proteomics Reveals Novel Drosophila Seminal Fluid Proteins Transferred at Mating

    PubMed Central

    Findlay, Geoffrey D; Yi, Xianhua; MacCoss, Michael J; Swanson, Willie J

    2008-01-01

    Across diverse taxa, seminal fluid proteins (Sfps) transferred at mating affect the reproductive success of both sexes. Such reproductive proteins often evolve under positive selection between species; because of this rapid divergence, Sfps are hypothesized to play a role in speciation by contributing to reproductive isolation between populations. In Drosophila, individual Sfps have been characterized and are known to alter male sperm competitive ability and female post-mating behavior, but a proteomic-scale view of the transferred Sfps has been missing. Here we describe a novel proteomic method that uses whole-organism isotopic labeling to detect transferred Sfps in mated female D. melanogaster. We identified 63 proteins, which were previously unknown to function in reproduction, and confirmed the transfer of dozens of predicted Sfps. Relative quantification of protein abundance revealed that several of these novel Sfps are abundant in seminal fluid. Positive selection and tandem gene duplication are the prevailing forces of Sfp evolution, and comparative proteomics with additional species revealed lineage-specific changes in seminal fluid content. We also report a proteomic-based gene discovery method that uncovered 19 previously unannotated genes in D. melanogaster. Our results demonstrate an experimental method to identify transferred proteins in any system that is amenable to isotopic labeling, and they underscore the power of combining proteomic and evolutionary analyses to shed light on the complex process of Drosophila reproduction. PMID:18666829

  12. Direct visualization reveals kinetics of meiotic chromosome synapsis

    DOE PAGES

    Rog, Ofer; Dernburg, Abby  F.

    2015-03-17

    The synaptonemal complex (SC) is a conserved protein complex that stabilizes interactions along homologous chromosomes (homologs) during meiosis. The SC regulates genetic exchanges between homologs, thereby enabling reductional division and the production of haploid gametes. Here, we directly observe SC assembly (synapsis) by optimizing methods for long-term fluorescence recording in C. elegans. We report that synapsis initiates independently on each chromosome pair at or near pairing centers—specialized regions required for homolog associations. Once initiated, the SC extends rapidly and mostly irreversibly to chromosome ends. Quantitation of SC initiation frequencies and extension rates reveals that initiation is a rate-limiting step inmore » homolog interactions. Eliminating the dynein-driven chromosome movements that accompany synapsis severely retards SC extension, revealing a new role for these conserved motions. This work provides the first opportunity to directly observe and quantify key aspects of meiotic chromosome interactions and will enable future in vivo analysis of germline processes.« less

  13. Ancient DNA sequence revealed by error-correcting codes.

    PubMed

    Brandão, Marcelo M; Spoladore, Larissa; Faria, Luzinete C B; Rocha, Andréa S L; Silva-Filho, Marcio C; Palazzo, Reginaldo

    2015-07-10

    A previously described DNA sequence generator algorithm (DNA-SGA) using error-correcting codes has been employed as a computational tool to address the evolutionary pathway of the genetic code. The code-generated sequence alignment demonstrated that a residue mutation revealed by the code can be found in the same position in sequences of distantly related taxa. Furthermore, the code-generated sequences do not promote amino acid changes in the deviant genomes through codon reassignment. A Bayesian evolutionary analysis of both code-generated and homologous sequences of the Arabidopsis thaliana malate dehydrogenase gene indicates an approximately 1 MYA divergence time from the MDH code-generated sequence node to its paralogous sequences. The DNA-SGA helps to determine the plesiomorphic state of DNA sequences because a single nucleotide alteration often occurs in distantly related taxa and can be found in the alternative codon patterns of noncanonical genetic codes. As a consequence, the algorithm may reveal an earlier stage of the evolution of the standard code.

  14. Characteristics of the tomato chromoplast revealed by proteomic analysis.

    PubMed

    Barsan, Cristina; Sanchez-Bel, Paloma; Rombaldi, Cesar; Egea, Isabel; Rossignol, Michel; Kuntz, Marcel; Zouine, Mohamed; Latché, Alain; Bouzayen, Mondher; Pech, Jean-Claude

    2010-05-01

    Chromoplasts are non-photosynthetic specialized plastids that are important in ripening tomato fruit (Solanum lycopersicum) since, among other functions, they are the site of accumulation of coloured compounds. Analysis of the proteome of red fruit chromoplasts revealed the presence of 988 proteins corresponding to 802 Arabidopsis unigenes, among which 209 had not been listed so far in plastidial databanks. These data revealed several features of the chromoplast. Proteins of lipid metabolism and trafficking were well represented, including all the proteins of the lipoxygenase pathway required for the synthesis of lipid-derived aroma volatiles. Proteins involved in starch synthesis co-existed with several starch-degrading proteins and starch excess proteins. Chromoplasts lacked proteins of the chlorophyll biosynthesis branch and contained proteins involved in chlorophyll degradation. None of the proteins involved in the thylakoid transport machinery were discovered. Surprisingly, chromoplasts contain the entire set of Calvin cycle proteins including Rubisco, as well as the oxidative pentose phosphate pathway (OxPPP). The present proteomic analysis, combined with available physiological data, provides new insights into the metabolic characteristics of the tomato chromoplast and enriches our knowledge of non-photosynthetic plastids.

  15. Enhanced limonene production in cyanobacteria reveals photosynthesis limitations

    PubMed Central

    Wang, Xin; Liu, Wei; Xin, Changpeng; Zheng, Yi; Cheng, Yanbing; Sun, Su; Li, Runze; Zhu, Xin-Guang; Dai, Susie Y.; Rentzepis, Peter M.; Yuan, Joshua S.

    2016-01-01

    Terpenes are the major secondary metabolites produced by plants, and have diverse industrial applications as pharmaceuticals, fragrance, solvents, and biofuels. Cyanobacteria are equipped with efficient carbon fixation mechanism, and are ideal cell factories to produce various fuel and chemical products. Past efforts to produce terpenes in photosynthetic organisms have gained only limited success. Here we engineered the cyanobacterium Synechococcus elongatus PCC 7942 to efficiently produce limonene through modeling guided study. Computational modeling of limonene flux in response to photosynthetic output has revealed the downstream terpene synthase as a key metabolic flux-controlling node in the MEP (2-C-methyl-d-erythritol 4-phosphate) pathway-derived terpene biosynthesis. By enhancing the downstream limonene carbon sink, we achieved over 100-fold increase in limonene productivity, in contrast to the marginal increase achieved through stepwise metabolic engineering. The establishment of a strong limonene flux revealed potential synergy between photosynthate output and terpene biosynthesis, leading to enhanced carbon flux into the MEP pathway. Moreover, we show that enhanced limonene flux would lead to NADPH accumulation, and slow down photosynthesis electron flow. Fine-tuning ATP/NADPH toward terpene biosynthesis could be a key parameter to adapt photosynthesis to support biofuel/bioproduct production in cyanobacteria. PMID:27911807

  16. Diffusion tensor imaging reveals evolution of primate brain architectures.

    PubMed

    Zhang, Degang; Guo, Lei; Zhu, Dajiang; Li, Kaiming; Li, Longchuan; Chen, Hanbo; Zhao, Qun; Hu, Xiaoping; Liu, Tianming

    2013-11-01

    Evolution of the brain has been an inherently interesting problem for centuries. Recent studies have indicated that neuroimaging is a powerful technique for studying brain evolution. In particular, a variety of reports have demonstrated that consistent white matter fiber connection patterns derived from diffusion tensor imaging (DTI) tractography reveal common brain architecture and are predictive of brain functions. In this paper, based on our recently discovered 358 dense individualized and common connectivity-based cortical landmarks (DICCCOL) defined by consistent fiber connection patterns in DTI datasets of human brains, we derived 65 DICCCOLs that are common in macaque monkey, chimpanzee and human brains and 175 DICCCOLs that exhibit significant discrepancies amongst these three primate species. Qualitative and quantitative evaluations not only demonstrated the consistencies of anatomical locations and structural fiber connection patterns of these 65 common DICCCOLs across three primates, suggesting an evolutionarily preserved common brain architecture but also revealed regional patterns of evolutionarily induced complexity and variability of those 175 discrepant DICCCOLs across the three species.

  17. Genetic structure of the Kuwaiti population revealed by paternal lineages.

    PubMed

    Triki-Fendri, Soumaya; Sánchez-Diz, Paula; Rey-González, Danel; Alfadhli, Suad; Ayadi, Imen; Ben Marzoug, Riadh; Carracedo, Ángel; Rebai, Ahmed

    2016-01-01

    We analyzed the Y-chromosome haplogroup diversity in the Kuwaiti population to gain a more complete overview of its genetic landscape. A sample of 117 males from the Kuwaiti population was studied through the analysis of 22 Y-SNPs. The results were then interpreted in conjunction with those of other populations from the Middle East, South Asia, North and East Africa, and East Europe. The analyzed markers allowed the discrimination of 19 different haplogroups with a diversity of 0.7713. J-M304 was the most frequent haplogroup in the Kuwaiti population (55.5%) followed by E-M96 (18%). They revealed a genetic homogeneity between the Kuwaiti population and those of the Middle East (FST  = 6.1%, P-value < 0.0001), although a significant correlation between genetic and geographic distances was found (r = 0.41, P-value = 0.009). Moreover, the nonsignificant pairwise FST genetic distances between the Kuwait population on the one hand and the Arabs of Iran and those of Sudan on the other, corroborate the hypothesis of bidirectional gene flow between Arabia and both Iran and Sudan. Overall, we have revealed that the Kuwaiti population has experienced significant gene flow from neighboring populations like Saudi Arabia, Iran, and East Africa. Therefore, we have confirmed that the population of Kuwait is genetically coextensive with those of the Middle East. © 2015 Wiley Periodicals, Inc.

  18. Previously Unrecognized Large Lunar Impact Basins Revealed by Topographic Data

    NASA Technical Reports Server (NTRS)

    Frey, Herbert V.

    2008-01-01

    The discovery of a large population of apparently buried impact craters on Mars, revealed as Quasi- Circular Depressions (QCDs) in Mars Orbiting Laser Altimeter (MOLA) data [1,2,3] and as Circular Thin Areas (CTAs) [4] in crustal thickness model data [5] leads to the obvious question: are there unrecognized impact features on the Moon and other bodies in the solar system? Early analysis of Clementine topography revealed several large impact basins not previously known [6,7], so the answer certainly is "Yes." How large a population of previously undetected impact basins, their size frequency distribution, and how much these added craters and basins will change ideas about the early cratering history and Late Heavy Bombardment on the Moon remains to be determined. Lunar Orbiter Laser Altimeter (LOLA) data [8] will be able to address these issues. As a prelude, we searched the state-of-the-art global topographic grid for the Moon, the Unified Lunar Control Net (ULCN) [9] for evidence of large impact features not previously recognized by photogeologic mapping, as summarized by Wilhelms [lo].

  19. Membrane protein properties revealed through data-rich electrostatics calculations

    PubMed Central

    Guerriero, Christopher J.; Brodsky, Jeffrey L.; Grabe, Michael

    2015-01-01

    SUMMARY The electrostatic properties of membrane proteins often reveal many of their key biophysical characteristics, such as ion channel selectivity and the stability of charged membrane-spanning segments. The Poisson-Boltzmann (PB) equation is the gold standard for calculating protein electrostatics, and the software APBSmem enables the solution of the PB equation in the presence of a membrane. Here, we describe significant advances to APBSmem including: full automation of system setup, per-residue energy decomposition, incorporation of PDB2PQR, calculation of membrane induced pKa shifts, calculation of non-polar energies, and command-line scripting for large scale calculations. We highlight these new features with calculations carried out on a number of membrane proteins, including the recently solved structure of the ion channel TRPV1 and a large survey of 1,614 membrane proteins of known structure. This survey provides a comprehensive list of residues with large electrostatic penalties for being embedded in the membrane potentially revealing interesting functional information. PMID:26118532

  20. Economic choices reveal probability distortion in macaque monkeys.

    PubMed

    Stauffer, William R; Lak, Armin; Bossaerts, Peter; Schultz, Wolfram

    2015-02-18

    Economic choices are largely determined by two principal elements, reward value (utility) and probability. Although nonlinear utility functions have been acknowledged for centuries, nonlinear probability weighting (probability distortion) was only recently recognized as a ubiquitous aspect of real-world choice behavior. Even when outcome probabilities are known and acknowledged, human decision makers often overweight low probability outcomes and underweight high probability outcomes. Whereas recent studies measured utility functions and their corresponding neural correlates in monkeys, it is not known whether monkeys distort probability in a manner similar to humans. Therefore, we investigated economic choices in macaque monkeys for evidence of probability distortion. We trained two monkeys to predict reward from probabilistic gambles with constant outcome values (0.5 ml or nothing). The probability of winning was conveyed using explicit visual cues (sector stimuli). Choices between the gambles revealed that the monkeys used the explicit probability information to make meaningful decisions. Using these cues, we measured probability distortion from choices between the gambles and safe rewards. Parametric modeling of the choices revealed classic probability weighting functions with inverted-S shape. Therefore, the animals overweighted low probability rewards and underweighted high probability rewards. Empirical investigation of the behavior verified that the choices were best explained by a combination of nonlinear value and nonlinear probability distortion. Together, these results suggest that probability distortion may reflect evolutionarily preserved neuronal processing.

  1. Blue whale earplug reveals lifetime contaminant exposure and hormone profiles

    PubMed Central

    Trumble, Stephen J.; Robinson, Eleanor M.; Berman-Kowalewski, Michelle; Potter, Charles W.; Usenko, Sascha

    2013-01-01

    Lifetime contaminant and hormonal profiles have been reconstructed for an individual male blue whale (Balaenoptera musculus, Linnaeus 1758) using the earplug as a natural aging matrix that is also capable of archiving and preserving lipophilic compounds. These unprecedented lifetime profiles (i.e., birth to death) were reconstructed with a 6-mo resolution for a wide range of analytes including cortisol (stress hormone), testosterone (developmental hormone), organic contaminants (e.g., pesticides and flame retardants), and mercury. Cortisol lifetime profiles revealed a doubling of cortisol levels over baseline. Testosterone profiles suggest this male blue whale reached sexual maturity at approximately 10 y of age, which corresponds well with and improves on previous estimates. Early periods of the reconstructed contaminant profiles for pesticides (such as dichlorodiphenyltrichloroethanes and chlordanes), polychlorinated biphenyls, and polybrominated diphenyl ethers demonstrate significant maternal transfer occurred at 0–12 mo. The total lifetime organic contaminant burden measured between the earplug (sum of contaminants in laminae layers) and blubber samples from the same organism were similar. Total mercury profiles revealed reduced maternal transfer and two distinct pulse events compared with organic contaminants. The use of a whale earplug to reconstruct lifetime chemical profiles will allow for a more comprehensive examination of stress, development, and contaminant exposure, as well as improve the assessment of contaminant use/emission, environmental noise, ship traffic, and climate change on these important marine sentinels. PMID:24043814

  2. Are Extreme T Dwarf Color Outliers Revealing Their Ages?

    NASA Astrophysics Data System (ADS)

    Mace, Gregory N.

    2014-01-01

    Brown dwarfs emerge as the low-mass products of the star formation process and then continue to cool. Those with temperatures between 500-1000K correspond to late-type T dwarf (≥ T7) spectral types. Using the Wide-field Infrared Survey Explorer (WISE) we have septupled the number of T dwarfs in this temperature regime, thereby creating a sizable sample with which to study overall trends and to identify outliers. I will present my spectrophotometric studies of this expanded population and compare the WISE discoveries to the samples revealed by 2MASS and UKIDSS. Additionally, I will discuss the newly discovered T8 subdwarf companion to Wolf 1130 and its utility as a high-gravity, low-metallicity benchmark. Late-type T dwarfs with redder J-H and bluer Y-J colors, as well as suppressed K-band flux, are likely revealing their old age. A broad survey of the most extreme late-type T dwarf color outliers can provide useful indicators of physical parameters. These indicators can then be applied to the diverse sample of directly imaged exoplanet and Y dwarf discoveries.

  3. Microsatellite genotyping reveals a signature in breast cancer exomes.

    PubMed

    McIver, L J; Fonville, N C; Karunasena, E; Garner, H R

    2014-06-01

    Genomic instability at microsatellite loci is a hallmark of many cancers, including breast cancer. However, much of the genomic variation and many of the hereditary components responsible for breast cancer remain undetected. We hypothesized that variation at microsatellites could provide additional genomic markers for breast cancer risk assessment. A total of 1,345 germline and tumor DNA samples from individuals diagnosed with breast cancer, exome sequenced as part of The Cancer Genome Atlas, were analyzed for microsatellite variation. The comparison group for our analysis, representing healthy individuals, consisted of 249 females which were exome sequenced as part of the 1,000 Genomes Project. We applied our microsatellite-based genotyping pipeline to identify 55 microsatellite loci that can distinguish between the germline of individuals diagnosed with breast cancer and healthy individuals with a sensitivity of 88.4 % and a specificity of 77.1 %. Further, we identified additional microsatellite loci that are potentially useful for distinguishing between breast cancer subtypes, revealing a possible fifth subtype. These findings are of clinical interest as possible risk diagnostics and reveal genes that may be of potential therapeutic value, including genes previously not associated with breast cancer.

  4. Invoking Thomas Kuhn: What Citation Analysis Reveals about Science Education

    NASA Astrophysics Data System (ADS)

    Loving, Cathleen C.; Cobern, William W.

    This paper analyzes how Thomas Kuhn's writings are used by others, especially science education researchers. Previous research in citation analysis is used to frame questions related to who cites Kuhn, in what manner and why. Research questions first focus on the variety of disciplines invoking Kuhn and to what extent Structure of Scientific Revolutions (SSR) is cited. The Web of Science database provides material from 1982 for this analysis. The science education literature is analyzed using back issues from 1985 of the Journal of Research in Science Teaching and Science Education. An article analysis reveals trends in terms of what Kuhnian ideas are most frequently invoked. Results indicate a wide array of disciplines from beekeeping to law cite Kuhn - especially generic citations to SSR. The science education journal analysis reveals pervasive use of the term paradigm, although use is quite varied. The two areas of research in science education most impacted by Kuhn appear to be conceptual change theory and constructivist epistemologies. Additional uses of Kuhn are discussed. The degree to which Kuhn is invoked in ways supporting the theoretical framework of citation analysis, whether his work is misappropriated, and the impact of Kuhn are discussed.

  5. [Research reveals a market for a veterinary behaviour clinic].

    PubMed

    Jonckheer-Sheehy, Valerie; Endenburg, Nienke

    2009-11-01

    An enquiry into the requirement of a university veterinary behaviour clinic in The Netherlands revealed that there is a clear call for such a service. The specific demands and wishes of first line practicing veterinarians and companion animal owners were investigated. The research revealed that veterinarians are regular confronted with behaviour problems in companion animals and that they are willing to refer these cases to the University. They also expressed their need for access to continuing professional development opportunities in the field of veterinary behavioural medicine (which is something that most veterinary behaviour clinics associated with veterinary faculties provide). The demand from companion animal owners was also examined. It can be concluded that a large number of them had animals with behaviour problems and that they were willing to seek veterinary advice on these matters. In response to the above mentioned demands the University of Utrecht will open a veterinary behaviour clinic, providing high quality service for animals, their owners and the referring veterinarians. This service will be based on sound scientific practice and delivered by both veterinarians specialised in this field and recognised animal behaviour therapists.

  6. Diffusion Tensor Imaging Reveals Evolution of Primate Brain Architectures

    PubMed Central

    Zhang, Degang; Guo, Lei; Zhu, Dajiang; Li, Kaiming; Li, Longchuan; Chen, Hanbo; Zhao, Qun; Hu, Xiaoping; Liu, Tianming

    2013-01-01

    Evolution of the brain has been an inherently interesting problem for centuries. Recent studies have indicated that neuroimaging is a powerful technique for studying brain evolution. In particular, a variety of reports have demonstrated that consistent white matter fiber connection patterns derived from diffusion tensor imaging (DTI) tractography reveal common brain architecture and are predictive of brain functions. In this paper, based on our recently discovered 358 Dense Individualized and Common Connectivity-based Cortical Landmarks (DICCCOL) defined by consistent fiber connection patterns in DTI datasets of human brains, we derived 65 DICCCOLs that are common in macaque monkey, chimpanzee and human brains and 175 DICCCOLs that exhibit significant discrepancies amongst these three primate species. Qualitative and quantitative evaluations not only demonstrated the consistencies of anatomical locations and structural fiber connection patterns of these 65 common DICCCOLs across three primates, suggesting an evolutionarily-preserved common brain architecture, but also revealed regional patterns of evolutionarily-induced complexity and variability of those 175 discrepant DICCCOLs across the three species. PMID:23135357

  7. Genome Sequencing Reveals a Phage in Helicobacter pylori

    PubMed Central

    Lehours, Philippe; Vale, Filipa F.; Bjursell, Magnus K.; Melefors, Ojar; Advani, Reza; Glavas, Steve; Guegueniat, Julia; Gontier, Etienne; Lacomme, Sabrina; Alves Matos, António; Menard, Armelle; Mégraud, Francis; Engstrand, Lars; Andersson, Anders F.

    2011-01-01

    ABSTRACT Helicobacter pylori chronically infects the gastric mucosa in more than half of the human population; in a subset of this population, its presence is associated with development of severe disease, such as gastric cancer. Genomic analysis of several strains has revealed an extensive H. pylori pan-genome, likely to grow as more genomes are sampled. Here we describe the draft genome sequence (63 contigs; 26× mean coverage) of H. pylori strain B45, isolated from a patient with gastric mucosa-associated lymphoid tissue (MALT) lymphoma. The major finding was a 24.6-kb prophage integrated in the bacterial genome. The prophage shares most of its genes (22/27) with prophage region II of Helicobacter acinonychis strain Sheeba. After UV treatment of liquid cultures, circular DNA carrying the prophage integrase gene could be detected, and intracellular tailed phage-like particles were observed in H. pylori cells by transmission electron microscopy, indicating that phage production can be induced from the prophage. PCR amplification and sequencing of the integrase gene from 341 H. pylori strains from different geographic regions revealed a high prevalence of the prophage (21.4%). Phylogenetic reconstruction showed four distinct clusters in the integrase gene, three of which tended to be specific for geographic regions. Our study implies that phages may play important roles in the ecology and evolution of H. pylori. PMID:22086490

  8. Blue whale earplug reveals lifetime contaminant exposure and hormone profiles.

    PubMed

    Trumble, Stephen J; Robinson, Eleanor M; Berman-Kowalewski, Michelle; Potter, Charles W; Usenko, Sascha

    2013-10-15

    Lifetime contaminant and hormonal profiles have been reconstructed for an individual male blue whale (Balaenoptera musculus, Linnaeus 1758) using the earplug as a natural aging matrix that is also capable of archiving and preserving lipophilic compounds. These unprecedented lifetime profiles (i.e., birth to death) were reconstructed with a 6-mo resolution for a wide range of analytes including cortisol (stress hormone), testosterone (developmental hormone), organic contaminants (e.g., pesticides and flame retardants), and mercury. Cortisol lifetime profiles revealed a doubling of cortisol levels over baseline. Testosterone profiles suggest this male blue whale reached sexual maturity at approximately 10 y of age, which corresponds well with and improves on previous estimates. Early periods of the reconstructed contaminant profiles for pesticides (such as dichlorodiphenyltrichloroethanes and chlordanes), polychlorinated biphenyls, and polybrominated diphenyl ethers demonstrate significant maternal transfer occurred at 0-12 mo. The total lifetime organic contaminant burden measured between the earplug (sum of contaminants in laminae layers) and blubber samples from the same organism were similar. Total mercury profiles revealed reduced maternal transfer and two distinct pulse events compared with organic contaminants. The use of a whale earplug to reconstruct lifetime chemical profiles will allow for a more comprehensive examination of stress, development, and contaminant exposure, as well as improve the assessment of contaminant use/emission, environmental noise, ship traffic, and climate change on these important marine sentinels.

  9. Reticulated lipid probe fluorescence reveals MDCK cell apical membrane topography.

    PubMed

    Colarusso, Pina; Spring, Kenneth R

    2002-02-01

    High spatial resolution confocal microscopy of young MDCK cells stained with the lipophilic probe 1,1'-dihexadecyl-3,3,3',3'- tetramethylindocarbocyanine perchlorate (DiIC(16)) revealed a reticulated fluorescence pattern on the apical membrane. DiIC(16) was delivered as crystals to live cells to minimize possible solvent perturbations of the membrane lipids. The ratio of the integrated fluorescence intensities in the bright versus dim regions was 1.6 +/- 0.1 (n = 13). Deconvolved images of the cells were consistent with exclusive plasma membrane staining. Multi-spectral and fluorescence anisotropy microscopy did not reveal differences between bright and dim regions. Bright regions coincided with microvilli and microridges observed by differential interference contrast microscopy and were stable for several minutes. Fluorescence recovery after photobleaching yielded similar diffusion coefficients (pooled D = 1.5 +/- 0.6 x 10(-9) cm(2)/s, n = 40) for both bright and dim regions. Line fluorescence recovery after photobleaching showed that the reticulated pattern was maintained as the fluorescence recovered in the bleached areas. Cytochalasin D did not affect the staining pattern, but the pattern was eliminated by cholesterol depletion with methyl-beta-cyclodextrin. We conclude that the reticulated fluorescence pattern was caused by increased optical path lengths through the microvilli and microridges compared with the flat areas on the apical membrane.

  10. Reticulated lipid probe fluorescence reveals MDCK cell apical membrane topography.

    PubMed Central

    Colarusso, Pina; Spring, Kenneth R

    2002-01-01

    High spatial resolution confocal microscopy of young MDCK cells stained with the lipophilic probe 1,1'-dihexadecyl-3,3,3',3'- tetramethylindocarbocyanine perchlorate (DiIC(16)) revealed a reticulated fluorescence pattern on the apical membrane. DiIC(16) was delivered as crystals to live cells to minimize possible solvent perturbations of the membrane lipids. The ratio of the integrated fluorescence intensities in the bright versus dim regions was 1.6 +/- 0.1 (n = 13). Deconvolved images of the cells were consistent with exclusive plasma membrane staining. Multi-spectral and fluorescence anisotropy microscopy did not reveal differences between bright and dim regions. Bright regions coincided with microvilli and microridges observed by differential interference contrast microscopy and were stable for several minutes. Fluorescence recovery after photobleaching yielded similar diffusion coefficients (pooled D = 1.5 +/- 0.6 x 10(-9) cm(2)/s, n = 40) for both bright and dim regions. Line fluorescence recovery after photobleaching showed that the reticulated pattern was maintained as the fluorescence recovered in the bleached areas. Cytochalasin D did not affect the staining pattern, but the pattern was eliminated by cholesterol depletion with methyl-beta-cyclodextrin. We conclude that the reticulated fluorescence pattern was caused by increased optical path lengths through the microvilli and microridges compared with the flat areas on the apical membrane. PMID:11806917

  11. Fluorescent aminoglycosides reveal intracellular trafficking routes in mechanosensory hair cells

    PubMed Central

    Hailey, Dale W.; Esterberg, Robert; Linbo, Tor H.; Rubel, Edwin W.; Raible, David W.

    2016-01-01

    Aminoglycosides (AGs) are broad-spectrum antibiotics that are associated with kidney damage, balance disorders, and permanent hearing loss. This damage occurs primarily by killing of proximal tubule kidney cells and mechanosensory hair cells, though the mechanisms underlying cell death are not clear. Imaging molecules of interest in living cells can elucidate how molecules enter cells, traverse intracellular compartments, and interact with sites of activity. Here, we have imaged fluorescently labeled AGs in live zebrafish mechanosensory hair cells. We determined that AGs enter hair cells via both nonendocytic and endocytic pathways. Both routes deliver AGs from the extracellular space to lysosomes, and structural differences between AGs alter the efficiency of this delivery. AGs with slower delivery to lysosomes were immediately toxic to hair cells, and impeding lysosome delivery increased AG-induced death. Therefore, pro-death cascades induced at early time points of AG exposure do not appear to derive from the lysosome. Our findings help clarify how AGs induce hair cell death and reveal properties that predict toxicity. Establishing signatures for AG toxicity may enable more efficient evaluation of AG treatment paradigms and structural modifications to reduce hair cell damage. Further, this work demonstrates how following fluorescently labeled drugs at high resolution in living cells can reveal important details about how drugs of interest behave. PMID:27991862

  12. Computational modeling reveals molecular details of epidermal growth factor binding

    PubMed Central

    Mayawala, Kapil; Vlachos, Dionisios G; Edwards, Jeremy S

    2005-01-01

    Background The ErbB family of receptors are dysregulated in a number of cancers, and the signaling pathway of this receptor family is a critical target for several anti-cancer drugs. Therefore a detailed understanding of the mechanisms of receptor activation is critical. However, despite a plethora of biochemical studies and recent single particle tracking experiments, the early molecular mechanisms involving epidermal growth factor (EGF) binding and EGF receptor (EGFR) dimerization are not as well understood. Herein, we describe a spatially distributed Monte Carlo based simulation framework to enable the simulation of in vivo receptor diffusion and dimerization. Results Our simulation results are in agreement with the data from single particle tracking and biochemical experiments on EGFR. Furthermore, the simulations reveal that the sequence of receptor-receptor and ligand-receptor reaction events depends on the ligand concentration, receptor density and receptor mobility. Conclusion Our computer simulations reveal the mechanism of EGF binding on EGFR. Overall, we show that spatial simulation of receptor dynamics can be used to gain a mechanistic understanding of receptor activation which may in turn enable improved cancer treatments in the future. PMID:16318625

  13. Circadian acetylome reveals regulation of mitochondrial metabolic pathways

    PubMed Central

    Masri, Selma; Patel, Vishal R.; Eckel-Mahan, Kristin L.; Peleg, Shahaf; Forne, Ignasi; Ladurner, Andreas G.; Baldi, Pierre; Imhof, Axel; Sassone-Corsi, Paolo

    2013-01-01

    The circadian clock is constituted by a complex molecular network that integrates a number of regulatory cues needed to maintain organismal homeostasis. To this effect, posttranslational modifications of clock proteins modulate circadian rhythms and are thought to convert physiological signals into changes in protein regulatory function. To explore reversible lysine acetylation that is dependent on the clock, we have characterized the circadian acetylome in WT and Clock-deficient (Clock−/−) mouse liver by quantitative mass spectrometry. Our analysis revealed that a number of mitochondrial proteins involved in metabolic pathways are heavily influenced by clock-driven acetylation. Pathways such as glycolysis/gluconeogenesis, citric acid cycle, amino acid metabolism, and fatty acid metabolism were found to be highly enriched hits. The significant number of metabolic pathways whose protein acetylation profile is altered in Clock−/− mice prompted us to link the acetylome to the circadian metabolome previously characterized in our laboratory. Changes in enzyme acetylation over the circadian cycle and the link to metabolite levels are discussed, revealing biological implications connecting the circadian clock to cellular metabolic state. PMID:23341599

  14. The Microbiome of Brazilian Mangrove Sediments as Revealed by Metagenomics

    PubMed Central

    Andreote, Fernando Dini; Jiménez, Diego Javier; Chaves, Diego; Dias, Armando Cavalcante Franco; Luvizotto, Danice Mazzer; Dini-Andreote, Francisco; Fasanella, Cristiane Cipola; Lopez, Maryeimy Varon; Baena, Sandra; Taketani, Rodrigo Gouvêa; de Melo, Itamar Soares

    2012-01-01

    Here we embark in a deep metagenomic survey that revealed the taxonomic and potential metabolic pathways aspects of mangrove sediment microbiology. The extraction of DNA from sediment samples and the direct application of pyrosequencing resulted in approximately 215 Mb of data from four distinct mangrove areas (BrMgv01 to 04) in Brazil. The taxonomic approaches applied revealed the dominance of Deltaproteobacteria and Gammaproteobacteria in the samples. Paired statistical analysis showed higher proportions of specific taxonomic groups in each dataset. The metabolic reconstruction indicated the possible occurrence of processes modulated by the prevailing conditions found in mangrove sediments. In terms of carbon cycling, the sequences indicated the prevalence of genes involved in the metabolism of methane, formaldehyde, and carbon dioxide. With respect to the nitrogen cycle, evidence for sequences associated with dissimilatory reduction of nitrate, nitrogen immobilization, and denitrification was detected. Sequences related to the production of adenylsulfate, sulfite, and H2S were relevant to the sulphur cycle. These data indicate that the microbial core involved in methane, nitrogen, and sulphur metabolism consists mainly of Burkholderiaceae, Planctomycetaceae, Rhodobacteraceae, and Desulfobacteraceae. Comparison of our data to datasets from soil and sea samples resulted in the allotment of the mangrove sediments between those samples. The results of this study add valuable data about the composition of microbial communities in mangroves and also shed light on possible transformations promoted by microbial organisms in mangrove sediments. PMID:22737213

  15. Exoproteome of Staphylococcus aureus reveals putative determinants of nasal carriage.

    PubMed

    Muthukrishnan, Gowrishankar; Quinn, Gerry A; Lamers, Ryan P; Diaz, Carolyn; Cole, Amy L; Chen, Sixue; Cole, Alexander M

    2011-04-01

    Due to the increasing prevalence of nosocomial and community-acquired antibiotic resistant Staphylococcus aureus (SA), understanding the determinants of SA nasal carriage has become a major imperative. Previous research has revealed many host and bacterial factors that contribute to SA nasal carriage. To assess bacterial factors that facilitate nasal carriage, we compared the exoproteome of a nasal carrier strain of SA to a genetically similar noncarrier strain. Additionally, the carrier strain biofilm exoproteome was also compared against its planktonic counterpart. Using high throughput proteomics, it was observed that the carrier strain of SA secretes a greater number of proteins that may promote successful colonization of the human nose, including cell attachment and immunoevasive proteins, than the noncarrier strain. Similarly, SA carrier strain biofilm exoproteome contains a greater number of immunoevasive proteins than its planktonic counterpart. Analysis of the most abundant immunoevasive proteins revealed that Staphylococcal protein A was present at significantly higher levels in carrier than in noncarrier strains of SA, suggesting an association with nasal carriage. While further analyses of specific differences between carrier and noncarrier strains of SA are required, many of the differentially expressed proteins identified can be considered to be putative determinants of nasal carriage.

  16. Exoproteome of Staphylococcus aureus reveals putative determinants of nasal carriage

    PubMed Central

    Muthukrishnan, Gowrishankar; Quinn, Gerry A.; Lamers, Ryan P.; Diaz, Carolyn; Cole, Amy L.; Chen, Sixue; Cole, Alexander M.

    2011-01-01

    Summary Due to the increasing prevalence of nosocomial and community-acquired antibiotic resistant Staphylococcus aureus (SA), understanding the determinants of SA nasal carriage has become a major imperative. Previous research has revealed many host and bacterial factors that contribute to SA nasal carriage. To assess bacterial factors that facilitate nasal carriage, we compared the exoproteome of a nasal carrier strain of SA to a genetically similar non-carrier strain. Additionally, the carrier strain biofilm exoproteome was also compared against its planktonic counterpart. Using high throughput proteomics, it was observed that the carrier strain of SA secretes a greater number of proteins that may promote successful colonization of the human nose, including cell attachment and immunoevasive proteins, than the non-carrier strain. Similarly, SA carrier strain biofilm exoproteome contains a greater number of immunoevasive proteins than its planktonic counterpart. Analysis of the most abundant immunoevasive proteins revealed that Staphylococcal protein A was present at significantly higher levels in carrier than in non-carrier strains of SA, suggesting an association with nasal carriage. While further analyses of specific differences between carrier and non-carrier strains of SA are required, many of the differentially expressed proteins identified can be considered to be putative determinants of nasal carriage. PMID:21338050

  17. Circulating protein synthesis rates reveal skeletal muscle proteome dynamics

    PubMed Central

    Shankaran, Mahalakshmi; King, Chelsea L.; Angel, Thomas E.; Holmes, William E.; Li, Kelvin W.; Colangelo, Marc; Price, John C.; Turner, Scott M.; Bell, Christopher; Hamilton, Karyn L.; Miller, Benjamin F.; Hellerstein, Marc K.

    2015-01-01

    Here, we have described and validated a strategy for monitoring skeletal muscle protein synthesis rates in rodents and humans over days or weeks from blood samples. We based this approach on label incorporation into proteins that are synthesized specifically in skeletal muscle and escape into the circulation. Heavy water labeling combined with sensitive tandem mass spectrometric analysis allowed integrated synthesis rates of proteins in muscle tissue across the proteome to be measured over several weeks. Fractional synthesis rate (FSR) of plasma creatine kinase M-type (CK-M) and carbonic anhydrase 3 (CA-3) in the blood, more than 90% of which is derived from skeletal muscle, correlated closely with FSR of CK-M, CA-3, and other proteins of various ontologies in skeletal muscle tissue in both rodents and humans. Protein synthesis rates across the muscle proteome generally changed in a coordinate manner in response to a sprint interval exercise training regimen in humans and to denervation or clenbuterol treatment in rodents. FSR of plasma CK-M and CA-3 revealed changes and interindividual differences in muscle tissue proteome dynamics. In human subjects, sprint interval training primarily stimulated synthesis of structural and glycolytic proteins. Together, our results indicate that this approach provides a virtual biopsy, sensitively revealing individualized changes in proteome-wide synthesis rates in skeletal muscle without a muscle biopsy. Accordingly, this approach has potential applications for the diagnosis, management, and treatment of muscle disorders. PMID:26657858

  18. The microbiome of Brazilian mangrove sediments as revealed by metagenomics.

    PubMed

    Andreote, Fernando Dini; Jiménez, Diego Javier; Chaves, Diego; Dias, Armando Cavalcante Franco; Luvizotto, Danice Mazzer; Dini-Andreote, Francisco; Fasanella, Cristiane Cipola; Lopez, Maryeimy Varon; Baena, Sandra; Taketani, Rodrigo Gouvêa; de Melo, Itamar Soares

    2012-01-01

    Here we embark in a deep metagenomic survey that revealed the taxonomic and potential metabolic pathways aspects of mangrove sediment microbiology. The extraction of DNA from sediment samples and the direct application of pyrosequencing resulted in approximately 215 Mb of data from four distinct mangrove areas (BrMgv01 to 04) in Brazil. The taxonomic approaches applied revealed the dominance of Deltaproteobacteria and Gammaproteobacteria in the samples. Paired statistical analysis showed higher proportions of specific taxonomic groups in each dataset. The metabolic reconstruction indicated the possible occurrence of processes modulated by the prevailing conditions found in mangrove sediments. In terms of carbon cycling, the sequences indicated the prevalence of genes involved in the metabolism of methane, formaldehyde, and carbon dioxide. With respect to the nitrogen cycle, evidence for sequences associated with dissimilatory reduction of nitrate, nitrogen immobilization, and denitrification was detected. Sequences related to the production of adenylsulfate, sulfite, and H(2)S were relevant to the sulphur cycle. These data indicate that the microbial core involved in methane, nitrogen, and sulphur metabolism consists mainly of Burkholderiaceae, Planctomycetaceae, Rhodobacteraceae, and Desulfobacteraceae. Comparison of our data to datasets from soil and sea samples resulted in the allotment of the mangrove sediments between those samples. The results of this study add valuable data about the composition of microbial communities in mangroves and also shed light on possible transformations promoted by microbial organisms in mangrove sediments.

  19. Economic Choices Reveal Probability Distortion in Macaque Monkeys

    PubMed Central

    Lak, Armin; Bossaerts, Peter; Schultz, Wolfram

    2015-01-01

    Economic choices are largely determined by two principal elements, reward value (utility) and probability. Although nonlinear utility functions have been acknowledged for centuries, nonlinear probability weighting (probability distortion) was only recently recognized as a ubiquitous aspect of real-world choice behavior. Even when outcome probabilities are known and acknowledged, human decision makers often overweight low probability outcomes and underweight high probability outcomes. Whereas recent studies measured utility functions and their corresponding neural correlates in monkeys, it is not known whether monkeys distort probability in a manner similar to humans. Therefore, we investigated economic choices in macaque monkeys for evidence of probability distortion. We trained two monkeys to predict reward from probabilistic gambles with constant outcome values (0.5 ml or nothing). The probability of winning was conveyed using explicit visual cues (sector stimuli). Choices between the gambles revealed that the monkeys used the explicit probability information to make meaningful decisions. Using these cues, we measured probability distortion from choices between the gambles and safe rewards. Parametric modeling of the choices revealed classic probability weighting functions with inverted-S shape. Therefore, the animals overweighted low probability rewards and underweighted high probability rewards. Empirical investigation of the behavior verified that the choices were best explained by a combination of nonlinear value and nonlinear probability distortion. Together, these results suggest that probability distortion may reflect evolutionarily preserved neuronal processing. PMID:25698750

  20. Ananke: temporal clustering reveals ecological dynamics of microbial communities

    PubMed Central

    Rohwer, Robin R.; Perrie, Jonathan; McMahon, Katherine D.

    2017-01-01

    Taxonomic markers such as the 16S ribosomal RNA gene are widely used in microbial community analysis. A common first step in marker-gene analysis is grouping genes into clusters to reduce data sets to a more manageable size and potentially mitigate the effects of sequencing error. Instead of clustering based on sequence identity, marker-gene data sets collected over time can be clustered based on temporal correlation to reveal ecologically meaningful associations. We present Ananke, a free and open-source algorithm and software package that complements existing sequence-identity-based clustering approaches by clustering marker-gene data based on time-series profiles and provides interactive visualization of clusters, including highlighting of internal OTU inconsistencies. Ananke is able to cluster distinct temporal patterns from simulations of multiple ecological patterns, such as periodic seasonal dynamics and organism appearances/disappearances. We apply our algorithm to two longitudinal marker gene data sets: faecal communities from the human gut of an individual sampled over one year, and communities from a freshwater lake sampled over eleven years. Within the gut, the segregation of the bacterial community around a food-poisoning event was immediately clear. In the freshwater lake, we found that high sequence identity between marker genes does not guarantee similar temporal dynamics, and Ananke time-series clusters revealed patterns obscured by clustering based on sequence identity or taxonomy. Ananke is free and open-source software available at https://github.com/beiko-lab/ananke. PMID:28966891