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Sample records for rod-like pyreneperylene bisimide

  1. Phosphorus-containing bisimide resins

    NASA Technical Reports Server (NTRS)

    Varma, I. K.; Fohlen, G. M.; Parker, J. A. (Inventor)

    1981-01-01

    The production of fire-resistant resins particularly useful for making laminates with inorganic fibers such as graphite fibers is discussed. The resins are by (1) condensation of an ethylenically unsaturated cyclic anhydride with a bis(diaminophenyl) phosphine oxide, and (2) by addition polymerization of the bisimide so obtained. Up to about 50%, on a molar basis, of benzophenonetetracarboxylic acid anhydride can be substituted for some of the cyclic anhydride to alter the properties of the products. Graphite cloth laminates made with these resins show 800 C char yields greater than 70% by weight in nitrogen. Limiting oxygen indexes of more than 100% are determined for these resins.

  2. Entropical Colloidal Interaction in Rod-like Molecules Solution

    NASA Astrophysics Data System (ADS)

    Hohlfeld, Evan B.; Lin, Keng-Hui; Zeri, Ana Carolina; Crocker, John C.; Yodh, Arjun G.

    2001-03-01

    We report direct measurements of the functional form of the depletion interaction between two colloidal spheres in a rod-like molecule suspension the line-scanned optical tweezer. The rod like moleculses are bacteriaphage fd with length (L) 880 nm and diameter(D) 6.5 nm and TMV with L 300 nm and D 200 nm. We probed different ratios of sphere radius R and rod length L and compared with theoretical models of Yaman^. The experimental data agrees with the model with slight discrepancy due to the flexibility of rod molecules. At high salt concentration, we also observed the steric repulsion due rod molecule stuck on the spheres. We gratefully acknowledge support from the NSF (DMR-9623441) and MRSEC (DMR-9632598). K. Yaman, C. Jeppesen and C.M. Marques, Europhys. Lett., 42, 221 (1998).

  3. New phosphorus-containing bisimide resins

    NASA Technical Reports Server (NTRS)

    Varma, I. K.; Fohlen, G. M.; Hsu, M.-T.; Parker, J. A.

    1984-01-01

    Phosphorus-based flame retardants have been effectively used in a wide variety of polymeric materials. Such additives, however, may either influence the decomposition reaction in polymers or lack durability due to a tendency to be leached out by solvents. Attention is given to the synthesis, characterization, thermal stability and degradation mechanisms of bisimide resins, and an evaluation is conducted of the flammability and mechanical properties of graphite cloth-reinforced laminates fabricated from one of the six phosphorus-containing bisimide resins considered.

  4. New phosphorus-containing bisimide resins

    NASA Technical Reports Server (NTRS)

    Varma, I. K.; Fohlen, G. M.; Hsu, M.-T.; Parker, J. A.

    1984-01-01

    Phosphorus-based flame retardants have been effectively used in a wide variety of polymeric materials. Such additives, however, may either influence the decomposition reaction in polymers or lack durability due to a tendency to be leached out by solvents. Attention is given to the synthesis, characterization, thermal stability and degradation mechanisms of bisimide resins, and an evaluation is conducted of the flammability and mechanical properties of graphite cloth-reinforced laminates fabricated from one of the six phosphorus-containing bisimide resins considered.

  5. Swimming in a suspension of rod-like molecules

    NASA Astrophysics Data System (ADS)

    Shi, Juan; Powers, Thomas

    2016-11-01

    In nature, it is common for microorganisms to swim in fluids with microstructure, such as mucus. Motivated by this fact, there have been many recent theoretical, computational, and experimental studies of idealized swimmers in a dilute solution of flexible polymers. Here we study this problem from a different point of view by considering swimmers in a dilute solution of rigid rod-like polymers. We study the prescribed swimming problem of Taylor's sheet in a dilute suspension of non-Brownian rods. Using a simple continuum constitutive law for the suspension that describes the stress in terms of velocity gradient and local rod orientation, we calculate swimming speed to second order in the amplitude of the wave. Due to stresses induced by the presence of the rods, the first-order flow field differs from that of the Newtonian case. We find that the swimming speed increases linearly with rod concentration: the presence of the rods always makes the swimmer go faster. We also consider the problem of a finite swimmer by studying a two-dimensional circular squirmer. The squirmer is defined as a circle with a prescribed tangential slip velocity that leads to propulsion. By varying the prescribed slip boundary condition, we study both pushers and pullers.

  6. 2-Hydroxypropyltrimethylammonium xylan adsorption onto rod-like cellulose nanocrystal.

    PubMed

    Sim, Jae Hyun; Dong, Shuping; Röemhild, Katrin; Kaya, Abdulaziz; Sohn, Daewon; Tanaka, Keiji; Roman, Maren; Heinze, Thomas; Esker, Alan R

    2015-02-15

    Chemical incompatibility and relatively weak interaction between lignocellulosic fibers and synthetic polymers have made studies of wood fiber-thermoplastic composite more challenging. In this study, adsorption of 2-hydroxypropyltrimethylammonium xylans onto rod-like cellulose nanocrystals are investigated by zeta-potential measurements, and polarized and depolarized dynamic light scattering as a factor for better understanding of lignocellulosic fibers and cellulose nanocrystals. Zeta-potential measurements show xylan derivative adsorption onto cellulose nanocrystals. Decay time distributions of the ternary system and binary system from dynamic light scattering show that aggregates exist in the binary system and they disappear in the ternary system. At low 2-hydroxypropyltrimethylammonium xylan concentrations relative to that of cellulose nanocrystal, xylan derivatives adsorbed onto some of the cellulose nanocrystal. Hence, more xylan derivatives adsorbed onto cellulose nanocrystal increased with increasing xylan derivative concentration. Also, the concentration dependence of the ratio of the rotational diffusion coefficient to the translational diffusion coefficient revealed a strong adsorptive interaction between xylan derivatives and the cellulose nanocrystals. Copyright © 2014 Elsevier Inc. All rights reserved.

  7. Giant faraday rotation in conjugated, rod-like molecules

    NASA Astrophysics Data System (ADS)

    Vleugels, Rick; Brullot, Ward; Verbiest, Thierry

    2016-09-01

    Faraday rotation is a magneto-optic phenomenon in which the polarization plane of light is rotated due to magnetically induced circular birefringence. It can be used in a variety of applications such as optical isolators, magnetic field sensors and current sensors. So far, most of the applications use inorganic, paramagnetic materials, which have Verdet constants up to millions of degrees per tesla per meter in the visible spectrum range. They are performant at telecommunication wavelengths, though with smaller Verdet constants, so thicker materials are used. Disadvantages of these materials are their magnetic saturation at low magnetic fields and their strong temperature dependency. Organic, diamagnetic materials on the contrary, saturate at much larger magnetic fields and are less temperature dependent. Furthermore, they also have the advantage of their flexibility and processability. Up to now, magneto-optical research on organic materials has mostly characterized materials with low magneto-optical activity in regions without absorption, but there are some exceptions. Some pi-conjugated polymers have been shown to have very large magneto-optic responses. Furthermore, a mesogenic, organic molecule has been reported with a very high Verdet constant. Conclusive explanations for these large Verdet constants are still lacking, but different possible hypotheses were proposed. In our ongoing search for organic materials with exceptional magneto-optical properties, we examined conjugated, rod-like molecules. Structural, these molecules show close resemblances with the earlier reported mesogenic, organic molecule. We measured giant Verdet constants for thin films of these molecules, reaching values almost as giant as the previous reported mesogenic molecule. These findings shed first preliminary light on a structure-activity relationship for giant Faraday rotation in diamagnetic organic materials.

  8. Orbital Processing of Eutectic Rod-Like Arrays

    NASA Technical Reports Server (NTRS)

    Larson, David J., Jr.

    1998-01-01

    The eutectic is one of only three solidification classes that exist. The others are isostructural and peritectic-class reactions, respectively. Simplistically, in a binaryeutectic phase diagram, a single liquid phase isothermally decomposes to two solid phases in a cooperative manner. The melting point minimum at the eutectic composition, isothermal solidification temperature, near-isocompositional solidification and refined solidification microstructure lend themselves naturally to such applications as brazing and soldering; industries that eutectic alloys dominate. Interest in direct process control of microstructures has led, more recently, to in-situ eutectic directional solidification with applications in electro-magnetics and electro-optics. In these cases, controlled structural refinement and the high aspect ratio and regularity of the distributed eutectic phases is highly significant to the fabrication and application of these in-situ natural composites. The natural pattern formation and scaling of the dispersed phase on a sub-micron scale has enormous potential application, since fabricating bulk materials on this scale mechanically has proven to be particularly difficult. It is thus of obvious importance to understand the solidification of eutectic materials since they are of great commercial significance. The dominant theory that describes eutectic solidification was derived for diffusion-controlled growth of alloys where both solid eutectic phases solidify metallically, i.e. without faceting at the solidification interface. Both high volume fraction (lamellar) and low volume fraction (rod-like) regular metallic arrays are treated by this theory. Many of the useful solders and brazements, however, and most of the regular in-situ composites are characterized by solidification reactions that are faceted/non-faceted in nature, rather than doubly non-faceted (metallic). Further, diffusion-controlled growth conditions are atypical terrestrially since

  9. Water-soluble and fluorescent dendritic perylene bisimides for live-cell imaging.

    PubMed

    Gao, Baoxiang; Li, Hongxia; Liu, Hongmei; Zhang, Licui; Bai, Qianqian; Ba, Xinwu

    2011-04-07

    We prepared dendritic perylene bisimide probes with triblock structures: perylene bisimides fluorescence cores, branched oligo(glutamic acid)s and polyethylene glycol chains. These probes showed good water solubility, low cytotoxicity and strong fluorescence in live cells.

  10. Structural, morphological, and optoelectronic properties of rod-like iron pyrite nanocrystals for solar cell applications

    NASA Astrophysics Data System (ADS)

    Tam Nguyen Truong, Nguyen; Nguyen, Thao Phuong Ngoc; Thanh Hau Pham, Viet; Thanh Trinh, Kieu; Lee, Sang-hoon; Park, Chinho

    2015-04-01

    Semiconducting, octadecylamine (ODA)-capped, rod-like FeS2 nanocrystals (NCs) are prepared and their properties are characterized. Transmission electron microscopy studies revealed the lattice fringes were clearly visible, confirming that the rod-like FeS2 NCs obtained in this study were highly crystalline. X-ray diffraction (XRD) studies indicated that the structure of FeS2 NCs is in cubic phase. Optical properties showed that the FeS2 NCs can be a promising candidate for the electron acceptor material in the bulk hetero-junction (BHJ) solar cell applications. The power conversion efficiency of the BHJ solar cells using polymer and the rod-like FeS2 NCs with a structure of glass/ITO/PEDOT:PSS/(FeS2+polymer)/Al was found to be ∼0.45%.

  11. Size Dependent Cellular Uptake of Rod-like Bionanoparticles with Different Aspect Ratios

    PubMed Central

    Liu, Xiangxiang; Wu, Fengchi; Tian, Ye; Wu, Man; Zhou, Quan; Jiang, Shidong; Niu, Zhongwei

    2016-01-01

    Understanding the cellular internalization mechanism of nanoparticles is essential to study their biological fate. Especially, due to the anisotropic properties, rod-like nanoparticles have attracted growing interest for the enhanced internalization efficiency with respect to spherical nanoparticles. Here, to elucidate the effect of aspect ratio of rod-like nanoparticles on cellular uptake, tobacco mosaic virus (TMV), a typical rod-like bionanoparticle, is developed as a model. Nanorods with different aspect ratios can be obtained by ultrasound treatment and sucrose density gradient centrifugation. By incubating with epithelial and endothelial cells, we found that the rod-like bionanoparticles with various aspect ratios had different internalization pathways in different cell lines: microtubules transport in HeLa and clathrin-mediated uptake in HUVEC for TMV4 and TMV8; caveolae-mediated pathway and microtubules transport in HeLa and HUVEC for TMV17. Differently from most nanoparticles, for all the three TMV nano-rods with different aspect ratios, macropinocytosis takes no effect on the internalization in both cell types. This work provides a fundamental understanding of the influence of aspect ratio on cellular uptake decoupled from charge and material composition. PMID:27080246

  12. Size Dependent Cellular Uptake of Rod-like Bionanoparticles with Different Aspect Ratios.

    PubMed

    Liu, Xiangxiang; Wu, Fengchi; Tian, Ye; Wu, Man; Zhou, Quan; Jiang, Shidong; Niu, Zhongwei

    2016-04-15

    Understanding the cellular internalization mechanism of nanoparticles is essential to study their biological fate. Especially, due to the anisotropic properties, rod-like nanoparticles have attracted growing interest for the enhanced internalization efficiency with respect to spherical nanoparticles. Here, to elucidate the effect of aspect ratio of rod-like nanoparticles on cellular uptake, tobacco mosaic virus (TMV), a typical rod-like bionanoparticle, is developed as a model. Nanorods with different aspect ratios can be obtained by ultrasound treatment and sucrose density gradient centrifugation. By incubating with epithelial and endothelial cells, we found that the rod-like bionanoparticles with various aspect ratios had different internalization pathways in different cell lines: microtubules transport in HeLa and clathrin-mediated uptake in HUVEC for TMV4 and TMV8; caveolae-mediated pathway and microtubules transport in HeLa and HUVEC for TMV17. Differently from most nanoparticles, for all the three TMV nano-rods with different aspect ratios, macropinocytosis takes no effect on the internalization in both cell types. This work provides a fundamental understanding of the influence of aspect ratio on cellular uptake decoupled from charge and material composition.

  13. System Plus Reservoir Approach to Quantum Brownian Motion of a Rod-Like Particle

    NASA Astrophysics Data System (ADS)

    Nasr, Z.; Kheirandish, F.

    2017-07-01

    Quantum Brownian motion of a rod-like particle is investigated in the frame work of system plus reservoir model. The quantum mechanical and classical limit for both translational and rotational motions are discussed. Correlation functions, fluctuation-dissipation relations and mean squared values of translational and rotational motions are obtained.

  14. Theory and simulations of toroidal and rod-like structures in single-molecule DNA condensation.

    PubMed

    Cortini, Ruggero; Caré, Bertrand R; Victor, Jean-Marc; Barbi, Maria

    2015-03-14

    DNA condensation by multivalent cations plays a crucial role in genome packaging in viruses and sperm heads, and has been extensively studied using single-molecule experimental methods. In those experiments, the values of the critical condensation forces have been used to estimate the amplitude of the attractive DNA-DNA interactions. Here, to describe these experiments, we developed an analytical model and a rigid body Langevin dynamics assay to investigate the behavior of a polymer with self-interactions, in the presence of a traction force applied at its extremities. We model self-interactions using a pairwise attractive potential, thereby treating the counterions implicitly. The analytical model allows to accurately predict the equilibrium structures of toroidal and rod-like condensed structures, and the dependence of the critical condensation force on the DNA length. We find that the critical condensation force depends strongly on the length of the DNA, and finite-size effects are important for molecules of length up to 10(5)μm. Our Langevin dynamics simulations show that the force-extension behavior of the rod-like structures is very different from the toroidal ones, so that their presence in experiments should be easily detectable. In double-stranded DNA condensation experiments, the signature of the presence of rod-like structures was not unambiguously detected, suggesting that the polyamines used to condense DNA may protect it from bending sharply as needed in the rod-like structures.

  15. Getting into shape: How do rod-like bacteria control their geometry?

    PubMed

    Amir, Ariel; van Teeffelen, Sven

    2014-09-01

    Rod-like bacteria maintain their cylindrical shapes with remarkable precision during growth. However, they are also capable to adapt their shapes to external forces and constraints, for example by growing into narrow or curved confinements. Despite being one of the simplest morphologies, we are still far from a full understanding of how shape is robustly regulated, and how bacteria obtain their near-perfect cylindrical shapes with excellent precision. However, recent experimental and theoretical findings suggest that cell-wall geometry and mechanical stress play important roles in regulating cell shape in rod-like bacteria. We review our current understanding of the cell wall architecture and the growth dynamics, and discuss possible candidates for regulatory cues of shape regulation in the absence or presence of external constraints. Finally, we suggest further future experimental and theoretical directions which may help to shed light on this fundamental problem.

  16. Preparation of hydroxyapatite rod-like crystals by protein precursor method

    SciTech Connect

    Han Yingchao; Li Shipu . E-mail: zlhyc@yahoo.com.cn; Wang Xinyu; Jia Li; He Jianhua

    2007-06-05

    Hydroxyapatite (HAP) rod-like crystals were successfully prepared by thermolysis of bovine serum albumin (BSA)/calcium-phosphate (CaP) colloidal precursors. The precursors were obtained by precipitation method from Ca(H{sub 2}PO{sub 4}){sub 2} and Ca(OH){sub 2}, in which BSA was added as regulation additive and ultrasound irradiation was utilized as assistant technology. The properties of the precursors, such as size distribution, morphology, thermodynamic changes, were determined by DLS, SPM and TGA-DTA. The characterization results from DLS, SPM, TG-DTA, XRD and SEM indicated that BSA interacted with CaP particles and formed about 7-130 nm BSA/CaP hybrid colloidal particles between 2 and 4 g/L of BSA concentration. With the increasing of sintering temperature, BSA disintegrated and burned out, and rod-like HAP crystals formed at about 600 deg. C. With the increasing of BSA concentration, the phase composition of products did not change and the HAP crystals became more uniform and smaller. The ratio of length to width ranged from 7.6 to 12 at 4 g/L BSA concentration. This method provides for a controllable bottom-up fabrication of HAP rod-like crystals.

  17. Rod-like bacterial shape is maintained by feedback between cell curvature and cytoskeletal localization

    PubMed Central

    Ursell, Tristan S.; Nguyen, Jeffrey; Monds, Russell D.; Colavin, Alexandre; Billings, Gabriel; Ouzounov, Nikolay; Gitai, Zemer; Shaevitz, Joshua W.; Huang, Kerwyn Casey

    2014-01-01

    Cells typically maintain characteristic shapes, but the mechanisms of self-organization for robust morphological maintenance remain unclear in most systems. Precise regulation of rod-like shape in Escherichia coli cells requires the MreB actin-like cytoskeleton, but the mechanism by which MreB maintains rod-like shape is unknown. Here, we use time-lapse and 3D imaging coupled with computational analysis to map the growth, geometry, and cytoskeletal organization of single bacterial cells at subcellular resolution. Our results demonstrate that feedback between cell geometry and MreB localization maintains rod-like cell shape by targeting cell wall growth to regions of negative cell wall curvature. Pulse-chase labeling indicates that growth is heterogeneous and correlates spatially and temporally with MreB localization, whereas MreB inhibition results in more homogeneous growth, including growth in polar regions previously thought to be inert. Biophysical simulations establish that curvature feedback on the localization of cell wall growth is an effective mechanism for cell straightening and suggest that surface deformations caused by cell wall insertion could direct circumferential motion of MreB. Our work shows that MreB orchestrates persistent, heterogeneous growth at the subcellular scale, enabling robust, uniform growth at the cellular scale without requiring global organization. PMID:24550515

  18. Biotemplating rod-like viruses for the synthesis of copper nanorods and nanowires

    PubMed Central

    2012-01-01

    Background In the past decade spherical and rod-like viruses have been used for the design and synthesis of new kind of nanomaterials with unique chemical positioning, shape, and dimensions in the nanosize regime. Wild type and genetic engineered viruses have served as excellent templates and scaffolds for the synthesis of hybrid materials with unique properties imparted by the incorporation of biological and organic moieties and inorganic nanoparticles. Although great advances have been accomplished, still there is a broad interest in developing reaction conditions suitable for biological templates while not limiting the material property of the product. Results We demonstrate the controlled synthesis of copper nanorods and nanowires by electroless deposition of Cu on three types of Pd-activated rod-like viruses. Our aqueous solution-based method is scalable and versatile for biotemplating, resulting in Cu-nanorods 24–46 nm in diameter as measured by transmission electron microscopy. Cu2+ was chemically reduced onto Pd activated tobacco mosaic virus, fd and M13 bacteriophages to produce a complete and uniform Cu coverage. The Cu coating was a combination of Cu0 and Cu2O as determined by X- ray photoelectron spectroscopy analysis. A capping agent, synthesized in house, was used to disperse Cu-nanorods in aqueous and organic solvents. Likewise, reactions were developed to produce Cu-nanowires by metallization of polyaniline-coated tobacco mosaic virus. Conclusions Synthesis conditions described in the current work are scalable and amenable for biological templates. The synthesized structures preserve the dimensions and shape of the rod-like viruses utilized during the study. The current work opens the possibility of generating a variety of nanorods and nanowires of different lengths ranging from 300 nm to micron sizes. Such biological-based materials may find ample use in nanoelectronics, sensing, and cancer therapy. PMID:22548773

  19. Effect of the ortho alkylation of perylene bisimides on the alignment and self-assembly properties.

    PubMed

    Dasgupta, Debarshi; Kendhale, Amol M; Debije, Michael G; Ter Schiphorst, Jeroen; Shishmanova, Ivelina K; Portale, Giuseppe; Schenning, Albertus P H J

    2014-08-01

    The effect of the ortho alkylation of perylene bisimides on the alignment and self-assembly properties has been studied. It was found that the dichroic properties of perylene bisimides in a liquid crystal host can be reversed with a single synthetic step by ortho alkylation. Furthermore, a solvent-induced growth of ultralong organic n-type semiconducting fibrils from non-ortho-alkylated perylene bisimide was observed. Ortho substitution of the perylene bisimide core alters the mode of fibrillar growth, leading to isotropic crystallization.

  20. Evaluation of two bisimide additives in LARC-TPI adhesive

    NASA Technical Reports Server (NTRS)

    Progar, Donald J.; Stclair, Terry L.

    1990-01-01

    The processability of aromatic polyimides can be improved by the addition of bis (amide) acids or bisimides to LARC-TPI. These low molecular weight additives apparently lower the melt viscosity of aromatic polyimides without affecting the glass transition temperature. Well-consolidated, fiber reinforced composites were fabricated using this technology. LARC-TPI can be processed as a thermoplastic polyimide to form high strength bonds, however, this is generally accomplished by processing at relatively high bonding pressures. An adhesive investigation is presented on the effects of two bisimide additives to LARC-TPI in an attempt to improve the bonding process by lowering the viscosity of the material to achieve improved bond strength properties. Apparently, the high flow which is exhibited by the additives when they melt, tended to be masked by the more viscous LARC-TPI.

  1. High performance mixed bisimide resins and composites based thereon

    NASA Technical Reports Server (NTRS)

    Parker, J. A.; ations.

    1986-01-01

    Mixtures of bismaleimide/biscitraconirnide resins produces materials which have better handling, processing or mechanical and thermal properties, particularly in graphite composites, than materials made with the individual resins. The mechanical strength of cured graphite composites prepared from a 1:1 copolymer of such bisimide resins is excellent at both ambient and elevated temperatures. The copolymer mixture provides improved composites which are lighter than metals and replace metals in many aerospace applications.

  2. Dynamic light scattering studies on charged rod-like fd-virus in dilute aqueous solution

    NASA Astrophysics Data System (ADS)

    Schulz, Susanne F.; Maier, Erich E.; Krause, Rainer; Hagenbüchle, Martin; Deggelmann, Martin; Weber, Reinhart

    1990-06-01

    Time correlation functions of the scattered light intensity are studied in aqueous solutions of charged rod-like fd-virus (L=880 nm, d=6 nm) at various ionic strengths. The short time behavior of the correlation function is dominated by the static structure factor S(q) which is also independently determined from static light scattering experiments. Comparison of correlation functions of solutions with high ionic strength (screened Coulomb interaction) and those of solutions with liquid-like nearest neighbor order (strong Coulomb interaction) shows different single particle diffusion coefficients on medium time scales at high scattering vectors, where mainly single particle properties are observed by light scattering. The single particle diffusion coefficient decreases with increasing structure peak height of the solutions. At low scattering vectors an extra slow mode component of the correlation function is observed for solutions with Coulomb interaction.

  3. Statistical foundations of liquid-crystal theory: I. Discrete systems of rod-like molecules.

    PubMed

    Seguin, Brian; Fried, Eliot

    2012-12-01

    We develop a mechanical theory for systems of rod-like particles. Central to our approach is the assumption that the external power expenditure for any subsystem of rods is independent of the underlying frame of reference. This assumption is used to derive the basic balance laws for forces and torques. By considering inertial forces on par with other forces, these laws hold relative to any frame of reference, inertial or noninertial. Finally, we introduce a simple set of constitutive relations to govern the interactions between rods and find restrictions necessary and sufficient for these laws to be consistent with thermodynamics. Our framework provides a foundation for a statistical mechanical derivation of the macroscopic balance laws governing liquid crystals.

  4. Distinct Tissue Mineral Density in Plate- and Rod-like Trabeculae of Human Trabecular Bone.

    PubMed

    Wang, Ji; Kazakia, Galateia J; Zhou, Bin; Shi, X Tony; Guo, X Edward

    2015-09-01

    Trabecular bone quality includes both microstructural and intrinsic tissue mineralization properties. However, the tissue mineralization in individual trabeculae of different trabecular types and orientations has not yet been investigated. The aim of this study was to develop an individual trabecula mineralization (ITM) analysis technique to determine tissue mineral density (TMD) distributions in plate- and rod-like trabeculae, respectively, and to compare the TMD of trabeculae along various orientations in micro-computed tomography (μCT) images of trabecular bone samples from the femoral neck, greater trochanter, and proximal tibia. ITM analyses indicated that trabecular plates, on average, had significantly higher TMD than trabecular rods. In addition, the distribution of TMD in trabecular plates depended on trabecular orientation with the lowest TMD in longitudinal plates and the highest TMD in transverse plates. Conversely, there was a relatively uniform distribution of TMD among trabecular rods, with respect to trabecular orientation. Further analyses of TMD distribution revealed that trabecular plates had higher mean and peak TMD, whereas trabecular rods had a wider TMD distribution and a larger portion of low mineralized trabeculae. Comparison of apparent Young's moduli derived from micro-finite element models with and without heterogeneous TMD demonstrated that heterogeneous TMD in trabecular plates had a significant influence on the elastic mechanical property of trabecular bone. In conclusion, this study revealed differences in TMD between plate- and rod-like trabeculae and among various trabecular orientations. The observation of less mineralized longitudinal trabecular plates suggests interesting implications of these load-bearing plates in bone remodeling. The newly developed ITM analysis can be a valuable technique to assess the influence of metabolic bone diseases and their pharmaceutical treatments on not only microstructure of trabecular bone but

  5. Building multistate redox-active architectures using metal-complex functionalized perylene bis-imides.

    PubMed

    Goretzki, Gudrun; Davies, E Stephen; Argent, Stephen P; Warren, John E; Blake, Alexander J; Champness, Neil R

    2009-11-02

    A series of multistate redox-active architectures has been synthesized, structurally characterized, and their optical and redox properties investigated. Specifically, two redox-active ferrocene or cobalt-dithiolene moieties have been introduced to the "bay" region of perylene-bisimides. Three of these disubstituted perylene-bisimide species have been structurally characterized by single crystal X-ray diffraction, confirming the twisted nature of the central perylene core. The first isomeric pair of disubstituted perylene-bisimide isomers, N,N'-di-(n-butyl)-1,7-diferrocenyl-perylene-3,4:9,10-tetracarboxylic acid bisimide (2) and N,N'-di-(n-butyl)-1,6-diferrocenyl-perylene-3,4:9,10-tetracarboxylic acid bisimide (3), structurally characterized by single crystal X-ray diffraction are reported and compared. Structural characterization of the cobalt-dithiolene substituted perylene-bisimide, N,N'-di-(n-butyl)-1,7-dicyclopentadienyl-cobalt(II)-dithiolenyl-perylene-3,4:9,10-tetracarboxylic acid bisimide (4), reveals the expected twisting of the perylene core and confirms the ene-dithiolate geometry of the cobalt dithiolene moiety. Cyclic voltammetry measurements, coupled with spectroelectrochemcial and electron paramagnetic resonance studies, of 1-4, where 1 is N,N'-di-(n-butyl)-1,7-diethynylferrocenyl-perylene-3,4:9,10-tetracarboxylic acid bisimide, reveal the two anticipated perylene-bisimide based reductions. In addition, for the ferrocene substituted compounds, 1-3, a single reversible two-electron oxidation is seen with only a small degree of communication between the ferrocene groups observed in the 1,6-isomer where the two ferrocene groups are attached to the same naphthyl moiety. In the case of 4, two reversible reductions associated with the cobalt-dithiolene moieties are observed, confirming communication across the reduced perylene core.

  6. LptA Assembles into Rod-Like Oligomers Involving Disorder-to-Order Transitions

    NASA Astrophysics Data System (ADS)

    Santambrogio, Carlo; Sperandeo, Paola; Villa, Riccardo; Sobott, Frank; Polissi, Alessandra; Grandori, Rita

    2013-10-01

    LptA is a periplasmic protein involved in the transport of lipopolysaccharide (LPS) from the inner membrane (IM) to the outer membrane (OM) of Gram-negative bacteria. Growing evidence supports a model in which LptA assembles into oligomers, forming a physical bridge connecting IM and OM. This work investigates assembly and architecture of LptA oligomers. Circular dichroism and "native" electrospray-ionization ion-mobility mass spectrometry (ESI-IM-MS) are employed to test concentration dependence of LptA structural features and to analyze the morphology of higher-order aggregates. The results show that LptA progressively assembles into rod-like oligomers without fixed stoichiometry, and grows by an n + 1 mechanism up to at least the pentamer. The oligomerization process induces disorder-to-order transitions in the polypeptide chain. Comparison with crystallographic and computational data suggests that these conformational changes likely involve short disordered regions at the N- and C-termini of monomeric LptA. The protein response to thermal denaturation displays strong concentration dependence, indicating that oligomerization increases protein stability. LptA conformational stability can also be enhanced by in vitro LPS binding. The genesis of these fibrillar structures could be relevant for the correct transport of LPS across the bacterial periplasm.

  7. Rod-like cyanophenyl probe molecules nanoconfined to oxide particles: Density of adsorbed surface species

    NASA Astrophysics Data System (ADS)

    Frunza, Stefan; Frunza, Ligia; Ganea, Constantin Paul; Zgura, Irina; Brás, Ana Rita; Schönhals, Andreas

    2016-02-01

    Surface layers have already been observed by broadband dielectric spectroscopy for composite systems formed by adsorption of rod-like cyanophenyl derivates as probe molecules on the surface of oxide particles. In this work, features of the surface layer are reported; samples with different amounts of the probe molecules adsorbed onto oxide (nano) particles were prepared in order to study their interactions with the surface. Thermogravimetric analysis (TGA) was applied to analyze the amount of loaded probe molecules. The density of the surface species ns was introduced and its values were estimated from quantitative Fourier transform infrared spectroscopy (FTIR) coupled with TGA. This parameter allows discriminating the composites into several groups assuming a similar interaction of the probe molecules with the hosts of a given group. An influence factor H is further proposed as the ratio of the number of molecules in the surface layer showing a glassy dynamics and the number of molecules adsorbed tightly on the surface of the support: It was found for aerosil composites and used for calculating the maximum filling degree of partially filled silica MCM-41 composites showing only one dielectric process characteristic for glass-forming liquids and a bulk behavior for higher filling degrees.

  8. [Biomimetic mineralization of rod-like cellulose nano-whiskers and spectrum analysis].

    PubMed

    Qu, Ping; Wang, Xuan; Cui, Xiao-xia; Zhang, Li-ping

    2012-05-01

    Cellulose nano-whiskers/nano-hydroxyapatite composite was prepared with biomimetic mineralization using rod-like cellulose nano-whiskers as template. The cellulose nano-whiskers and cellulose nano-whiskers/nano-hydroxyapatite composite were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscope-energy dispersive analysis of X-rays (SEM-EDXA). Variation and distribution of carbon, oxygen, calcium, and phosphorus in the composites were studied. The morphologies and growth mechanism of nano-hydroxyapatite were analyzed. The results showed that nano-hydroxyapatite was formed on the surface of cellulose nano-whiskers; the carbon-oxygen ratio of cellulose nano-whiskers and cellulose nano-whiskers/nano-hydroxyapatite composite was 1.81 and 1.54, respectively; the calcium-phosphorus ratio of the composite was 1.70. The nucleation of nano-hydroxyapatite was around the hydroxyl groups of cellulose nano-whiskers. It is suggested that there is coordination between the hydroxyl groups of cellulose nano-whiskers and calcium ions of nano-hydroxyapatite. The nano-hydroxyapatite can distribute in the matrix of cellulose nano-whiskers. From the atomic force microscope (AFM) images, we can see that the diameter of the spherical nano-hydroxyapatite particles was about 20 nm.

  9. Translation of rod-like template sequences into homochiral assemblies of stacked helical oligomers

    NASA Astrophysics Data System (ADS)

    Gan, Quan; Wang, Xiang; Kauffmann, Brice; Rosu, Frédéric; Ferrand, Yann; Huc, Ivan

    2017-05-01

    At the molecular level, translation refers to the production of a new entity according to a template that has a different chemical composition. In this way, chemical information may be translated from one molecule to another. The process is useful to synthesize structures and thus functions that might be difficult to create otherwise, and it reaches exquisite levels of efficiency in biological systems, as illustrated by protein expression from mRNA templates or by the assembly of the tobacco mosaic virus capsid protein according to the length of its RNA. In synthetic systems, examples of template-directed syntheses are numerous, but general and versatile schemes in which a non-natural sequence actually encodes the information necessary to produce a different sequence are few and far from being optimized. Here we show a high-fidelity enzyme-free translation of long rod-like alkylcarbamate oligomers into well-defined sequences of stacked helical aromatic oligoamides. The features present in the rods, which include the number and distance between carbamate functions and stereogenic centres, template the self-assembly of complementary stacks of helices that each have a defined right (P) or left (M) handedness, length and single or double helicity. This process enables the production of very large (>20 kDa) abiotic artificial folded architectures (foldamers) that may, for example, serve as scaffolds to organize appended functional features at positions in space defined with atomic precision across nanometric distances.

  10. DNA-wrapped Carbon nanotubes as a model rod-like colloid system

    NASA Astrophysics Data System (ADS)

    Zheng, Ming

    2013-03-01

    Single-wall carbon nanotubes (SWCNTs) exhibit many fascinating physical behavior as the result of their quasi one-dimensional crystalline structures. SWCNTs can be dispersed into rod-like colloid particles by a few small molecules and polymers, among which the most effect one is single-stranded DNA (Nature Materials 2, 338, 2003). The structure of a DNA-SWCNT hybrid is controlled by both the sequence of the wrapping DNA, and the atomic configuration, or chirality, of the SWCNT (Science 302, 1545, 2003). This has been exploited by us to purify single-chirality SWCNTs from synthetic mixtures via liquid chromatography (Nature 460, 250, 2009; JACS 133, 12998, 2011). DNA-SWCNTs have well-defined surface structures, tunable aspect-ratios, and ultra-small diameters. These attributes provide unique advantages to the DNA-SWCNT colloid system in probing inter-particle interactions in crowded and high salt environment (ACS Nano 5, 8258, 2011). In this talk, I will present some recent observations we made on DNA-SWCNT clustering that shed new light on the Hofmeister effect.

  11. Molecular dynamics in rod-like liquid crystals probed by muon spin resonance spectroscopy.

    PubMed

    McKenzie, Iain; Scheuermann, Robert; Sedlak, Kamil; Stoykov, Alexey

    2011-08-04

    Muoniated spin probes were produced by the addition of muonium (Mu) to two rod-like liquid crystals: N-(4-methoxybenzylidene)-4'-n-butylaniline (MBBA) and cholesteryl nonanoate (CN). Avoided level crossing muon spin resonance spectroscopy was used to characterize the muoniated spin probes and to probe dynamics at the molecular level. In MBBA Mu adds predominantly to the carbon of the bridging imine group and the muon and methylene proton hyperfine coupling constants (hfccs) of the resulting radical shift in the nematic phase due to the dipolar hyperfine coupling, the ordering of the molecules along the applied magnetic field and fluctuations about the local director. The amplitude of these fluctuations in in the nematic phase of MBBA is determined from the temperature dependence of the methylene proton hfcc. Mu adds to the double bond of the steroidal ring system of CN and the temperature dependence of the Δ(1) line width provides information about the amplitude of the fluctuations about the local director in the chiral nematic phase and the slow isotropic reorientation in the isotropic phase.

  12. Size-controlled synthesis of rod-like α-FeOOH nanostructure.

    PubMed

    Wei, Chengzhen; Qiao, Penghui; Nan, Zhaodong

    2012-08-01

    One-dimensional goethite (α-FeOOH) nanorods were successfully fabricated by a hydrothermal route without any template. Experimental results reveal that concentrations of Fe(3+) and ethylenediaminetetraacetic disodium salt (Na2EDTA) affect the phase composition and size of the as-synthesized products. The size of the rod-like α-FeOOH increased when the concentration of Na2EDTA was increased, where Na2EDTA acts as a nucleation inhibitor. α-Fe2O3 nanoparticles were produced when the concentration of Fe(3+) was increased from 0.02 to 0.08 and 0.40 M. A possible formation mechanism was proposed based on the results of the time dependent experiments. Different electrolytes and surfactants can affect the size and the aspect ratio of the as-prepared nanorod-like α-FeOOH. Na2SO4 induced the decreasing of the size of the as-prepared sample. KCl and PVP affected the aspect ratio of the nanorods.

  13. Transformation of amorphous calcium carbonate to rod-like single crystal calcite via "copying" collagen template.

    PubMed

    Xue, Zhonghui; Hu, Binbin; Dai, Shuxi; Du, Zuliang

    2015-10-01

    Collagen Langmuir films were prepared by spreading the solution of collagen over deionized water, CaCl2 solution and Ca(HCO3)2 solution. Resultant collagen Langmuir monolayers were then compressed to a lateral pressure of 10 mN/m and held there for different duration, allowing the crystallization of CaCO3. The effect of crystallization time on the phase composition and microstructure of CaCO3 was investigated. It was found that amorphous calcium carbonate (ACC) was obtained at a crystallization time of 6 h. The amorphous CaCO3 was transformed to rod-like single crystal calcite crystals at an extended crystallization time of 12 h and 24 h, via "copying" the symmetry and dimensionalities of collagen fibers. Resultant calcite crystallites were well oriented along the longitudinal axis of collagen fibers. The ordered surface structure of collagen fibers and electrostatic interactions played key roles in tuning the oriented nucleation and growth of the calcite crystallites. The mineralized collagen possessing both desired mechanical properties of collagen fiber and good biocompatibility of calcium carbonate may be assembled into an ideal biomaterial for bone implants.

  14. Mucin aggregation from a rod-like meso-scale model

    NASA Astrophysics Data System (ADS)

    Moreno, Nicolas; Perilla, Jairo E.; Colina, Coray M.; Lísal, Martin

    2015-05-01

    Dissipative particle dynamics, a meso-scale particle-based model, was used to study the aggregation of mucins in aqueous solutions. Concentration, strength of the mucin-water interactions, as well as the effects of size, shape, and composition of the model molecules were studied. Model proteins were represented as rod-like objects formed by coarse-grained beads. In the first model, only one type of beads formed the mucin. It was found that all the surfaces were available to form aggregates and the conformation of the aggregates was a function of the strength of the mucin-water interaction. With this model, the number of aggregates was unaffected by the initial position of the mucins in the simulation box, except for the lowest mucin concentration. In a more refined mucin model, two kinds of beads were used in the molecule in order to represent the existence of cysteine-like terminal groups in the actual molecule. With this new scheme, aggregation took place by the interaction of the terminal groups between model molecules. The kinetic analysis of the evolution of the number of aggregates with time was also studied for both mucin models.

  15. Perylene bisimide derivatives as innovative sensitizers for photorefractive composites

    NASA Astrophysics Data System (ADS)

    Schemme, Thomas; Ditte, Katharina; Travkin, Evgenij; Jiang, Wei; Wang, Zhaohui; Denz, Cornelia

    2012-06-01

    In photorefractive composites, we replace the commonly used fullerene derivative phenyl-C61-butyric acid methyl ester (PCBM) by the perylene bisimide dimer DiPBI. In samples, wherein poly-n-vinylcarbazole (PVK) is the charge transporting agent and 4-cyano-4-n-pentylbiphenyl (5CB) the nonlinear optical unit, we observe dramatic enhancements in the overall performance of the composites. When we replace PVK by N,N-diphenyl-N, N-bis(3-methylphenyl)-[1, 1-biphenyl]-4, 4-diamine (TPD) doped polystyrene (PS), the internal photocurrent efficiency is further improved by a factor 11.

  16. Electric Field Light Scattering by Rod-Like Polyelectrolytes in Aqueous Suspensions

    NASA Astrophysics Data System (ADS)

    Martin, C.; Weyerich, B.; Biegel, J.; Deike, R.; Johner, C.; Klein, R.; Weber, R.

    1995-05-01

    Static light scattering measurements are presented for rod-like fd-virus particles (L=880 nm, D= 9 nm) subjected to a pulsed alternating electric field in aqueous suspensions at very low ionic strength. In aqueous suspensions the dispersed fd-particles are negatively charged and surrounded by a diffuse Debye counterion cloud. In an external electric field an induced dipole originating from a deformation of the diffuse counterion cloud causes the alignment of the macromolecules. The anisotropic orientation distribution of the particles in the presence of the electric field results in a change of the angular distribution of the scattered light intensity with regard to the isotropic case. The steady-state electric field light scattering effect Δ I/I_0 is measured as a function of the electric field strength and its frequency at a fixed scattering angle. The determination of the anisotropy of the electric polarizability Δα_el of a fd-virus particle at higher electric field strengths, above the Kerr regime, shows a decrease of Δα_el with increasing field. This is interpreted as a destruction of the diffuse Debye cloud in high electric fields. The orientational order parameter has been found to be as large as 0.93 indicating an almost complete particle orientation along the external field at the highest fields. It is also shown that in the frequency regime below 1 kHz electrostatically interacting rods can align perpendicular to the external electric field, whereas at higher frequencies this anomalous behaviour disappears. From the scattered intensity the form-factor and the static structure factor of interacting fd-virus particles have been determined. With increasing fields a substantial increase in the peak height of the static structure factor is found. The data is in good agreement with Monte Carlo simulations using a simple interaction model for the system. The orientation of the macromolecules in the presence of an electric field is affected by the

  17. Competing mechanisms in the wear resistance behavior of biomineralized rod-like microstructures

    NASA Astrophysics Data System (ADS)

    Escobar de Obaldia, Enrique; Herrera, Steven; Grunenfelder, Lessa Kay; Kisailus, David; Zavattieri, Pablo

    2016-11-01

    guidelines for abrasion resistance rod-like microstructures in composites with high volume fraction of brittle minerals or ceramics with tailored performance for specific applications.

  18. Green and highly efficient synthesis of perylene and naphthalene bisimides in nothing but water.

    PubMed

    Baumgartner, Bettina; Svirkova, Anastasiya; Bintinger, Johannes; Hametner, Christian; Marchetti-Deschmann, Martina; Unterlass, Miriam M

    2017-01-19

    High-purity, symmetrically substituted perylene and naphthalene bisimides were obtained by hydrothermal condensation of monoamines with the corresponding bisanhydride. The hydrothermal imidization proceeds quantitatively, without the need for organic solvents, catalysts or excess of the amines.

  19. Donor-linked di(perylene bisimide)s: arrays exhibiting fast electron transfer for photosynthesis mimics.

    PubMed

    Wu, Yishi; Zhen, Yonggang; Wang, Zhaohui; Fu, Hongbing

    2013-02-28

    The first example of donor-linked di(perylene bisimide)s is reported. UV-vis absorption spectra of these newly synthesized dyads showed intense absorption across the entire visible region, demonstrating their excellent light-harvesting activities. The severe fluorescence quenching event probed by steady-state fluorescence spectroscopy and the free-energy calculations suggested the possibility of electron transfer (ET) in these arrays upon photoexcitation. Further femtosecond transient absorption spectra clarified that the fluorescence quenching was due to fast intramolecular ET. The rate of the charge separation (CS) was found to be as high as 10(12) s(-1) in CH(2)Cl(2). It was suggested that the large ET driving forces, strong donor-acceptor electronic coupling, and relatively small reorganization energy of diPBI accounted for the rapid ET process in a synergic manner. The fate of the generated radical ion pair depended on the solvent used. Rapid charge recombination to ground state occurred for the dyads in polar CH(2)Cl(2) and for diPBI-TPA in nonpolar toluene. However, sufficient (3)diPBI* population was attained via efficient spin-orbit coupled intersystem crossing from the charge-separated state for diPBI-PdTPP in toluene. These photophysical properties are interpreted as the cooperation between thermodynamic feasibility and kinetic manipulation.

  20. Synthesis of Titanate/polypyrrole Composite Rod-Like Particles and the Role of Conducting Polymer on Electrorheological Efficiency

    NASA Astrophysics Data System (ADS)

    Mrlik, Miroslav; Pavlinek, Vladimir; Cheng, Qilin; Saha, Petr

    In this paper, we study the preparation of titanate/polypyrrole core-shell rod-like composite particles. The mere titanate rod-like particles were prepared as core material and PPy was polymerized on their surface in different amounts. Rheological measurements showed that under an applied external electric field, shear stress of these materials significantly increased with amount of PPy in the shell layer. The yield stresses obtained from the Cho-Choi-Jhon model were correlated with dielectric properties of suspensions. Polarizability as a measure of particle polarization obtained from Havriliak-Negami model of dielectric spectra increases with the content of PPy in the samples. Furthermore, role of particle concentration and silicone oil viscosity was also investigated.

  1. Magnetorheology of core-shell carbonyl iron/ZnO rod-like particle silicone oil suspensions under oscillatory shear

    NASA Astrophysics Data System (ADS)

    Mrlik, M.; Machovsky, M.; Pavlinek, V.; Kuritka, I.

    2015-04-01

    The aim of this study is a preparation and application of inorganic coating on the surface of carbonyl iron particles. The two step solvothermal synthesis provides core-shell CI/ZnO rod-like morphology. Compact coating of particles has a slightly negative impact on their magnetic properties (measured for magnetic field strength in the range from 0 to 213 mT); however, there is a suitable magnetorheological performance investigated under oscillatory shear, suitable to be applied in real applications.

  2. Synthesis and predetermined supramolecular chirality of carbohydrate-functionalized perylene bisimide derivatives.

    PubMed

    Wang, Ke-Rang; Han, Dan; Cao, Guo-Jing; Li, Xiao-Liu

    2015-05-01

    Eight carbohydrate-modified perylene bisimides (PBI-4 lac-2 lac, PBI-4 lac-2 Man, PBI-4 lac-2 Gal, PBI-4 lac-2 Mal, PBI-4 Man-2 Man, PBI-4 Man-2 lac, PBI-4 Man-2 Gal and PBI-4 Man-2 Mal) were synthesized, and the following predetermined supramolecular chirality rule was found: perylene bisimides modified with disaccharides (D-lactose and D-maltose) at the imide position generated right-handed chirality, and those modified with monosaccharides (D-mannose and D-galactose) generated left-handed chirality, when D-lactose or D-mannose was substituted in the bay positions of perylene bisimides with amide bonds as the linking spacers. These results may be because of the difference in the stacking angle of the perylene bisimide backbones induced by the steric effect and the additional hydrogen bonds between the disaccharide residues. This study provides an important design rule for predetermined chiral self-assembly of perylene bisimides.

  3. TiO{sub 2} supported on rod-like mesoporous silica SBA-15: Preparation, characterization and photocatalytic behaviour

    SciTech Connect

    Li, Yanjuan; Li, Nan; Tu, Jinchun; Li, Xiaotian; Wang, Beibei; Chi, Yue; Liu, Darui; Yang, Dianfan

    2011-12-15

    Highlights: Black-Right-Pointing-Pointer Rod-like SBA-15 and normal SBA-15 were used to prepare TiO{sub 2}/SBA-15 composites. Black-Right-Pointing-Pointer TiO{sub 2}/SBA-15 composites were studied as catalysts for methyl orange photodegradation. Black-Right-Pointing-Pointer TiO{sub 2}/Rod-SBA-15 exhibited higher photocatalytic activity than TiO{sub 2}/Nor-SBA-15. Black-Right-Pointing-Pointer The higher catalytic activity was a result of the controlled morphology of SBA-15. -- Abstract: TiO{sub 2} nanoparticles have been successfully incorporated in the pores of mesoporous silica SBA-15 with different morphologies by a wet impregnation method. The composites were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), inductively coupled plasma (ICP) emission spectroscopy, transmission electron microscopy (TEM), N{sub 2}-sorption and UV-Vis diffuse reflectance spectroscopy. The photodegradation of methyl orange (MO) was used to study their photocatalytic property. It is indicated that the morphology of SBA-15 had a great influence on the photocatalytic activity of the composites. When TiO{sub 2}/SBA-15 composite was prepared by loading TiO{sub 2} nanoparticles on uniform rod-like SBA-15 of 1 {mu}m length, it showed higher photocatalytic degradation rate than that on less regular but much larger SBA-15 support. This difference was rationalized in terms of the homogeneously distributed and shorter channels of rod-like SBA-15, which favored mass transport and improved the efficient utilization of the pore surface.

  4. Highly active ZnO rod-like nanomaterials: Synthesis, characterization and photocatalytic activity for dye removal

    NASA Astrophysics Data System (ADS)

    Hafez, Hoda S.

    2012-04-01

    Highly active ZnO rod-like nanostructures with pointed-shape ends have been synthesized via a simple hydrothermal method using acetic acid as an organic capping agent. The X-ray diffraction (XRD) pattern of the prepared sample reveals that the ZnO rod-like nanostructures are of pure hexagonal wurtzite structure. Morphology of the nanorods has been investigated by transmission electron microscope (TEM), which showed the formation of pointed nanorods of 30-50 nm in diameter and 400-650 nm in length. Optical properties have been investigated by UV-vis diffuse reflectance and photoluminescence spectroscopy. UV-vis absorption spectrum indicated that the ZnO nanorods have higher visible light harvesting as compared to the other morphologies in the literature. Intense room temperature green-red photoluminescence peaks at 486 nm and 564 nm has been observed for the prepared ZnO. This gives a good evidence of the presence of ionized oxygen vacancies which are favorable for photocatalytic reactions. The BET surface area and the average (BJH) adsorption pore size were 269.86 m2/g and 2.86 nm, respectively. The photocatalytic activity of the prepared sample was tested on the degradability of an industrial textile dye, Reactive Yellow 15 (Yellow GR), under sunlight irradiation. A 85.7% dye removal was achieved by applications of these rod-like nanostructures as a photocatalyst. The reusability of the synthesized ZnO nanomaterial has been investigated under the same experimental conditions for three time to evaluate the photoactivity of the photocatalyst.

  5. Electrorheological behaviour under oscillatory shear of TiO2 rod-like particles prepared via microwave-assisted molten-salt synthesis

    NASA Astrophysics Data System (ADS)

    Sedlacik, M.; Mrlik, M.; Pavlinek, V.; Kozakova, Z.; Saha, P.

    2013-02-01

    Titanium dioxide (TiO2) rod-like particles were synthesized by a simple and rapid microwave-assisted molten-salt method. The X-ray diffraction analysis and electron microscopy provided information on particle composition and morphology, respectively. It was found that during the synthesis process the crystalline phase of TiO2 transformed from anatase into rutile while the morphology changed from nanospheres into micrometer sized rod-like particles. The electrorheological (ER) properties were investigated via oscillatory shear tests. It was found that TiO2 rod-like particles based silicone oil suspensions exhibited higher ER activity than those of original anatase TiO2 nanoparticles probably due to side-by-side solid friction between particles as well as shorter time of their polarization. The changes in ER properties of rod-like particle based suspensions as a function of the applied electric field strength and particles weight fraction were also investigated.

  6. Anatomical evidence for cone and rod-like receptors in the gray squirrel, ground squirrel, and prairie dog retinas.

    PubMed

    West, R W; Dowling, J E

    1975-02-15

    In the gray squirrel (Sciurus carolinensis), the prairie dog (Cynomys ludovicianus), and the Mexican and 13-line ground squirrels (Citellus mexicanus and C. tridecemlineatus) there exist two distinct classes of photo-receptors that have cone-like and rod-like anatomical features respectively. These two receptor classes were previously known to exist in the gray squirrel, but only the cone-like (C) receptor had been observed in the other species. We have now found small numbers of rod-like (R) receptors in the other species as well. R-receptors comprise about 40% of the receptors in the gray squirrel, 10% of the receptors in the prairie dog, and 4-5% of the receptors in the two species of ground squirrel. This paper describes certain light and electron microscopic features of these two receptor classes including their synaptic connections with second-order cells and with each other. We find that the C-receptor has a morphology and synaptic organization characteristic of other mammalian cones. However, the R-receptor differs from other mammalian rods in certain morphological respects, and its synaptic organization has both cone and rod characteristics as well as some unusual features.

  7. Functional and Molecular Characterization of Rod-like Cells from Retinal Stem Cells Derived from the Adult Ciliary Epithelium

    PubMed Central

    Demontis, Gian Carlo; Aruta, Claudia; Comitato, Antonella; De Marzo, Anna; Marigo, Valeria

    2012-01-01

    In vitro generation of photoreceptors from stem cells is of great interest for the development of regenerative medicine approaches for patients affected by retinal degeneration and for high throughput drug screens for these diseases. In this study, we show unprecedented high percentages of rod-fated cells from retinal stem cells of the adult ciliary epithelium. Molecular characterization of rod-like cells demonstrates that they lose ciliary epithelial characteristics but acquire photoreceptor features. Rod maturation was evaluated at two levels: gene expression and electrophysiological functionality. Here we present a strong correlation between phototransduction protein expression and functionality of the cells in vitro. We demonstrate that in vitro generated rod-like cells express cGMP-gated channels that are gated by endogenous cGMP. We also identified voltage-gated channels necessary for rod maturation and viability. This level of analysis for the first time provides evidence that adult retinal stem cells can generate highly homogeneous rod-fated cells. PMID:22432014

  8. Rod-like β-FeOOH@poly(dopamine)-Au-poly(dopamine) nanocatalysts with improved recyclable activities.

    PubMed

    Mao, Ya; Jiang, Wanquan; Xuan, Shouhu; Fang, Qunling; Leung, Ken Cham-Fai; Ong, Beng S; Wang, Sheng; Gong, Xinglong

    2015-05-28

    A novel rod-like β-FeOOH@poly(dopamine)-Au-poly(dopamine) nanocomposite is developed for recyclable catalysis. Firstly, the rod-like β-FeOOH template was coated in situ by a layer of poly(dopamine) (PDA) to form a core/shell nanostructure. Then the negatively charged Au nanocatalysts were well-immobilized onto the periphery of the β-FeOOH@PDA nanorod. To protect the Au nanocrystals from leaching during the catalytic reactions, another PDA layer was coated onto the above particles to form a sandwich-like PDA-Au-PDA shell on the β-FeOOH rod core. The reduction of Rhodamine B (RhB) was introduced as a model reaction to evaluate the catalytic activity of the as-prepared nanocomposites. It was found that the catalytic rate sharply increased with an increasing amount of the nanocatalyst. Benefitting from the thin outer layer of PDA, the recyclability of the nanocatalyst dramatically increased. After five times of catalytic reaction, the activity was maintained as high as 98.3%, while the β-FeOOH@PDA-Au showed it to be retained at only 73.4%.

  9. Syntheses and Chemosensory of Anthracene and Phenanthrene Bisimide Derivatives

    NASA Technical Reports Server (NTRS)

    Bogusz, Zachary A.

    2004-01-01

    As the present technology of biochemical weapons advances, it is essential for science to attempt to prepare our nation for such an occurrence. Various areas of current research are devoted to precautionary measures and potential antidotes for national security. A practical application of these precautions would be the development of a chemical capable of detecting harmful gas. The benefits of being capable to synthesis a chemical compound that would warn and identify potentially deadly gases would ensure a higher level of safety. The chemicals in question can be generalized as bisimide anthracene derivatives. The idea behind these compounds is that in the presence of certain nerve gases, the compound will actually fluoresce, giving an indication that there is a strong likelihood of the presence of a nerve gas and ensure the proper precautionary measures are taken. The fluorescence is due to the quenching of an electric proton transfer within the structure of the molecule. The system proves to be very unique on account of the fact that the fluorescence can be "turned off" by reducing the system. By utilizing the synthesis designed by Dr. Faysal Ilhan, four distinct compounds can be synthesized through photochemical reactions involving para- and ortho- diketones. The photochemistry involved is very modem and much research is being devoted to fully understanding the possibilities and alternative applications of such materials. and meta-nitro anthracene bisimide (ABI-NO2), the amine of each (ABI-NH2), a para- and meta-nitro phenanthrene bisimjde (PBI-NO2), and the amine of each (PBI-NH2). Upon synthesizing these distinct compounds, I must then purify and analyze them in order to obtain any relevant trends, behaviors, and characteristics. The chemical composition analyses that will be conducted are the procedures taken by Dr. Daniel Tyson on previous experiments. The results generated from the data will point further research in the correct direction and hopefully

  10. Syntheses and Chemosensory of Anthracene and Phenanthrene Bisimide Derivatives

    NASA Technical Reports Server (NTRS)

    Bogusz, Zachary A.

    2004-01-01

    As the present technology of biochemical weapons advances, it is essential for science to attempt to prepare our nation for such an occurrence. Various areas of current research are devoted to precautionary measures and potential antidotes for national security. A practical application of these precautions would be the development of a chemical capable of detecting harmful gas. The benefits of being capable to synthesis a chemical compound that would warn and identify potentially deadly gases would ensure a higher level of safety. The chemicals in question can be generalized as bisimide anthracene derivatives. The idea behind these compounds is that in the presence of certain nerve gases, the compound will actually fluoresce, giving an indication that there is a strong likelihood of the presence of a nerve gas and ensure the proper precautionary measures are taken. The fluorescence is due to the quenching of an electric proton transfer within the structure of the molecule. The system proves to be very unique on account of the fact that the fluorescence can be "turned off" by reducing the system. By utilizing the synthesis designed by Dr. Faysal Ilhan, four distinct compounds can be synthesized through photochemical reactions involving para- and ortho- diketones. The photochemistry involved is very modem and much research is being devoted to fully understanding the possibilities and alternative applications of such materials. and meta-nitro anthracene bisimide (ABI-NO2), the amine of each (ABI-NH2), a para- and meta-nitro phenanthrene bisimjde (PBI-NO2), and the amine of each (PBI-NH2). Upon synthesizing these distinct compounds, I must then purify and analyze them in order to obtain any relevant trends, behaviors, and characteristics. The chemical composition analyses that will be conducted are the procedures taken by Dr. Daniel Tyson on previous experiments. The results generated from the data will point further research in the correct direction and hopefully

  11. Random copolyesters containing perylene bisimide: flexible films and fluorescent fibers.

    PubMed

    Nisha, S Kumari; Asha, S K

    2014-08-13

    Random copolyesters of poly(l-lactic acid) (PLLA) and [poly(1,4-cyclohexylenedimethylene-1,4- cyclohexanedicarboxylate)] (PCCD) incorporating varying mol ratios of perylene bisimide (PBI) were developed via a high-temperature solution-blending approach. PCCD incorporating PBI was developed by melt polycondenzation followed by a polyester-polyester transesterification reaction between PCCD-PBI and PLLA. The polymers exhibited good solubility in common organic solvents and formed free-standing films, which showed bright red emission upon irradiation with ultraviolet radiation. A solid state fluorescence quantum yield of 10% was observed for this PBI based polyester, which was much higher than that reported in literature for PBI based polymers in the solid state (<1%). Strong red fluorescent nanofibers of these polymers were successfully constructed by electrospinning technique. A random copolyester incorporating donor based on oligo(p-pheneylenevinylene) (OPV) and PBI as acceptor chromophore was also synthesized and fluorescence microscopy images of the electrospun fibers of this polymer exhibited blue, green and red emission upon excitation at different wavelengths. The high temperature solution blending approach involving a high molecular weight polymer and a suitably functionalized π conjugated molecule described here is a unique method by which 1D nanostructures of a wide range of π-conjugated chromophores could be fabricated having strong fluorescence, with the scope of application in nanoscale optoelectronics, biological devices, as well as sensing.

  12. Assembly of DNA triangles mediated by perylene bisimide caps.

    PubMed

    Menacher, Florian; Stepanenko, Vladimir; Würthner, Frank; Wagenknecht, Hans-Achim

    2011-06-06

    Perylene bisimides (PBI) have been synthetically incorporated as caps onto a Y-shaped DNA triple strand. These PBI caps serve as "sticky" ends in the spontaneous assembly of larger DNA ensembles, linking the triangular DNA through stacking interactions. This, in turn, yields a hypsochromic shift in the absorption and a red shift in the fluorescence as characteristic optical readouts. This assembly occurs spontaneously without any enzymatic ligation process and without the use of overhanging DNA as sticky ends. Instead, dimerizations of the PBI chromophores in the assembly are controlled by the DNA as a structural scaffold. Thereby, the PBI-driven assembly is fully reversible. Due to the fact that PBI dimerization does not occur in the single strand, the aggregates can be destroyed by thermal dehybridization of the DNA scaffold and reassembled by reannealing of the DNA construct. In view of the fact that PBI forms stable radical anions, the presented DNA architectures are not only interesting optical biomaterials, but are also promising materials for molecular electronics with DNA.

  13. Tetrahedral Arrangements of Perylene Bisimide Columns via Supramolecular Orientational Memory.

    PubMed

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

    2017-01-24

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

  14. Complete separation of macroscopic rod-like bimetallic nanoassembly perpendicular and parallel on substrate for simultaneous sensing of microorganisms

    NASA Astrophysics Data System (ADS)

    Jia, HaoWei; Wang, Jin; Qiu, Li; Ge, HongGua

    2015-10-01

    Although two kinds of macroscopic ordered tridimensional nanoassemblies, i.e., alignment of nanorods, can be yielded by controllable droplet evaporation methods, complete separation of the nanoassembly perpendicular or parallel to substrate is quite challenging. It can, however, be realized by the aid of facet blocking combined with the tuning of ionic strength and colloidal concentration. The as-fabricated rod-like bimetallic nanoassembly has proved to be an excellent SERS active substrate compared to random aggregates. It should be mentioned that macroscopic ordered tridimensional nanoassembly perpendicular to the substrate can be used as a highly active SERS substrate with good uniformity and can be successfully applied for finely discriminating two microorganisms: Escherichia coli bacteria and Saccharomycetes.

  15. Penetration of spherical and rod-like gold nanoparticles into intact and barrier-disrupted human skin

    NASA Astrophysics Data System (ADS)

    Graf, Christina; Nordmeyer, Daniel; Ahlberg, Sebastian; Raabe, Jörg; Vogt, Annika; Lademann, Jürgen; Rancan, Fiorenza; Rühl, Eckart

    2015-03-01

    The penetration of spherical and rod-like gold nanoparticles into human skin is reported. Several skin preparation techniques are applied, including cryo techniques, such as plunge freezing and freeze drying, and the use of wet cells. Their advantages and drawbacks for observing nanoparticle uptake are discussed. Independent of the particle shape no uptake into intact skin is observed by a combination of imaging approaches, including scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), and scanning X-ray microscopy (STXM). These results are discussed along with suitable skin preparation approaches. Experiments on barrier-disrupted skin, i.e. mechanical lesions made by pricking, indicate, however, that gold particles can be identified deep in the dermis, as follows from STXM studies on wet skin samples.

  16. Controllable synthesis of novel zinc molybdate rod-like nanostructures via simple surfactant-free precipitation route

    NASA Astrophysics Data System (ADS)

    Shahri, Zahra; Bazarganipour, Mehdi; Salavati-Niasari, Masoud

    2013-11-01

    Zinc molybdate rod-like nanostructures have been successfully synthesized by precipitation method process and using a solid organometallic molecular precursor [bis(salicylaldehydato)zinc(II)], Zn(sal)2, and (NH4)6Mo7O24·4H2O as starting materials. Some parameters including time effect, temperature effect, and surfactant effect were investigated to reach the optimum conditions. The as synthesized nanostructures were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmittance electron microscopy (TEM) and Fourier transform infrared (FT-IR) spectra. Facile preparation and separation are important features of this route. This work has provided a general, simple, and effective method to control the composition and morphology of zinc molybdate in aqueous solution, which will be important for inorganic synthesis methodology.

  17. Directional Freezing of Nanocellulose Dispersions Aligns the Rod-Like Particles and Produces Low-Density and Robust Particle Networks.

    PubMed

    Munier, Pierre; Gordeyeva, Korneliya; Bergström, Lennart; Fall, Andreas B

    2016-05-09

    We show that unidirectional freezing of nanocellulose dispersions produces cellular foams with high alignment of the rod-like nanoparticles in the freezing direction. Quantification of the alignment in the long direction of the tubular pores with X-ray diffraction shows high orientation of cellulose nanofibrils (CNF) and cellulose nanocrystals (CNC) at particle concentrations above 0.2 wt % (CNC) and 0.08 wt % (CNF). Aggregation of CNF by pH decrease or addition of salt significantly reduces the particle orientation; in contrast, exceeding the concentration where particles gel by mobility constraints had a relatively small effect on the orientation. The dense nanocellulose network formed by directional freezing was sufficiently strong to resist melting. The formed hydrogels were birefringent and displayed anisotropic laser diffraction patterns, suggesting preserved nanocellulose alignment and cellular structure. Nondirectional freezing of the hydrogels followed by sublimation generates foams with a pore structure and nanocellulose alignment resembling the structure of the initial directional freezing.

  18. Binary mixtures of rod-like colloids under shear: microscopically-based equilibrium theory and order-parameter dynamics.

    PubMed

    Lugo-Frías, Rodrigo; Klapp, Sabine H L

    2016-06-22

    This paper is concerned with the dynamics of a binary mixture of rod-like, repulsive colloidal particles driven out of equilibrium by means of a steady shear flow (Couette geometry). To this end we first derive, starting from a microscopic density functional in Parsons-Lee approximation, a mesoscopic free energy functional whose main variables are the orientational order parameter tensors. Based on this mesoscopic functional we then explore the stability of isotropic and nematic equilibrium phases in terms of composition and rod lengths. Second, by combining the equilibrium theory with the Doi-Hess approach for the order parameter dynamics under shear, we investigate the orientational dynamics of binary mixtures for a range of shear rates and coupling parameters. We find a variety of dynamical states, including synchronized oscillatory states of the two components, but also symmetry breaking behavior where the components display different in-plane oscillatory states.

  19. Local viscosity and solvent relaxation experienced by rod-like fluorophores in AOT/4-chlorophenol/m-xylene organogels

    NASA Astrophysics Data System (ADS)

    Dandapat, Manika; Mandal, Debabrata

    2017-01-01

    Organogels prepared from AOT/4-chlorophenol/m-xylene are immobile in the macroscopic sense, with a well-characterized internal structure. However, the molecular level dynamics inside the gels is not too clear, although a very slow structural relaxation has been reported previously. Using a set of rod-like fluorophores, we find that the rotational mobility of a small guest molecule inside the gel can be extremely fast, indicating presence of sufficiently low-microviscosity domains. These domains consist of m-xylene solvent molecules trapped in the interstices of fiber bundles comprising columnar stacks of 4-chlorophenol surrounded by AOT molecules. However, interstitial trapping of m-xylene does retard its own dynamics, which explains the slow solvent relaxation inside the gels. Hence, the state of m-xylene in the organogel may be characterized as "bound", in contrast to the "free" state in neat m-xylene.

  20. Rod-like particles matching algorithm based on SOM neural network in dispersed two-phase flow measurements

    NASA Astrophysics Data System (ADS)

    Abbasi Hoseini, Afshin; Zavareh, Zahra; Lundell, Fredrik; Anderson, Helge I.

    2014-04-01

    A matching algorithm based on self-organizing map (SOM) neural network is proposed for tracking rod-like particles in 2D optical measurements of dispersed two-phase flows. It is verified by both synthetic images of elongated particles mimicking 2D suspension flows and direct numerical simulations-based results of prolate particles dispersed in a turbulent channel flow. Furthermore, the potential benefit of this algorithm is evaluated by applying it to the experimental data of rod-like fibers tracking in wall turbulence. The study of the behavior of elongated particles suspended in turbulent flows has a practical importance and covers a wide range of applications in engineering and science. In experimental approach, particle tracking velocimetry of the dispersed phase has a key role together with particle image velocimetry of the carrier phase to obtain the velocities of both phases. The essential parts of particle tracking are to identify and match corresponding particles correctly in consecutive images. The present study is focused on the development of an algorithm for pairing non-spherical particles that have one major symmetry axis. The novel idea in the algorithm is to take the orientation of the particles into account for matching in addition to their positions. The method used is based on the SOM neural network that finds the most likely matching link in images on the basis of feature extraction and clustering. The fundamental concept is finding corresponding particles in the images with the nearest characteristics: position and orientation. The most effective aspect of this two-frame matching algorithm is that it does not require any preliminary knowledge of neither the flow field nor the particle behavior. Furthermore, using one additional characteristic of the non-spherical particles, namely their orientation, in addition to its coordinate vector, the pairing is improved both for more reliable matching at higher concentrations of dispersed particles and

  1. Structural and optical properties of a perylene bisimide in aqueous media

    NASA Astrophysics Data System (ADS)

    Burian, Max; Rigodanza, Francesco; Amenitsch, Heinz; Almásy, László; Khalakhan, Ivan; Syrgiannis, Zois; Prato, Maurizio

    2017-09-01

    The aggregation of a water soluble, dicationic perylene bisimide derivative was studied by means of absorption and emission spectroscopies, X-ray and neutron scattering techniques as well as electron microscopy. The results provide evidence for the existence of higher order molecular aggregates in solution, potentially utilizable in device fabrication as super molecular building blocks.

  2. Photoinduced processes in self-assembled porphyrin/perylene bisimide metallosupramolecular boxes.

    PubMed

    Indelli, M Teresa; Chiorboli, Claudio; Scandola, Franco; Iengo, Elisabetta; Osswald, Peter; Würthner, Frank

    2010-11-18

    Two new supramolecular boxes, (ZnMC)(2)(rPBI)(2) and (ZnMC)(2)(gPBI)(2), have been obtained by axial coordination of N,N'-dipyridyl-functionalized perylene bisimide (PBI) dyes to the zinc ion centers of two 2+2 porphyrin metallacycles (ZnMC = [trans,cis,cis-RuCl(2)(CO)(2)(Zn·4'-cis-DPyP)](2)). The two molecular boxes involve PBI pillars with different substituents at the bay area: the "red" PBI (rPBI = N,N'-di(4-pyridyl)-1,6,7,12-tetra(4-tert-butylphenoxy)perylene-3,4:9,10-tetracarboxylic acid bisimide) containing tert-butylphenoxy substituents and the "green" PBI (gPBI = N,N'-di(4-pyridyl)-1,7-bis(pyrrolidin-1-yl)perylene-3,4:9,10-tetracarboxylic acid bisimide) bearing pyrrolidinyl substituents. Due to the rigidity of the modules and the simultaneous formation of four pyridine-zinc bonds, these discrete adducts self-assemble quantitatively and are remarkably stable in dichloromethane solution. The photophysical behavior of the new supramolecular boxes has been studied in dichloromethane by emission spectroscopy and ultrafast absorption techniques. A different photophysical behavior is observed for the two systems. In (ZnMC)(2)(rPBI)(2), efficient electron transfer quenching of both perylene bisimide and zinc porphyrin chromophores is observed, leading to a charge separated state, PBI(-)-Zn(+), in which a perylene bisimide unit is reduced and zinc porphyrin is oxidized. In the deactivation of the perylene bisimide localized excited state, an intermediate zwitterionic charge transfer state of type PBI(-)-PBI(+) seems to play a relevant role. In (ZnMC)(2)(gPBI)(2), singlet energy transfer from the Zn porphyrin chromophores to the perylene bisimide units occurs with an efficiency of 0.7. This lower than unity value is due to a competing electron transfer quenching, leading to the charge separated state PBI(-)-Zn(+). The distinct photophysical behavior of these two supramolecular boxes is interpreted in terms of energy changes occurring upon replacement of the "red" r

  3. Facile Synthesis of Rod-like Cu2-x Se and Insight into its Improved Lithium-Storage Property.

    PubMed

    Li, He; Jiang, Jiali; Wang, Feng; Huang, Jianxing; Wang, Yunhui; Zhang, Yiyong; Zhao, Jinbao

    2017-05-22

    A rod-like Cu2-x Se is synthesized by a facile water evaporation process. The electrochemical reaction mechanism is investigated by ex situ X-ray diffraction (XRD). By adopting an ether-based electrolyte instead of a carbonate-based electrolyte, the electrochemical performance of Cu2-x Se electrodes improved significantly. The Cu2-x Se electrodes exhibit outstanding cycle performance: after 1000 cycles, 160 mA h g(-1) can be maintained with a retention of 80.3 %. At current densities of 100, 200, 500, and 1000 mA g(-1) , the capacity of a Cu2-x Se/Li battery was 208, 202, 200, and 198 mA h g(-1) , respectively, showing excellent rate capability. The 4-probe conductivity measurements along with electrochemical impendence spectroscopy (EIS) and cyclic voltammetry (CV) tests illustrate that the Cu2-x Se electrodes display high specific conductivity and impressive lithium-ion diffusion rate, which makes the Cu2-x Se a promising anode material for lithium-ion batteries. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Shape control synthesis of spheroid and rod-like silver nanostructures in organic-inorganic sol-gel composite

    NASA Astrophysics Data System (ADS)

    Saraidarov, T.; Levchenko, V.; Popov, I.; Reisfeld, R.

    2009-07-01

    The synthesis of a variety of spheroid and rod-like silver nanoparticles in hybrid organic-inorganic sol-gel composite films was examined. The sol-gel matrix used in this work involves urethane terminated silica network which acts as a stabilizing and coupling agent and can complex with silver atoms through its secondary amine functionality and form stable colloid dispersions. The parameters determining the particles size and shape are the starting concentrations of silver ions, the coordination and reduction abilities of the solvent and the reaction kinetics and temperature. In this work the reduction process of silver ion was performed by DMF in sol-gel polyurethane precursor solution at two reaction temperatures: (a) 40 ∘C and (b) reflux at boiling temperature. The effects of concentration and temperature of solution on the morphology and uniformity of silver nanorods were investigated by UV-VIS spectroscopy, SEM and TEM. Spheroid nanoparticles size was as 10-12 nm. Electron diffraction shows that all nanoparticles have a silver face-centered cubic crystal lattice. The silver nanoparticles obtained in composite films exhibit a strong characteristic extinction peak, due to surface plasmon resonance occurring nearly 420-440 nm.

  5. Light scattering studies on solutions of charged rod-like fd-virus at very low ionic strength

    NASA Astrophysics Data System (ADS)

    Schulz, Susanne F.; Maier, Erich E.; Weber, R.

    1989-01-01

    Light scattering experiments are reported on semidilute, aqueous solutions of rod-like fd-virus (length L=880 nm, molecular weight 16.4×106 dalton) near the overlap concentration c*=1 particle/length3. In solutions of very low ionic strength, a liquid-like structure with a significant intensity maximum of the elastically scattered light is observed. The structure is caused by the electrostatic interaction of the charged rods. It vanishes, when enough salt is added so that the interaction potential is screened on the interparticle distance. The scattering vector qmax of the maximum scales with the fd concentration as c1/2. The experimental values for qmaxL fit very well to Monto Carlo simulations if the concentration is scaled to c*. Dynamic light scattering of the fd solutions reflects the influence of the static structure factor in the same way as observed for interacting spherical macromolecules: The first cumulant of the field correlation function divided by the square of the scattering vector shows a behavior reciprocal to that of the static structure factor.

  6. Numerical simulations on active rod like particles as a model for the collective behavior of Myxococcus xanthus

    NASA Astrophysics Data System (ADS)

    Wigbers, Manon; Thutupalli, Shashi; Shaevitz, Joshua

    2015-03-01

    We study collective behavior of Myxococcus xanthus using numerical simulations. Under starvation conditions, these social bacteria organize into multi-cellular structures, called ``fruiting bodies,'' within which cells sporulate. During the process of fruiting body formation, cells show various collective motion patterns. One of the most striking of these patterns is the so called rippling motility, characterized by standing density waves of reversing bacteria. Similar rippling behaviour is also observed during predatory feeding of the bacteria. Until now, the principles underlying this rippling behavior are not fully elucidated. Analogous to the well studied liquid crystalline phases in condensed matter physics, the ordering of the baceria within these rippling waves resembles a smectic like layered structure. In contrast to active nematic liquid crystalline phases widely studied in recent times, this represents the first known empirical example of an active smectic phase. Inspired by single-cell resolution experimental data of the bacteria, we develop a modelof active rod like particles and use numerical simulations to study the organizing principles that drive the transitions between the various active liquid crystalline phases in the myxobacterial collective behavior.

  7. Review of crystalline structures of some selected homologous series of rod-like molecules capable of forming liquid crystalline phases.

    PubMed

    Zugenmaier, Peter

    2011-01-01

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

  8. Late stages of phase separation/gelation of isotropic solutions of rod-like polymers by video microscopy

    NASA Astrophysics Data System (ADS)

    Chowdhury, Aslam H.; Russo, Paul S.

    1990-05-01

    The late stages of phase separation/gelation in concentrated solutions of poly(γ-benzyl-α, L-glutamate) in N,N-dimethylformamide containing 2% added water have been observed by video optical microscopy. Microscopic phase separation is directly evident on cooling homogeneous, isotropic solutions. Within the phase separating mixture, diffuse structural features are separated from one another by a characteristic distance. Fourier transforms of the real space images, equivalent to scattering patterns, show a radially symmetric ring, which collapses to lower wave number as gelation proceeds. The wave number associated with the maximum intensity, qm, obeys a scaling relationship consistent with the Lifshitz-Slyozov evaporation/condensation model, also consistent with the Binder-Stauffer cluster dynamics model: qm=t-1/3, where t is time. A more general scaling relationship proposed by Furukawa is obeyed very well if the dimensionality of the growth of the new phases is 3. The advantages of video microscopy for such studies and possible implications for the role of spinodal decomposition in rod-like polymer solutions are discussed.

  9. Controlled synthesis of rod-like LiVMoO6 nanocrystals for application in lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Liang, Yongguang; Han, Xiaoyan; Cong, Changjie; Yi, Zonghui; Zhou, Liqun; Sun, Jutang; Zhang, Keli; Zhou, Yunhong

    2007-04-01

    This paper reports a newly developed method for the shape and size control of transition metal composite oxides, such as LiVMoO6, to obtain significantly enhanced electrode properties for lithium-ion batteries. Rod-like LiVMoO6 nanocrystals were synthesized through a designed route of partial reduction, self-assembly and re-oxidation. V5+ and Mo6+ ions were used with low-grade starting materials to get a mixed valence of V and Mo. It is believed that ion pairs of V5+/V4+ or Mo6+/Mo5+ in the resultant mixture play an important role in the formation of a template precursor by self-assembly during a rheological phase reaction, although further explanation is required. The electrochemical performance of the LiVMoO6 obtained has been much improved due to the increased crystallinity and reduced particle size of this material. 176 mA h g-1 and 166 mA h g-1 capacity was delivered in the initial discharge with a reversible capacity retention of 94.8% and 95.3% after 100 cycles in the range of 3.6-1.80 V versus metallic Li at 1 and 3 C current rate, respectively.

  10. Rod-like microglia are restricted to eyes with laser-induced ocular hypertension but absent from the microglial changes in the contralateral untreated eye.

    PubMed

    de Hoz, Rosa; Gallego, Beatriz I; Ramírez, Ana I; Rojas, Blanca; Salazar, Juan J; Valiente-Soriano, Francisco J; Avilés-Trigueros, Marcelino; Villegas-Perez, Maria P; Vidal-Sanz, Manuel; Triviño, Alberto; Ramírez, José M

    2013-01-01

    In the mouse model of unilateral laser-induced ocular hypertension (OHT) the microglia in both the treated and the normotensive untreated contralateral eye have morphological signs of activation and up-regulation of MHC-II expression in comparison with naïve. In the brain, rod-like microglia align to less-injured neurons in an effort to limit damage. We investigate whether: i) microglial activation is secondary to laser injury or to a higher IOP and; ii) the presence of rod-like microglia is related to OHT. Three groups of mice were used: age-matched control (naïve, n=15); and two lasered: limbal (OHT, n=15); and non-draining portion of the sclera (scleral, n=3). In the lasered animals, treated eyes as well as contralateral eyes were analysed. Retinal whole-mounts were immunostained with antibodies against, Iba-1, NF-200, MHC-II, CD86, CD68 and Ym1. In the scleral group (normal ocular pressure) no microglial signs of activation were found. Similarly to naïve eyes, OHT-eyes and their contralateral eyes had ramified microglia in the nerve-fibre layer related to the blood vessel. However, only eyes with OHT had rod-like microglia that aligned end-to-end, coupling to form trains of multiple cells running parallel to axons in the retinal surface. Rod-like microglia were CD68+ and were related to retinal ganglion cells (RGCs) showing signs of degeneration (NF-200+RGCs). Although MHC-II expression was up-regulated in the microglia of the NFL both in OHT-eyes and their contralateral eyes, no expression of CD86 and Ym1 was detected in ramified or in rod-like microglia. After 15 days of unilateral lasering of the limbal and the non-draining portion of the sclera, activated microglia was restricted to OHT-eyes and their contralateral eyes. However, rod-like microglia were restricted to eyes with OHT and degenerated NF-200+RGCs and were absent from their contralateral eyes. Thus, rod-like microglia seem be related to the neurodegeneration associated with HTO.

  11. Rod-Like Microglia Are Restricted to Eyes with Laser-Induced Ocular Hypertension but Absent from the Microglial Changes in the Contralateral Untreated Eye

    PubMed Central

    de Hoz, Rosa; Gallego, Beatriz I.; Ramírez, Ana I.; Rojas, Blanca; Salazar, Juan J.; Valiente-Soriano, Francisco J.; Avilés-Trigueros, Marcelino; Villegas-Perez, Maria P.; Vidal-Sanz, Manuel; Triviño, Alberto; Ramírez, José M.

    2013-01-01

    In the mouse model of unilateral laser-induced ocular hypertension (OHT) the microglia in both the treated and the normotensive untreated contralateral eye have morphological signs of activation and up-regulation of MHC-II expression in comparison with naïve. In the brain, rod-like microglia align to less-injured neurons in an effort to limit damage. We investigate whether: i) microglial activation is secondary to laser injury or to a higher IOP and; ii) the presence of rod-like microglia is related to OHT. Three groups of mice were used: age-matched control (naïve, n=15); and two lasered: limbal (OHT, n=15); and non-draining portion of the sclera (scleral, n=3). In the lasered animals, treated eyes as well as contralateral eyes were analysed. Retinal whole-mounts were immunostained with antibodies against, Iba-1, NF-200, MHC-II, CD86, CD68 and Ym1. In the scleral group (normal ocular pressure) no microglial signs of activation were found. Similarly to naïve eyes, OHT-eyes and their contralateral eyes had ramified microglia in the nerve-fibre layer related to the blood vessel. However, only eyes with OHT had rod-like microglia that aligned end-to-end, coupling to form trains of multiple cells running parallel to axons in the retinal surface. Rod-like microglia were CD68+ and were related to retinal ganglion cells (RGCs) showing signs of degeneration (NF-200+RGCs). Although MHC-II expression was up-regulated in the microglia of the NFL both in OHT-eyes and their contralateral eyes, no expression of CD86 and Ym1 was detected in ramified or in rod-like microglia. After 15 days of unilateral lasering of the limbal and the non-draining portion of the sclera, activated microglia was restricted to OHT-eyes and their contralateral eyes. However, rod-like microglia were restricted to eyes with OHT and degenerated NF-200+RGCs and were absent from their contralateral eyes. Thus, rod-like microglia seem be related to the neurodegeneration associated with HTO. PMID:24367610

  12. A Single Aspiration of Rod-like Carbon Nanotubes Induces Asbestos-like Pulmonary Inflammation Mediated in Part by the IL-1 Receptor.

    PubMed

    Rydman, Elina M; Ilves, Marit; Vanhala, Esa; Vippola, Minnamari; Lehto, Maili; Kinaret, Pia A S; Pylkkänen, Lea; Happo, Mikko; Hirvonen, Maija-Riitta; Greco, Dario; Savolainen, Kai; Wolff, Henrik; Alenius, Harri

    2015-09-01

    Carbon nanotubes (CNT) have been eagerly studied because of their multiple applications in product development and potential risks on health. We investigated the difference of two different CNT and asbestos in inducing proinflammatory reactions in C57BL/6 mice after single pharyngeal aspiration exposure. We used long tangled and long rod-like CNT, as well as crocidolite asbestos at a dose of 10 or 40 µg/mouse. The mice were sacrificed 4 and 16 h or 7, 14, and 28 days after the exposure. To find out the importance of a major inflammatory marker IL-1β in CNT-induced pulmonary inflammation, we used etanercept and anakinra as antagonists as well as Interleukin 1 (IL-1) receptor (IL-1R-/-) mice. The results showed that rod-like CNT, and asbestos in lesser extent, induced strong pulmonary neutrophilia accompanied by the proinflammatory cytokines and chemokines 16 h after the exposure. Seven days after the exposure, neutrophilia had essentially disappeared but strong pulmonary eosinophilia peaked in rod-like CNT and asbestos-exposed groups. After 28 days, pulmonary granulomas, goblet cell hyperplasia, and Charcot-Leyden-like crystals containing acidophilic macrophages were observed especially in rod-like CNT-exposed mice. IL-1R-/- mice and antagonists-treated mice exhibited a significant decrease in neutrophilia and messenger ribonucleic acid (mRNA) levels of proinflammatory cytokines at 16 h. However, rod-like CNT-induced Th2-type inflammation evidenced by the expression of IL-13 and mucus production was unaffected in IL-1R-/- mice at 28 days. This study provides knowledge about the pulmonary effects induced by a single exposure to the CNT and contributes to hazard assessment of carbon nanomaterials on airway exposure. © The Author 2015. Published by Oxford University Press on behalf of the Society of Toxicology. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

  13. High excimer-state emission of perylene bisimides and recognition of latent fingerprints.

    PubMed

    Wang, Ke-Rang; Yang, Zi-Bo; Li, Xiao-Liu

    2015-04-07

    High excimer-state emission in the H-type aggregate of a novel asymmetric perylene bisimide derivative, 6, with triethyleneglycol chains and lactose functionalization was achieved in water. Furthermore, its application for enhancing the visualization of transfer latent fingerprints from glass slides to the poly(vinylidene fluoride) (PVDF) membrane was explored, which showed clear images of the latent fingerprint in daylight and under 365 nm ultraviolet illumination.

  14. An Electron Acceptor with Porphyrin and Perylene Bisimides for Efficient Non-Fullerene Solar Cells.

    PubMed

    Zhang, Andong; Li, Cheng; Yang, Fan; Zhang, Jianqi; Wang, Zhaohui; Wei, Zhixiang; Li, Weiwei

    2017-03-01

    A star-shaped electron acceptor based on porphyrin as a core and perylene bisimide as end groups was constructed for application in non-fullerene organic solar cells. The new conjugated molecule exhibits aligned energy levels, good electron mobility, and complementary absorption with a donor polymer. These advantages facilitate a high power conversion efficiency of 7.4 % in non-fullerene solar cells, which represents the highest photovoltaic performance based on porphyrin derivatives as the acceptor.

  15. Fabrication and characterization of rod-like nano-hydroxyapatite on MAO coating supported on Mg-Zn-Ca alloy

    NASA Astrophysics Data System (ADS)

    Gao, J. H.; Guan, S. K.; Chen, J.; Wang, L. G.; Zhu, S. J.; Hu, J. H.; Ren, Z. W.

    2011-01-01

    The poor corrosion resistance of magnesium alloys is a dominant problem that limits their clinical application. In order to solve this challenge, micro-arc oxidation (MAO) was used to fabricate a porous coating on magnesium alloys and then electrochemical deposition (ED) was done to fabricate rod-like nano-hydroxyapatite (RNHA) on MAO coating. The cross-section morphology of the composite coatings and its corresponding energy dispersion spectroscopy (EDS) surficial scanning map of calcium revealed that HA rods were successfully deposited into the pores. The three dimensional morphology and scanning electron microscopy (SEM) image of the composite coatings showed that the distribution of the HA rods was dense and uniform. Atomic force microscope (AFM) observation of the composite coatings showed that the diameters of HA rods varied from 95 nm to 116 nm and the root mean square roughness (RMS) of the composite coatings was about 42 nm, which were favorable for cellular survival. The bonding strength between the HA film and MAO coating increased to 12.3 MPa, almost two times higher than that of the direct electrochemical deposition coating (6.3 MPa). Compared with that of the substrate, the corrosion potential of Mg-Zn-Ca alloy with composite coatings increased by 161 mV and its corrosion current density decreased from 3.36 × 10 -4 A/cm 2 to 2.40 × 10 -7 A/cm 2 which was due to the enhancement of bonding strength and the deposition of RNHA in the MAO pores. Immersion tests were carried out at 36.5 ± 0.5 °C in simulated body fluid (SBF). It was found that RNHA can induce the rapid precipitation of calcium orthophosphates in comparison with conventional HA coatings. Thus magnesium alloy coated with the composite coatings is a promising candidate as biodegradable bone implants.

  16. Three-dimensional Brownian diffusion of rod-like macromolecules in the presence of randomly distributed spherical obstacles: molecular dynamics simulation.

    PubMed

    Sakha, Farzaneh; Fazli, Hossein

    2010-12-21

    Brownian diffusion of rod-like polymers in the presence of randomly distributed spherical obstacles is studied using molecular dynamics simulations. It is observed that dependence of the reduced diffusion coefficient of these macromolecules on the available volume fraction can be described reasonably by a power law function. Despite the case of obstructed diffusion of flexible polymers in which reduced diffusion coefficient has a weak dependence on the polymer length, this dependence is noticeably strong in the case of rod-like polymers. Diffusion of these macromolecules in the presence of obstacles is observed that is anomalous at short time scales and normal at long times. Duration time of the anomalous diffusion regime is found that increases very rapidly with increasing both the polymer length and the obstructed volume fraction. Dynamics of diffusion of these polymers is observed that crosses over from Rouse to reptation type with increasing the density of obstacles.

  17. Solid-state chemical synthesis of rod-like fluorine-doped β-Bi2O3 and their enhanced photocatalytic property under visible light

    NASA Astrophysics Data System (ADS)

    Liang, Zhiting; Cao, Yali; Li, Yizhao; Xie, Jing; Guo, Nana; Jia, Dianzeng

    2016-12-01

    The pure β-Bi2O3 and fluorine-doped β-Bi2O3 rod-like microstructures were successfully prepared by a facile solid-state chemical reaction process. The composition, structure and morphology of the samples were determined by XRD, EDS, SEM, TEM, HRTEM, XPS and PL. Photocatalytic activities of all samples were investigated via the degradation of methyl orange (MO) under the irradiation of visible light. The fluorine-doped β-Bi2O3 rods exhibited higher photocatalytic activities than the pure β-Bi2O3 rod-like structures and commercial sample. The 82% MO can be degraded by the fluorine-doped β-Bi2O3 rods after irradiation for 2 h under visible light, which is 2-3 times higher than that of counterparts. The enhanced properties of the fluorine-doped samples attribute to their higher separation efficiency of electron-hole pairs and strong oxidation potential of valance band holes. The results show that the as-prepared rod-like fluorine-doped β-Bi2O3 materials are potential candidates for photocatalysts irradiated by visible light.

  18. Zinc(II)-selective ratiometric fluorescent probe based on perylene bisimide derivative.

    PubMed

    Zhao, Yingjie; Sun, Juanjuan; Shi, Zhiqiang; Pan, Cuicui; Xu, Maoyou

    2011-01-01

    A fluorescent probe of N,N'-biscyclohexyl-1,7-di(3-pyridoxy)-perylene-3,4:9,10-tetracarboxylic acid diimide has been synthesized, and exhibited excellent selectivity and sensitivity for Zn(2+) over other competing biological cations. The Zn(2+) -selective fluorescence blue-shift and enhancing property in conjunction with a visible colorimetric change from orange to green could be observed. With favorable photophysical properties in the visible region, the perylene bisimide derivatives remarkably improved the performance of the probe.

  19. Extending the short and long wavelength limits of bacteriochlorin near-infrared absorption via dioxo- and bisimide-functionalization.

    PubMed

    Vairaprakash, Pothiappan; Yang, Eunkyung; Sahin, Tuba; Taniguchi, Masahiko; Krayer, Michael; Diers, James R; Wang, Alfred; Niedzwiedzki, Dariusz M; Kirmaier, Christine; Lindsey, Jonathan S; Bocian, David F; Holten, Dewey

    2015-03-26

    Six new bacteriochlorins expanding the range of the strong near-infrared (NIR) absorption (Qy band) to both shorter and longer wavelengths (∼690 to ∼900 nm) have been synthesized and characterized. The architectures include bacteriochlorin-bisimides that have six-membered imide rings spanning the 3,5- and 13,15-macrocycle positions or five-membered imide rings spanning the β-pyrrolic 2,3- and 12,13-positions. Both bisimide types absorb at significantly longer wavelength than the bacteriochlorin precursors (no fused rings), whereas oxo-groups at the 7- or 7,17-positions shift the Qy band to a new short wavelength limit. Surprisingly, bacteriochlorin-bisimides with five-membered β-pyrrolic-centered imide rings have a Qy band closer to that of six-membered bacteriochlorin-monoimides. However, the five-membered bisimides (versus the six-membered bacteriochlorin-monoimides) have significantly enhanced absorption intensity that is paralleled by an ∼2-fold higher fluorescence yield (∼0.16 vs ∼0.07) and longer singlet excited-state lifetime (∼4 ns vs ∼2 ns). The photophysical enhancements derive in part from mixing of the lowest unoccupied frontier molecular orbitals of the five-membered imide ring with those of the bacteriochlorin framework. In general, all of the new bacteriochlorins have excited-state lifetimes (1-4 ns) that are sufficiently long for use in molecular-based systems for photochemical applications.

  20. Tetrahydrophthalic Anhydrides as Addition Curing Polyimide End Caps: Thermal Isomerization of Methylendianiline 3,6-Diphenyltetrahydrophthalic Bisimides

    NASA Technical Reports Server (NTRS)

    Frimer, Aryeh A.; Gilinsky-Sharon, Pessia; Gottlieb, Hugo E.; Meador, Mary Ann B.; Johnston, J. Christopher

    2005-01-01

    In depth NMR studies confirm that heating a 1:2 mixture of cis, cis, cis 3,6-diphenyltetrahydrophthalic anhydride (end cap 9c) with methylenedianiline at 316 C initially yields the corresponding highly congested cis, cis, cis 3,6-diphenyltetrahydrophthalic bisimide 11, which is converted at this temperature to the observed product, the less hindered trans, cis, trans isomer 12.

  1. Controllable synthesis of flower- and rod-like ZnO nanostructures by simply tuning the ratio of sodium hydroxide to zinc acetate

    NASA Astrophysics Data System (ADS)

    Zhang, Yunyan; Mu, Jin

    2007-02-01

    A controlled synthesis of flower- and rod-like ZnO nanostructures in a hydrothermal phase has been realized in the absence of an additional template. The well-defined morphologies are obtained by simply tuning the ratio of sodium hydroxide to zinc acetate in a narrow range. The products are characterized by powder x-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The growth mechanism is suggested to be that the supersaturation of the precursor Zn(OH)42- results in various nucleation habits, which induce the ZnO nanostructures with different morphologies.

  2. Functional bisimide dyes bound via electrostatic interactions to oxide nanostructures generated by AFM lithography

    NASA Astrophysics Data System (ADS)

    Baumgärtel, T.; Rehm, S.; Würthner, F.; von Borczyskowski, C.; Graaf, H.

    2014-11-01

    Silicon oxide nanostructures have been functionalized by selective binding of a positively charged bisimide dye derivative. The structures were prepared by AFM nanolithography via local anodic oxidation (LAO) of dodecyl-terminated silicon and are negatively charged due to the production process. Therefore cationic spermine-functionalized perylene bisimide (sf-PBI) molecules can be bound to the structures by electrostatic interactions. The assembly of the sf-PBI units on the LAO nanostructures is verified by AFM height measurements and means of fluorescence microscopy. Emission spectra from the dye-functionalized oxide show that the molecules are able to form excimers. These excimers are characterized by a broad and featureless red-shifted emission band and an increased excited state life time. In contrast to the emission of sf-PBI films on uncharged silicon oxide, the excimer emission was found to decrease strongly low temperatures. This might be explained by a very tight binding due to the electrostatic attraction of the molecules to the LAO oxide.

  3. Rapid self-assembly of porous square rod-like nickel persulfide via a facile solution method for high-performance supercapacitors

    NASA Astrophysics Data System (ADS)

    Ruan, Yunjun; Jiang, Jianjun; Wan, Houzhao; Ji, Xiao; Miao, Ling; Peng, Lu; Zhang, Bao; Lv, Lin; Liu, Jia

    2016-01-01

    The square rod-like NiS2 with open ends is synthesized by a general solution method without substrate followed by a post annealing treatment. This method involves a rapid self-assembly and a spontaneous aging process controlled by the time of the solution reaction. And the one-step solution-controlled reaction benefits for the convenient fabrication of metal sulfide precursors. The NiS2 with the length varying from 3 to 8 μm and the width of 2 μm has both open ends, and the BET surface area and average pore diameter of the NiS2 are 59.2 m2 g-1 and 24.4 nm, respectively. The porous NiS2 square rods show a high specific capacitance (1020.2 F g-1 at 1 A g-1 and 534.9 F g-1 at 10 A g-1) as well as excellent cycle life (93.4% of the initial specific capacitance remains after 1000 cycles). Furthermore, an asymmetric supercapacitor device fabricated by using the NiS2 as the cathode and reduced graphene oxide as the anode delivers an energy density of 32.76 Wh kg-1 at a power density of 954 W kg-1. Therefore, the porous square rod-like NiS2 synthesized by an effective route exhibits outstanding electrochemical performance as a promising cathode material for supercapacitors.

  4. Poly(acrylic acid)-regulated Synthesis of Rod-Like Calcium Carbonate Nanoparticles for Inducing the Osteogenic Differentiation of MC3T3-E1 Cells.

    PubMed

    Yang, Wei; Yao, Chenxue; Cui, Zhengyang; Luo, Dandan; Lee, In-Seop; Yao, Juming; Chen, Cen; Kong, Xiangdong

    2016-05-06

    Calcium carbonate, especially with nanostructure, has been considered as a good candidate material for bone regeneration due to its excellent biodegradability and osteoconductivity. In this study, rod-like calcium carbonate nanoparticles (Rod-CC NPs) with desired water dispersibility were achieved with the regulation of poly (acrylic acid). Characterization results revealed that the Rod-CC NPs had an average length of 240 nm, a width of 90 nm with an average aspect ratio of 2.60 and a negative ζ-potential of -22.25 ± 0.35 mV. The degradation study illustrated the nanoparticles degraded 23% at pH 7.4 and 45% at pH 5.6 in phosphate-buffered saline (PBS) solution within three months. When cultured with MC3T3-E1 cells, the Rod-CC NPs exhibited a positive effect on the proliferation of osteoblast cells. Alkaline phosphatase (ALP) activity assays together with the osteocalcin (OCN) and bone sialoprotein (BSP) expression observations demonstrated the nanoparticles could induce the differentiation of MC3T3-E1 cells. Our study developed well-dispersed rod-like calcium carbonate nanoparticles which have great potential to be used in bone regeneration.

  5. GM130 is a parallel tetramer with a flexible rod-like structure and N-terminally open (Y-shaped) and closed (I-shaped) conformations.

    PubMed

    Ishida, Ryuichi; Yamamoto, Akitsugu; Nakayama, Kazuhisa; Sohda, Miwa; Misumi, Yoshio; Yasunaga, Takuo; Nakamura, Nobuhiro

    2015-06-01

    GM130 is a cytoplasmic peripheral membrane protein localized on the cis side of the Golgi apparatus. GM130 is proposed to function as a membrane skeleton, maintaining the structure of the Golgi apparatus, and as a vesicle tether that facilitates vesicle fusion to the Golgi membrane. More than 60% of the GM130 molecule is believed to exist as coiled-coil structures with a probability above 90%, based on its primary amino acid sequence. The predicted coiled-coil region was similar to that of yeast Uso1p and its mammalian homolog, p115, both of which form coiled-coil homodimers. Therefore, GM130 has long been thought to form a homodimer with a rod-like shape. However, our biochemical and electron microscopical analyses revealed that GM130 is a parallel homotetramer with a flexible rod-like structure with I- and Y-shaped conformations. The structure of the N-terminal region may interchange between an open conformation (branched or Y-shaped) and a closed conformation (non-branched or I-shaped), possibly with the help of interacting molecules. This conformational change may alter the oligomeric state of the GM130 molecules and the function of GM130 in the vesicle tethering and the maintenance of the Golgi structure. © 2015 FEBS.

  6. Porous rod-like MgO complex membrane with good anti-bacterial activity directed by conjugated linolenic acid polymer

    NASA Astrophysics Data System (ADS)

    Wang, Hua-Jie; Chen, Meng; Mi, Li-Wei; Shi, Li-Hua; Cao, Ying

    2016-02-01

    The problem of infection in the tissue engineering substitutes is driving us to seek new coating materials. We previously found that conjugated linolenic acid (CLnA) has well biocompatibility and excellent membrane-forming property. The objective of this study is to endow the anti-bacterial activity to CLnA membra ne by linking with MgO. The results showed that the CLnA polymer membrane can be loaded with porous rod-like MgO and such complex membrane showed anti-bacterial sensitivity against gram-positive bacteria ( Staphylococcus aureus) even at the low concentration (0.15 μg/mm2). In the present study, the best zone of inhibition got to 18.2 ± 0.8 mm when the amount of MgO reach 2.42 ± 0.58 μg/mm2. It was deduced that the porous rod-like structure of MgO was directed by CLnA in its polymerization process. Such CLnA/MgO complex membrane can be helpful in the tissue engineering, medicine, food engineering, food preservation, etc. on the basis of its good anti-bacterial activity.

  7. Poly(acrylic acid)-regulated Synthesis of Rod-Like Calcium Carbonate Nanoparticles for Inducing the Osteogenic Differentiation of MC3T3-E1 Cells

    PubMed Central

    Yang, Wei; Yao, Chenxue; Cui, Zhengyang; Luo, Dandan; Lee, In-Seop; Yao, Juming; Chen, Cen; Kong, Xiangdong

    2016-01-01

    Calcium carbonate, especially with nanostructure, has been considered as a good candidate material for bone regeneration due to its excellent biodegradability and osteoconductivity. In this study, rod-like calcium carbonate nanoparticles (Rod-CC NPs) with desired water dispersibility were achieved with the regulation of poly (acrylic acid). Characterization results revealed that the Rod-CC NPs had an average length of 240 nm, a width of 90 nm with an average aspect ratio of 2.60 and a negative ζ-potential of −22.25 ± 0.35 mV. The degradation study illustrated the nanoparticles degraded 23% at pH 7.4 and 45% at pH 5.6 in phosphate-buffered saline (PBS) solution within three months. When cultured with MC3T3-E1 cells, the Rod-CC NPs exhibited a positive effect on the proliferation of osteoblast cells. Alkaline phosphatase (ALP) activity assays together with the osteocalcin (OCN) and bone sialoprotein (BSP) expression observations demonstrated the nanoparticles could induce the differentiation of MC3T3-E1 cells. Our study developed well-dispersed rod-like calcium carbonate nanoparticles which have great potential to be used in bone regeneration. PMID:27164090

  8. Rapid Facile Microwave-assisted Solvothermal Synthesis of Rod-like CuO/TiO2 for High Efficiency photocatalytic Hydrogen Evolution

    NASA Astrophysics Data System (ADS)

    Yu, Yi-Hsien; Chen, Ying-Pin; Cheng, Zhengdong

    2015-03-01

    Rod-like CuO/TiO2 was prepared by a rapid facile microwave-assisted solvothermal method for high efficiency photocatalytic hydrogen evolution. The structure of obtained CuO/TiO2 samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), high resolution transmission electron microscopy (HR-TEM), and the amount of produced hydrogen was analyzed by gas chromatography (GC). CuO decorated TiO2 rods exhibited greatly improvement of photocatalytic hydrogen evolution. Utilizing 30 mg of CuO/TiO2 rods sample showed highest hydrogen evolution rate over utilizing 50 mg and 100 mg. Comparing to hydrogen evolution rate of 45.4 μmol h-1 g1 by using bare Rod-like TiO2, 1 wt% CuO loaded TiO2 rods presented the highest hydrogen evolution rate of 3508.7 μmol h-1 g-1 while hydrogen evolution rate of 0.5 wt%, 5 wt%, and 10 wt% CuO loaded TiO2 rods were 157.1, 2817, and 2595 μmol h-1 g-1, respectively. Such enhancement of photocatalytic activity could be ascribed to that CuO improves not only light harvesting but also enhanced separation of electron-hole charge carriers

  9. Polymerization of rod-like macromolecular monomers studied by stopped-flow, multiangle light scattering: set-up, data processing, and application to fibrin formation.

    PubMed Central

    Bernocco, S; Ferri, F; Profumo, A; Cuniberti, C; Rocco, M

    2000-01-01

    Many biological supramolecular structures are formed by polymerization of macromolecular monomers. Light scattering techniques can provide structural information from such systems, if suitable procedures are used to collect the data and then to extract the relevant parameters. We present an experimental set-up in which a commercial multiangle laser light scattering photometer is linked to a stopped-flow mixer, allowing, in principle, the time-resolved extrapolation of the weight-average molecular weight M(w) and of the z-average square radius of gyration (z) of the polymers from Zimm-like plots. However, if elongated structures are formed as the polymerization proceeds, curved plots rapidly arise, from which M(w) and (z) cannot be recovered by linear fitting. To verify the correctness of a polynomial fitting procedure, polydisperse collections of rod-like or worm-like particles of different lengths, generated at various stages during bifunctional polycondensations of rod-like macromolecular monomers, were considered. Then, the angular dependence of their time-averaged scattered intensity was calculated in the Rayleigh-Gans-Debye approximation, with random and systematic noise also added to the data. For relatively narrow size distributions, a third-degree polynomial fitting gave satisfactory results across a broad range of conversion degrees, yielding M(w) and (z) values within 2% and no greater than 10-20%, respectively, of the calculated values. When more broad size distributions were analyzed, the procedure still performed well for semiflexible polymers, but started to seriously underestimate both M(w) and (z) when rigid rod-like particles were analyzed, even at relatively low conversion degrees. The data were also analyzed in the framework of the Casassa approximation, from which the mass per unit length of the polymers can be derived. These procedures were applied to a set of data taken on the early stages of the thrombin

  10. Synthesis of biocompatible glycodendrimer based on fluorescent perylene bisimides and its bioimaging.

    PubMed

    Wang, Ke-Rang; An, Hong-Wei; Rong, Rui-Xue; Cao, Zhi-Ran; Li, Xiao-Liu

    2014-04-01

    A novel water-soluble fluorescent glycodendrimer based on perylene bisimides is synthesized, which exhibits high fluorescence quantum yield of 54%. While the binding interactions of PBI-Man with Concanavalin A (Con A) are studied by fluorescence spectra and CD spectra, which show strong binding affinity for Con A with the binding constant of 3.8 × 10(7) m(-1) for monomeric mannose, nearly four orders of magnitude higher affinity than the monovalent mannose ligand. Furthermore, the fluorescence imaging of macrophage cell with PBI-Man is investigated, and shows selectively binding interaction with the mannose receptor-medicated cell entry. Moreover, the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) activities of PBI-Man show that PBI-Man as a biocompatible agent is noncytotoxic to living cells.

  11. Intramolecular Charge-Transfer Interaction of Donor-Acceptor-Donor Arrays Based on Anthracene Bisimide.

    PubMed

    Iwanaga, Tetsuo; Ogawa, Marina; Yamauchi, Tomokazu; Toyota, Shinji

    2016-05-20

    We designed anthracene bisimide (ABI) derivatives having two triphenylamine (TPA) groups as donor units at the 9,10-positions to form a novel π-conjugated donor-acceptor system. These compounds and their analogues with ethynylene linkers were synthesized by Suzuki-Miyaura and Sonogashira coupling reactions, respectively. In UV-vis spectra, the linker-free derivatives showed broad absorption bands arising from intramolecular charge-transfer interactions. Introducing ethynylene linkers resulted in a considerable red shift of the absorption bands. In fluorescence spectra, the ethynylene derivatives showed intense emission bands at 600-650 nm. Their photophysical and electrochemical properties were compared with those of the corresponding mono TPA derivatives on the basis of theoretical calculations and cyclic voltammetry to evaluate the intramolecular electronic interactions between the donor and acceptor units.

  12. Rapid Energy Transfer Enabling Control of Emission Polarization in Perylene Bisimide Donor-Acceptor Triads.

    PubMed

    Menelaou, Christopher; ter Schiphorst, Jeroen; Kendhale, Amol M; Parkinson, Patrick; Debije, Michael G; Schenning, Albertus P H J; Herz, Laura M

    2015-04-02

    Materials showing rapid intramolecular energy transfer and polarization switching are of interest for both their fundamental photophysics and potential for use in real-world applications. Here, we report two donor-acceptor-donor triad dyes based on perylene-bisimide subunits, with the long axis of the donors arranged either parallel or perpendicular to that of the central acceptor. We observe rapid energy transfer (<2 ps) and effective polarization control in both dye molecules in solution. A distributed-dipole Förster model predicts the excitation energy transfer rate for the linearly arranged triad but severely underestimates it for the orthogonal case. We show that the rapid energy transfer arises from a combination of through-bond coupling and through-space transfer between donor and acceptor units. As they allow energy cascading to an excited state with controllable polarization, these triad dyes show high potential for use in luminescent solar concentrator devices.

  13. Preparation and electrochemical performances of rod-like LiV3O8/carbon composites using polyaniline as carbon source

    NASA Astrophysics Data System (ADS)

    Cao, Xiaoyu; Zhu, Limin; Wu, Hailian

    2015-07-01

    Rod-like LiV3O8/carbon composites were successfully prepared by the polymer graphitization of LiV3O8/polyaniline composites, which were synthesized through the in-situ oxidative polymerization method. The crystal phases of as-prepared samples, confirmed by X-ray diffraction, show that the interlayer spacing in LiV3O8/carbon composites is much wider than that of the pristine LiV3O8. Compared to the bare LiV3O8, the longer and smoother rod-like LiV3O8/carbon composites, investigated by scanning electron microscope and transmission electron microscope, were covered by a continuously thin layer of fluffy carbon with a thickness of approximate 20 nm. The optimal LiV3O8/carbon composite delivered a discharge capacity of 219.37 mAh g-1 in the initial cycle, and maintained a high capacity of 263.538 mAh g-1 at the 30th cycle, which was much higher than that of the pristine LiV3O8 (227.645 mAh g-1). Cyclic voltammetry measurements disclose that, after the carbon coating treatment, the phase transition of the optimal LiV3O8/carbon composite proceeds more reversibly and smoothly during charging/discharging. The improved cyclability of the optimal LiV3O8/carbon composite should be attributed to the confinement from thin carbon layer, the structural stability, the good interfacial compatibility, and the well-preserved electrode morphology after prolonged cycles. [Figure not available: see fulltext.

  14. Effects of molecular chirality on self-assembly and switching in liquid crystals at the cross-over between rod-like and bent shapes.

    PubMed

    Ocak, Hale; Poppe, Marco; Bilgin-Eran, Belkız; Karanlık, Gürkan; Prehm, Marko; Tschierske, Carsten

    2016-09-21

    A bent-core compound derived from a 4-cyanoresorcinol core unit with two terephthalate based rod-like wings and carrying chiral 3,7-dimethyloctyloxy side chains has been synthesized in racemic and enantiomerically pure form and characterized by polarizing microscopy, differential scanning calorimetry, X-ray diffraction and electro-optical investigations to study the influence of molecular chirality on the superstructural chirality and polar order in lamellar liquid crystalline phases. Herein we demonstrate that the coupling of molecular chirality with superstructural layer chirality in SmCsPF domain phases (forming energetically distinct diastereomeric pairs) can fix the tilt direction and thus stabilize synpolar order, leading to bistable ferroelectric switching in the SmC* phases of the (S)-enantiomer, whereas tristable modes determine the switching of the racemate. Moreover, the mechanism of electric field induced molecular reorganization changes from a rotation around the molecular long axis in the racemate to a rotation on the tilt-cone for the (S)-enantiomer. At high temperature the enantiomer behaves like a rod-like molecule with a chirality induced ferroelectric SmC* phase and an electroclinic effect in the SmA'* phase. At reduced temperature sterically induced polarization, due to the bent molecular shape, becomes dominating, leading to much higher polarization values, thus providing access to high polarization ferroelectric materials with weakly bent compounds having only "weakly chiral" stereogenic units. Moreover, the field induced alignment of the SmCsPF(()*()) domains gives rise to a special kind of electroclinic effect appearing even in the absence of molecular chirality. Comparison with related compounds indicates that the strongest effects of chirality appear for weakly bent molecules with a relatively short coherence length of polar order, whereas for smectic phases with long range polar order the effects of the interlayer interfaces can override

  15. Regime of aggregate structures and magneto-rheological characteristics of a magnetic rod-like particle suspension: Monte Carlo and Brownian dynamics simulations

    NASA Astrophysics Data System (ADS)

    Okada, Kazuya; Satoh, Akira

    2017-09-01

    In the present study, we address a suspension composed ferromagnetic rod-like particles to elucidate a regime change in the aggregate structures and the magneto-rheological characteristics. Monte Carlo simulations have been employed for investigating the aggregate structures in thermodynamic equilibrium, and Brownian dynamics simulations for magneto-rheological features in a simple shear flow. The main results obtained here are summarized as follows. For the case of thermodynamic equilibrium, the rod-like particles aggregate to form thick chain-like clusters and the neighboring clusters incline in opposite directions. If the external magnetic field is increased, the thick chain-like clusters in the magnetic field direction grow thicker by adsorbing the neighboring clusters that incline in the opposite direction. Hence, a significant phase change in the particle aggregates is not induced by an increase in the magnetic field strength. For the case of a simple shear flow, even a weak shear flow induces a significant regime change from the thick chain-like clusters of thermodynamic equilibrium into wall-like aggregates composed of short raft-like clusters. A strong external magnetic field drastically changes these aggregates into wall-like aggregates composed of thick chain-like clusters rather than the short raft-like clusters. The internal structure of these aggregates is not strongly influenced by a shear flow, and the formation of the short raft-like clusters is maintained inside the aggregates. The main contribution to the net viscosity is the viscosity component due to magnetic particle-particle interaction forces in relation to the present volumetric fraction. Hence, a larger magnetic interaction strength and also a stronger external magnetic field give rise to a larger magneto-rheological effect. However, the dependence of the viscosity on these factors is governed in a complex manner by whether or not the wall-like aggregates are composed mainly of short raft

  16. Synthesis, characterization, and photocatalytic activity of sonochemical/hydration-dehydration prepared ZnO rod-like architecture nano/microstructures assisted by a biotemplate.

    PubMed

    Alkaim, Ayad F; Alrobayi, Enas M; Algubili, Abrar M; Aljeboree, Aseel M

    2017-09-01

    ZnO nanoparticles of rod-like architecture have excellent potential to be used in wastewater treatment as a photocatalyst. They were synthesized by utilizing sonochemical/hydration- dehydration techniques using glutamine as a biotemplate. The effects of calcination temperatures, that is, 300°C, 500°C, and 700°C, on the crystallinity, optical properties, and photocatalytic activity of synthesized zinc oxide nanoparticles were investigated. X-ray diffraction (XRD) results indicated that all calcinated samples have a crystalline hexagonal wurtzite structure. Morphology and elemental compositions were investigated using field emission-scanning electron microscopy with energy-dispersive X-ray spectroscopy. The XRD and Fourier transform infrared (FTIR) spectra revealed that the samples were amorphous at 100°C; however, it changed into a crystalline structure amid the calcination process. Optical properties were determined using a UV-visible reflection spectrophotometer and showed abatement in the band gap with increasing annealing temperature. The progress of the photocatalytic degradation was monitored by a UV-visible spectrophotometer, while the mineralization ability was estimated by total organic carbon tests of ZnO-calcinated samples. The effect of various operational parameters the photocatalytic efficiency and rate of dye degradation was studied. High photocatalytic degradation of maxilon blue dye (GRL) was found at pH 6.3.

  17. Controlled synthesis of CeO2 microstructures from 1D rod-like to 3D lotus-like and their morphology-dependent properties

    NASA Astrophysics Data System (ADS)

    Gong, Jinfeng; Meng, Fanming; Fan, Zhenghua; Li, Huijie

    2016-10-01

    Monodisperse 3D lotus-like CeO2 microstructures have been successfully synthesized via controlling the morphology of CeCO3OH precursors under hydrothermal condition as well as subsequent calcination. The reaction time was systematically investigated. XRD, FT-IR, SEM, TEM, XPS, Raman scattering and Photoluminescence (PL) spectra were employed to characterize the samples. The lotus-like CeO2 hierarchical structures with an average of 4-6 μm are composed of many nanoplates of 100-200 nm in thickness as the petals stacking together to form open flowers and have a fluorite cubic structure. Based on the time-dependent morphology evolution evidences, a nucleation-dissolution-recrystallization mechanism has been proposed to explain the transformation from rod-like structures to lotus-like CeO2 hierarchical structures with the increase of reaction time. It is found that there are Ce3+ ions and oxygen vacancies in surface of samples. The magnetic and photoluminescence measurements indicated that all CeO2 samples exhibit excellent ferromagnetism and optical properties at room temperature, and while increasing the reaction time, the ferromagnetism and optical properties increase more, which can be reasonably explained for the influences of the different morphology of the particles and the concentration of oxygen vacancies and Ce3+ ions. [Figure not available: see fulltext.

  18. A conversion route towards tubular SiO{sub 2} using rod-like BaSiF{sub 6} as a novel template

    SciTech Connect

    Zhong Haoxiang; Huang Qingli; Ma Yingli; Hong Jianming; Chen Xuetai; Xue Ziling

    2009-07-15

    A simple hydrothermal reaction between Ba(NO{sub 3}){sub 2} and K{sub 2}SiF{sub 6} results in the formation of 1D rod-like BaSiF{sub 6}. The BaSiF{sub 6} rods can act as efficient precursors for production of tubular SiO{sub 2} by hydrothermal reaction in alkaline solutions. Powder X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), transmission electron microscopy (TEM), high resolution electron microscopy (HRTEM), and field emission scanning electron microscopy (FESEM) were used to characterize the phase and morphology of the final product. The experiments indicated the amount of NaOH, reaction temperature, and reaction time played important roles in the transformation process. A possible growth mechanism of tubular silica was proposed. - Graphical abstract: Tubular silica was prepared via a hydrothermal reaction between BaSiF{sub 6} and NaOH, in which BaSiF{sub 6} nanorods act as both a physical and chemical template. It was found that the amount of NaOH, reaction temperature, and reaction time played important roles in this transformation process.

  19. Reorganization of perylene bisimide J-aggregates: from delocalized collective to localized individual excitations

    NASA Astrophysics Data System (ADS)

    Tian, Yuxi; Stepanenko, Vladimir; Kaiser, Theo E.; Würthner, Frank; Scheblykin, Ivan G.

    2011-12-01

    Water-induced reorganization of individual one-dimensional J-aggregates of perylene bisimide (PBI) dyes was observed by fluorescence microscopy. Fluorescence spectra and decay kinetics of individual J-aggregates immobilized on glass surfaces were measured under a dry nitrogen atmosphere and under humid conditions. The fluorescence properties of PBI J-aggregates arisen from collective excitons under dry nitrogen atmosphere were changed to those of non-interacting dye monomers when water vapor was introduced into the environment (sample chamber). Time-dependent changes of the fluorescence spectra and lifetimes upon exposure to water vapor suggest an initial coordination of water molecules at defect sites leading to the formation of H-type dimer units that act as exciton quenchers, and a subsequent slower disintegration of the hydrogen-bonded J-aggregate into monomers that lack resonance coupling. Our present studies resulted in a direct demonstration of how drastically the optical properties of molecular ensembles and characteristics of their excited states can be changed by delicate reorganization of dye molecules at nanometre scales.Water-induced reorganization of individual one-dimensional J-aggregates of perylene bisimide (PBI) dyes was observed by fluorescence microscopy. Fluorescence spectra and decay kinetics of individual J-aggregates immobilized on glass surfaces were measured under a dry nitrogen atmosphere and under humid conditions. The fluorescence properties of PBI J-aggregates arisen from collective excitons under dry nitrogen atmosphere were changed to those of non-interacting dye monomers when water vapor was introduced into the environment (sample chamber). Time-dependent changes of the fluorescence spectra and lifetimes upon exposure to water vapor suggest an initial coordination of water molecules at defect sites leading to the formation of H-type dimer units that act as exciton quenchers, and a subsequent slower disintegration of the hydrogen

  20. Effect of N-substituents on redox, optical, and electronic properties of naphthalene bisimides used for field-effect transistors fabrication.

    PubMed

    Gawrys, Pawel; Djurado, David; Rimarcík, Ján; Kornet, Aleksandra; Boudinet, Damien; Verilhac, Jean-Marie; Lukes, Vladimír; Wielgus, Ireneusz; Zagorska, Malgorzata; Pron, Adam

    2010-02-11

    Three groups of naphthalene bisimides were synthesized and comparatively studied, namely, alkyl bisimides, alkylaryl ones, and novel bisimides containing the alkylthienyl moiety in the N-substituent. The experimental absorption spectra measured in CHCl(3) exhibit one intensive absorption band that is uniformly detected in the spectral range of 340 to 400 nm for all studied molecules. This band consists of three or four vibronic peaks. The introduction of an alkylthienyl group results in the appearance of an additional band (in the spectral range from 282 to 326 nm, depending on the position of the substituent) that can be ascribed to the pi-pi* transition in the thienyl chromophore. The minimal substituent effect on the lowest electronic transitions was explained using the quantum chemical calculations based on the time-dependent density functional theory. The investigation of the shapes of frontier orbitals have also shown that the oxidation of bisimides containing thiophene moiety is primary connected with the electron abstraction from the thienyl ring. To the contrary, the addition of an electron in the reduction process leads to an increase in the electron density in the central bisimide core. As shown by the electrochemical measurements, the onset of the first reduction potential (so-called "electrochemically determined LUMO level") is sensitive toward the type of the substituent being shifted from about -3.72 eV for bisimides with alkyl substituents to about -3.83 eV for alkylaryl ones and to about -3.94 eV for bisimides with thienyl groups. The presence of the thienyl ring also lowers the energy difference between the HOMO and LUMO orbitals. These experimental data can be well correlated with the DFT calculations in terms of HOMO/LUMO shapes and energies. Taking into account the low position of their LUMO level and their highly ordered supramolecular organization, the new bisimides are good candidates for the use in n-channel field effect transistors

  1. A perylene bisimide derivative with pyrene and cholesterol as modifying structures: synthesis and fluorescence behavior.

    PubMed

    Wang, Gang; Wang, Weina; Miao, Rong; Shang, Congdi; He, Meixia; Peng, Haonan; He, Gang; Fang, Yu

    2016-04-28

    A perylene bisimide (PBI) derivative (C-PBI-Py) of pyrene (Py) and cholesteryl residue (C) possessing intra-molecular energy transfer properties and three reference compounds (C-Py, C-PBI, PBI-Py) were designed and synthesized, where C was introduced in order to enhance the solubility of the relevant compounds in organic solvents. UV-vis absorption, steady-state fluorescence, cyclic voltammetric and theoretical calculation studies revealed that: (1) the PBI unit and Py moiety of C-PBI-Py could act as two individual chromophores, (2) the excited state energy of Py could transfer to PBI within a single molecule of the compound, and (3) the PBI moiety of the compound tends to form aggregates and shows PBI excimer emission. Time-resolved and temperature-dependent emission spectroscopy studies revealed the presence of both H-type excimer and J-type excimer, and formation of them via either the Birks' scheme or the pre-formed scheme due to strong π-π stacking that was elucidated by concentration-dependent (1)H NMR spectroscopy measurement. In addition, the studies also indicated that the energy transfer occurs via an electron exchange mechanism (Dexter scheme). Results of this study will be useful in the development of new solvatochromic and other environment-sensitive fluorophores based on alteration of intra-molecular energy transfer efficiency.

  2. Novel EDTA-ligands containing an integral perylene bisimide (PBI) core as an optical reporter unit.

    PubMed

    Marcia, Mario; Singh, Prabhpreet; Hauke, Frank; Maggini, Michele; Hirsch, Andreas

    2014-09-28

    The synthesis, characterization and metal complexation of a new class of perylene bisimides (PBIs) as an integral part of ethylenediaminetetraacetic acid (EDTA) are reported. The simplest representative, namely derivative 1a, was synthesized both by a convergent as well as a direct approach while the elongated derivatives, 1b and 1c, were obtained only via a convergent synthetic pathway. All these new prototypes of water-soluble perylenes are bolaamphiphiles and were fully characterized by (1)H- and (13)C-NMR spectroscopy, matrix assisted laser desorption ionization-time of flight (MALDI-TOF) mass spectrometry and IR spectroscopy. In order to acquaint ourselves with the behaviour in solution of our PBIs bearing dendritic wedges, the simplest derivative, 1a, was chosen and tested by means of UV/Vis and fluorescence spectroscopy as well as by zeta-potential measurements. A photoexcitation induced intramolecular photo-electron transfer (PET) can be observed in these molecules. Therefore their potential applications as sensors can be imagined. Model compound 1a efficiently coordinates trivalent metal cations both in water and dimethyl sulfoxide (DMSO). Significantly, the effects of the complexation strongly depend on the aggregation state of the PBI molecules in solution. As a matter of fact, in water, the presence of M(3+) ions triggers the formation of light emitting supramolecular aggregates (excimers). On the other hand, in DMSO-rich solutions metal complexation leads to the suppression of the PET and leads to a strong fluorescence enhancement.

  3. Hierarchical self-assembly of chiral rod-like molecules as a model for peptide β-sheet tapes, ribbons, fibrils, and fibers

    PubMed Central

    Aggeli, A.; Nyrkova, I. A.; Bell, M.; Harding, R.; Carrick, L.; McLeish, T. C. B.; Semenov, A. N.; Boden, N.

    2001-01-01

    A generic statistical mechanical model is presented for the self-assembly of chiral rod-like units, such as β-sheet-forming peptides, into helical tapes, which with increasing concentration associate into twisted ribbons (double tapes), fibrils (twisted stacks of ribbons), and fibers (entwined fibrils). The finite fibril width and helicity is shown to stem from a competition between the free energy gain from attraction between ribbons and the penalty because of elastic distortion of the intrinsically twisted ribbons on incorporation into a growing fibril. Fibers are stabilized similarly. The behavior of two rationally designed 11-aa residue peptides, P11-I and P11-II, is illustrative of the proposed scheme. P11-I and P11-II are designed to adopt the β-strand conformation and to self-assemble in one dimension to form antiparallel β-sheet tapes, ribbons, fibrils, and fibers in well-defined solution conditions. The energetic parameters governing self-assembly have been estimated from the experimental data using the model. The 8-nm-wide fibrils consist of eight tapes, are extremely robust (scission energy ≈200 kBT), and sufficiently rigid (persistence length l̃fibril ≈ 20–70 μm) to form nematic solutions at peptide concentration c ≈ 0.9 mM (volume fraction ≈0.0009 vol/vol), which convert to self-supporting nematic gels at c > 4 mM. More generally, these observations provide a new insight into the generic self-assembling properties of β-sheet-forming peptides and shed new light on the factors governing the structures and stability of pathological amyloid fibrils in vivo. The model also provides a prescription of routes to novel macromolecules based on a variety of self-assembling chiral units, and protocols for extraction of the associated energy changes. PMID:11592996

  4. Rigid rod-like dinuclear Ru(II)/Os(II) terpyridine-type complexes. Electrochemical behavior, absorption spectra, luminescence properties, and electronic energy transfer through phenylene bridges

    SciTech Connect

    Barigelletti, F.; Flamigni, L.; Balzani, V. ||

    1994-08-24

    The absorption spectra, the luminescence properties (at 293 and 77 K), and the electrochemical behavior of six dinuclear heterometallic compounds have been investigated. The compounds are made of Ru(tpy){sub 2}{sup 2+}- and Os(tpy){sub 2}{sup 2+}-type components (tpy = 2,2{prime}:6{prime},2 inches-terpyridine, which in some cases carries p-tolyl (Meph) or methylsulphone (MeO{sub 2}S) substituents in the 4{prime} position), connected by n phenylene (ph) spacers (n=0,1, and 2). In the resulting rigid rod-like structures of general formula (X{sub 1}tpy)Ru(tpy(ph){sub n}tpy)Os(tpyX{sub 2}){sup 4+} the metal-to-metal distance varies form 11 to 20 {Angstrom}. The absorption spectra of the two components are slightly perturbed in the dinuclear compounds, and metal-metal and ligand-ligand interactions are evidenced by the trends of the oxidation and reduction potentials. The luminescence of the Ru-based unit is quenched by the connected Os-based unit with practically unitary efficiency, regardless of the number of interposed phenylene spacers. Quenching is accompanied by quantitative sensitization of the Os-based luminescence. The rate of energy transfer at 293 K is larger than 10{sup 10} s{sup -1} in all cases. The Foerster (Coulombic) mechanism does not satisfactorily account for such a fast rate, particularly for the species with n=2. It is concluded that the observed energy-transfer processes take place most likely via a Dexter (electron exchange) mechanism. This is consistent with the strong electronic coupling of the Ru-based units in the compound with n=0, and with the relatively small insulating effect expected for the phenylene spacers. 37 refs., 7 figs., 3 tabs.

  5. Synthesis of α-Fe2O3 Sphere/Rod-Like Nanostructure via Simple Surfactant-Free Precipitation Route: Optical Properties and Formation Mechanism.

    PubMed

    Narayanan, S; Vijayal, J Judith; Adinaveen, T; Bououdina, M; Kennedy, L John

    2015-06-01

    Sphere/rod-like α-Fe2O3 nanostructure were successfully synthesized by simple surfactant-free precipitation route. The as-prepared samples were characterized by X-ray powder diffraction (XRD) to determine the phase purity and the crystal structure. The lattice parameter and crystallite size of the samples have been calculated from the Rietveld analysis. The crystallite size has been compared by Scherrer's formula and Rietveld method and both method showed increase of the grain size with the increase of the calcined temperature. The crystallite size was in the range of 5-30 nm. The high resolution scanning electron microscopy (HR-SEM) analysis of the samples shows that the morphology of the nanostructures changed from nanospheres into nanorods and it was confirmed by high resolution transmission electron microscopy (HR-TEM). Energy dispersive X-ray (EDX) analysis reveals the presence of O and Fe elements only. The optical properties of the as-prepared nanostructures were determined by photoluminescence (PL) spectra. The band gap energy was investigated by UV-Visible diffuse reflectance spectra (DRS) and calculated by means of the Kubelka-Munk method. The band gap values are decreased from 2.26 eV to 2.17 eV as the temperature increased from 300 degrees C to 400 degrees C with increasing the crystallite size. A Vibrating Sample Magnetometer (VSM) was used to study the magnetic properties of iron oxide (α-Fe2O3) nanostructures. Magnetic hysteresis (M-H) loops revealed that the as-prepared α-Fe2O3 samples displayed ferromagnetic behavior.

  6. Self-assembly of dendronized perylene bisimides into complex helical columns.

    PubMed

    Percec, Virgil; Peterca, Mihai; Tadjiev, Timur; Zeng, Xiangbing; Ungar, Goran; Leowanawat, Pawaret; Aqad, Emad; Imam, Mohammad R; Rosen, Brad M; Akbey, Umit; Graf, Robert; Sekharan, Sivakumar; Sebastiani, Daniel; Spiess, Hans W; Heiney, Paul A; Hudson, Steven D

    2011-08-10

    The synthesis of perylene 3,4:9,10-tetracarboxylic acid bisimides (PBIs) dendronized with first-generation dendrons containing 0 to 4 methylenic units (m) between the imide group and the dendron, (3,4,5)12G1-m-PBI, is reported. Structural analysis of their self-organized arrays by DSC, X-ray diffraction, molecular modeling, and solid-state (1)H NMR was carried out on oriented samples with heating and cooling rates of 20 to 0.2 °C/min. At high temperature, (3,4,5)12G1-m-PBI self-assemble into 2D-hexagonal columnar phases with intracolumnar order. At low temperature, they form orthorhombic (m = 0, 2, 3, 4) and monoclinic (m = 1) columnar arrays with 3D periodicity. The orthorhombic phase has symmetry close to hexagonal. For m = 0, 2, 3, 4 ,they consist of tetramers as basic units. The tetramers contain a pair of two molecules arranged side by side and another pair in the next stratum of the column, turned upside-down and rotated around the column axis at different angles for different m. In contrast, for m = 1, there is only one molecule in each stratum, with a four-strata 2(1) helical repeat. All molecules face up in one column, and down in the second column, of the monoclinic cell. This allows close and extended π-stacking, unlike in the disruptive up-down alteration from the case of m = 0, 2, 3, 4. Most of the 3D structures were observed only by cooling at rates of 1 °C/min or less. This complex helical self-assembly is representative for other classes of dendronized PBIs investigated for organic electronics and solar cells.

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

    PubMed

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

    2012-05-09

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

  8. Screening Libraries of Semifluorinated Arylene Bisimides to Discover and Predict Thermodynamically Controlled Helical Crystallization.

    PubMed

    Ho, Ming-Shou; Partridge, Benjamin E; Sun, Hao-Jan; Sahoo, Dipankar; Leowanawat, Pawaret; Peterca, Mihai; Graf, Robert; Spiess, Hans W; Zeng, Xiangbing; Ungar, Goran; Heiney, Paul A; Hsu, Chain-Shu; Percec, Virgil

    2016-12-12

    Synthesis, structural, and retrostructural analysis of a library containing 16 self-assembling perylene (PBI), 1,6,7,12-tetrachloroperylene (Cl4PBI), naphthalene (NBI), and pyromellitic (PMBI) bisimides functionalized with environmentally friendly AB3 chiral racemic semifluorinated minidendrons at their imide groups via m = 0, 1, 2, and 3 methylene units is reported. These semifluorinated compounds melt at lower temperatures than homologous hydrogenated compounds, permitting screening of all their thermotropic phases via structural analysis to discover thermodynamically controlled helical crystallization from propeller-like, cogwheel, and tilted molecules as well as lamellar-like structures. Thermodynamically controlled helical crystallization was discovered for propeller-like PBI, Cl4PBI and NBI with m = 0. Unexpectedly, assemblies of twisted Cl4PBIs exhibit higher order than those of planar PBIs. PBI with m = 1, 2, and 3 form a thermodynamically controlled columnar hexagonal 2D lattice of tilted helical columns with intracolumnar order. PBI and Cl4PBI with m = 1 crystallize via a recently discovered helical cogwheel mechanism, while NBI and PMBI with m = 1 form tilted helical columns. PBI, NBI and PMBI with m = 2 generate lamellar-like structures. 3D and 2D assemblies of PBI with m = 1, 2, and 3, NBI with m = 1 and PMBI with m = 2 exhibit 3.4 Å π-π stacking. The library approach applied here and in previous work enabled the discovery of six assemblies which self-organize via thermodynamic control into 3D and 2D periodic arrays, and provides molecular principles to predict the supramolecular structure of electronically active components.

  9. Synthesis, spectra, and electron-transfer reaction of aspartic acid-functionalized water-soluble perylene bisimide in aqueous solution.

    PubMed

    Zhong, Lina; Xing, Feifei; Shi, Wei; Yan, Liuming; Xie, Liqing; Zhu, Shourong

    2013-04-24

    An aspartic acid-functionalized water-soluble perylene bisimide, N,N'-di(2-succinic acid)-perylene-3,4,9,10-tetracarboxylic bisimide (PASP) was synthesized and characterized. It has absorbance maximum A(0-0) and A(0-1) at 527 and 498 nm (ε ≈ 1.7 × 10(4) L cm(-1) mol(-1)) respectively in pH 7.20 HEPES buffer. Two quasi-reversible redox processes with E1/2 at -0.17 and -0.71 V (vs Ag/AgCl) respectively in pH 7-12.5 aqueous solutions. PASP can react with Na2S in pure aqueous solution to form monoanion radical and dianion species consecutively. PASP(-•) has EPR signal with g = 1.998 in aqueous solution, whereas PASP(2-) is EPR silent. The monoanion radical formation is a first-order reaction with k = 8.9 × 10(-2) s(-1). Dianion species formation is a zero-order reaction and the rate constant is 4.3 × 10(-8) mol L(-1) s(-1). The presence of H2O2 greatly increases the radical formation rate constant. PASP as a two-electron transfer reagent is expected to be used in the water photolysis.

  10. Low and High Molecular Mass Dithienopyrrole-Naphthalene Bisimide Donor-Acceptor Compounds: Synthesis, Electrochemical and Spectroelectrochemical Behaviour.

    PubMed

    Rybakiewicz, Renata; Glowacki, Eric D; Skorka, Lukasz; Pluczyk, Sandra; Zassowski, Pawel; Apaydin, Dogukan Hazar; Lapkowski, Mieczyslaw; Zagorska, Malgorzata; Pron, Adam

    2017-02-24

    Two low molecular weight electroactive donor-acceptor-donor (DAD)-type molecules are reported, namely naphthalene bisimide (NBI) symmetrically core-functionalized with dithienopyrrole (NBI-(DTP)2 ) and an asymmetric core-functionalized naphthalene bisimide with dithienopyrrole (DTP) substituent on one side and 2-ethylhexylamine on the other side (NBI-DTP-NHEtHex). Both compounds are characterized by low optical bandgaps (1.52 and 1.65 eV, respectively). NBI-(DTP)2 undergoes oxidative electropolymerization giving the electroactive polymer of ambipolar character. Its two-step reversible reduction and oxidation is corroborated by complementary EPR and UV/Vis-NIR spectroelectrochemical investigations. The polymer turned out to be electrochemically active not only in aprotic solvents but also in aqueous electrolytes, showing a distinct photocathodic current attributed to proton reduction. Additionally, poly(NBI-(DTP)2 ) was successfully tested as a photodiode material. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Supramolecular block copolymers by kinetically controlled co-self-assembly of planar and core-twisted perylene bisimides

    PubMed Central

    Görl, Daniel; Zhang, Xin; Stepanenko, Vladimir; Würthner, Frank

    2015-01-01

    New synthetic methodologies for the formation of block copolymers have revolutionized polymer science within the last two decades. However, the formation of supramolecular block copolymers composed of alternating sequences of larger block segments has not been realized yet. Here we show by transmission electron microscopy (TEM), 2D NMR and optical spectroscopy that two different perylene bisimide dyes bearing either a flat (A) or a twisted (B) core self-assemble in water into supramolecular block copolymers with an alternating sequence of (AmBB)n. The highly defined ultralong nanowire structure of these supramolecular copolymers is entirely different from those formed upon self-assembly of the individual counterparts, that is, stiff nanorods (A) and irregular nanoworms (B), respectively. Our studies further reveal that the as-formed supramolecular block copolymer constitutes a kinetic self-assembly product that transforms into thermodynamically more stable self-sorted homopolymers upon heating. PMID:25959777

  12. Fabrication and humidity sensing performance studies of a fluorescent film based on a cholesteryl derivative of perylene bisimide

    NASA Astrophysics Data System (ADS)

    Zhang, Shujuan; Zhou, Feng; Peng, Haonan; Liu, Taihong; Ding, Liping; Fang, Yu

    2016-08-01

    A fluorescent film based on a cholesteryl derivative of perylene bisimide (PTCDI-co-CholDEA) was fabricated via utilization of an electrostatic spinning technique on a glass plate surface. SEM studies revealed that the film was characterized by fibrous network structure. It is the structure and the chemical composition that make the fluorescence emission of the film sensitive to the variation of local environmental humidity. The sensitivity of the sensing is 0.1497 (× 104 a.u. of the intensity)/1% RH, of which RH is the abbreviation of relative humidity. The maximum quenching efficiency of the film is 55.4% when humidity reaches 97% RH. Furthermore, the sensing process is fully reversible, and presence of other commonly found liquids shows little effect to the monitoring process.

  13. Subcomponent self-assembly of a 4 nm M4 L6 tetrahedron with Zn(II) vertices and perylene bisimide dye edges.

    PubMed

    Frischmann, Peter D; Kunz, Valentin; Stepanenko, Vladimir; Würthner, Frank

    2015-02-09

    Formation of a tetrahedron with >4 nm perylene bisimide (PBI) dye edges and Zn(II) vertices in a one-pot 22 component self-assembly reaction is reported. The luminescent polyhedron equilibrates to a Zn2 L3 helicate and disassembles upon dilution. Insights into the subcomponent self-assembly of extended PBI ligands help to refine design rules for constructing large photofunctional metallosupramolecular hosts.

  14. Non-covalent synthesis of thermo-responsive graphene oxide-perylene bisimides-containing poly(N-isopropylacrylamide) hybrid for organic pigment removal.

    PubMed

    Wang, Liang; Jiang, Lai; Su, Dan; Sun, Chen; Chen, Minfang; Goh, Kunli; Chen, Yuan

    2014-09-15

    In this work, thermo-responsive graphene oxide-perylene bisimides-containing poly(N-isopropylacrylamide) hybrid (TGO) was successfully prepared via non-covalent π-π stacking interactions of GO and perylene bisimides-containing poly(N-isopropylacrylamide) (PBI-PNIPAM). PBI-PNIPAM was synthesized by atom transfer radical polymerization of N-isopropylacrylamide, using bifunctional N,N'-bis[6-(2-chloropropionamide)hexyl] perylene-3,4,9,10-tetracarboxylic acid bisimide (PBI-Cl) as the initiator. The obtained polymer was then characterized by (1)H NMR and fluorescence spectroscopy. The surface chemical states, morphology, and composition of TGO were characterized by X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), respectively. This new hybrid showed reversible temperature-dependent self-assembly and disassembly at 35.9°C in water. Therefore, it may have great potentials as a convenient adsorbent for removing organic pigment, as exemplified as for removing methylene blue from water with excellent adsorption capacity of 568 mg/g, high removal efficiency of 99.5%, and facile temperature-controlled post-separation of the adsorbent.

  15. Synthesis and electrocatalytic performance for p-nitrophenol reduction of rod-like Co{sub 3}O{sub 4} and Ag/Co{sub 3}O{sub 4} composites

    SciTech Connect

    Pan, Lu; Tang, Jing; Wang, Fengwu

    2013-07-15

    Graphical abstract: The pure Co{sub 3}O{sub 4} and Ag/Co{sub 3}O{sub 4} composite with 5% Ag all exhibited rod-like morphology, and the microrods were actually composed of nanoparticles with mean size of 35 nm or so. - Highlights: • A facile route was designed to fabricate rod-like Co{sub 3}O{sub 4} and Ag/Co{sub 3}O{sub 4} composite nanomaterials. • Co{sub 3}O{sub 4} and Ag/Co{sub 3}O{sub 4} composite were modified on a GCE directly. • All samples exhibited enhanced catalytic property for p-nitrophenol reduction. - Abstract: Rod-like precursors of Co{sub 3}O{sub 4} and Ag/Co{sub 3}O{sub 4} composites with different Ag contents were synthesized via a co-precipitation method. Co{sub 3}O{sub 4} and Ag/Co{sub 3}O{sub 4} composite samples were fabricated by calcining each precursor at 400 °C for 3 h. The as-prepared samples were characterized by thermogravimetric analysis and differential thermal gravimetric analysis (TGA/DTA), X-ray diffraction (XRD), transmission electron microscopy (TEM), and field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), respectively. Co{sub 3}O{sub 4} and Ag/Co{sub 3}O{sub 4} composites were used as electrocatalyst modified on a glassy carbon electrode for p-nitrophenol reduction in basic solution. The results showed that p-nitrophenol could be reduced effectively on the modified electrode. By comparison with a bare glassy carbon electrode, peak current increased markedly with Co{sub 3}O{sub 4} and Ag/Co{sub 3}O{sub 4} samples, and peak potential decreased obviously with Ag/Co{sub 3}O{sub 4} samples. Ag/Co{sub 3}O{sub 4} composites with 4% Ag exhibited the highest electrocatalytic activity for p-nitrophenol reduction.

  16. Dissecting the secondary structure of the circular RNA of a nuclear viroid in vivo: A "naked" rod-like conformation similar but not identical to that observed in vitro.

    PubMed

    López-Carrasco, Amparo; Flores, Ricardo

    2016-08-30

    With a minimal (250-400 nt), non-protein-coding, circular RNA genome, viroids rely on sequence/structural motifs for replication and colonization of their host plants. These motifs are embedded in a compact secondary structure whose elucidation is crucial to understand how they function. Viroid RNA structure has been tackled in silico with algorithms searching for the conformation of minimal free energy, and in vitro by probing in solution with RNases, dimethyl sulphate and bisulphite, and with selective 2'-hydroxyl acylation analyzed by primer extension (SHAPE), which interrogates the RNA backbone at single-nucleotide resolution. However, in vivo approaches at that resolution have not been assayed. Here, after confirming by 3 termodynamics-based predictions and by in vitro SHAPE that the secondary structure adopted by the infectious monomeric circular (+) RNA of potato spindle tuber viroid (PSTVd) is a rod-like conformation with double-stranded segments flanked by loops, we have probed it in vivo with a SHAPE modification. We provide direct evidence that a similar, but not identical, rod-like conformation exists in PSTVd-infected leaves of Nicotiana benthamiana, verifying the long-standing view that this RNA accumulates in planta as a "naked" form rather than tightly associated with protecting host proteins. However, certain nucleotides of the central conserved region, including some of the loop E involved in key functions such as replication, are more SHAPE-reactive in vitro than in vivo. This difference is most likely due to interactions with proteins mediating some of these functions, or to structural changes promoted by other factors of the in vivo habitat.

  17. Direct observation of ultrafast coherent exciton dynamics in helical π-stacks of self-assembled perylene bisimides

    PubMed Central

    Sung, Jooyoung; Kim, Pyosang; Fimmel, Benjamin; Würthner, Frank; Kim, Dongho

    2015-01-01

    Ever since the discovery of dye self-assemblies in nature, there have been tremendous efforts to exploit biomimetic supramolecular assemblies for tailored artificial photon processing materials. This feature necessarily has resulted in an increasing demand for understanding exciton dynamics in the dye self-assemblies. In a sharp contrast with J-type aggregates, however, the detailed observation of exciton dynamics in H-type aggregates has remained challenging. In this study, as we succeed in measuring transient fluorescence from Frenkel state of π-stacked perylene tetracarboxylic acid bisimide dimer and oligomer aggregates, we present an experimental demonstration on Frenkel exciton dynamics of archetypal columnar π–π stacks of dyes. The analysis of the vibronic peak ratio of the transient fluorescence spectra reveals that unlike the simple π-stacked dimer, the photoexcitation energy in the columnar π-stacked oligomer aggregates is initially delocalized over at least three molecular units and moves coherently along the chain in tens of femtoseconds, preceding excimer formation process. PMID:26492820

  18. Understanding ground- and excited-state properties of perylene tetracarboxylic acid bisimide crystals by means of quantum chemical computations.

    PubMed

    Zhao, Hong-Mei; Pfister, Johannes; Settels, Volker; Renz, Manuel; Kaupp, Martin; Dehm, Volker C; Würthner, Frank; Fink, Reinhold F; Engels, Bernd

    2009-11-04

    Quantum chemical protocols explaining the crystal structures and the visible light absorption properties of 3,4:9,10-perylene tetracarboxylic acid bisimide (PBI) derivates are proposed. Dispersion-corrected density functional theory has provided an intermolecular potential energy of PBI dimers showing several energetically low-lying minima, which corresponds well with the packing of different PBI dyes in the solid state. While the dispersion interaction is found to be crucial for the binding strength, the minimum structures of the PESs are best explained by electrostatic interactions. Furthermore, a method is introduced, which reproduces the photon energies at the absorption maxima of PBI pigments within 0.1 eV. It is based on time-dependent Hartree-Fock (TD-HF) excitation energies calculated for PBI dimers with the next-neighbor arrangement in the pigment and incorporates crystal packing effects. This success provides clear evidence that the electronically excited states, which determine the color of these pigments, have no significant charge-transfer character. The developed protocols can be applied in a routine manner to understand and to predict the properties of such pigments, which are important materials for organic solar cells and (opto-)electronic devices.

  19. Can the Excited State Energy of a Pyrenyl Unit Be Directly Transferred to a Perylene Bisimide Moiety?

    PubMed

    Wang, Gang; Shang, Congdi; Wang, Li; Peng, Haonan; Yin, Shiwei; Fang, Yu

    2016-11-23

    A pyrenyl unit (Py) was chemically connected to a perylene bisimide (PBI) moiety through a long and flexible linker, 4,7,10-trioxa-1,13-tridecanediamine (TOA), resulting in a fluorescent dyad, PBI-TOA-Py. Ultraviolet-visible absorption and fluorescence studies revealed that the two fluorescent units of PBI-TOA-Py behave independently. However, efficient Förster resonance energy transfer (FRET) from the Py unit to the PBI moiety in solution state was also observed. Temperature and solvent effect studies demonstrated that the energy transfer efficiency is highly dependent upon solution temperature and solvent nature. Specifically, for the dimethylformamide (DMF) solution of PBI-TOA-Py, the FRET efficiency is close to 88% at temperatures below ∼40 °C, but the efficiency greatly decreases to nearly zero when the temperature exceeds ∼80 °C. Moreover, addition of HAc into the DMF solution at room temperature could reduce the energy transfer efficiency to nearly zero, suggesting that the excited state energy of Py cannot be directly transferred to the PBI structure even though they are properly and chemically bonded. On the basis of the observations and time-resolved studies, it is believed that the observed efficient FRET from the Py unit to the PBI moiety occurs mainly through Py excimer formation, which could be a result of intermolecular association of the compound. Thus, the applications of the fluorescent dyad in solvent discrimination and trace water determination in organic solvents were verified through example studies.

  20. Fluorescence turn-on sensing of protein based on mannose functionalized perylene bisimides and its fluorescence imaging.

    PubMed

    Wang, Ke-Rang; An, Hong-Wei; Rong, Rui-Xue; Cao, Zhi-Ran; Li, Xiao-Liu

    2014-08-15

    A new water-soluble glycocluster based on perylene bisimides PBI-12-Man has been designed and synthesized, and its specific and selective binding property with Concanavalin A (Con A) has been investigated by fluorescence spectroscopy and circular dichroism (CD) spectroscopy, which showed strong binding affinity for Con A with the binding constant of 8.2×10(5)M(-1) for monomeric mannose unit, two orders of magnitude higher than the corresponding monosaccharide ligand. Most interestingly, a fluorescence enhancement of PBI-12-Man was observed upon binding with Con A because of deaggregation of the self-assembly of PBI-12-Man induced by carbohydrate-protein interaction, and the further study of the fluorescence enhancement with macrophage cells showed that PBI-12-Man as a biocompatible agent had fluorescence imaging of the surface mannose receptor of the cells. Such fluorescence turn-on sensing of protein based on carbohydrate-protein interactions would facilitate the development of new protein-specific fluorescent probe for diagnosis and molecular imaging under live cell conditions.

  1. Modification of nanocrystalline WO3 with a dicationic perylene bisimide: applications to molecular level solar water splitting.

    PubMed

    Ronconi, Federico; Syrgiannis, Zois; Bonasera, Aurelio; Prato, Maurizio; Argazzi, Roberto; Caramori, Stefano; Cristino, Vito; Bignozzi, Carlo Alberto

    2015-04-15

    [(N,N'-Bis(2-(trimethylammonium)ethylene) perylene 3,4,9,10-tetracarboxylic acid bisimide)(PF6)2] (1) was observed to spontaneously adsorb on nanocrystalline WO3 surfaces via aggregation/hydrophobic forces. Under visible irradiation (λ > 435 nm), the excited state of 1 underwent oxidative quenching by electron injection (kinj > 10(8) s(-1)) to WO3, leaving a strongly positive hole (Eox ≈ 1.7 V vs SCE), which allows to drive demanding photo-oxidation reactions in photoelectrochemical cells (PECs). The casting of IrO2 nanoparticles (NPs), acting as water oxidation catalysts (WOCs) on the sensitized electrodes, led to a 4-fold enhancement in photoanodic current, consistent with hole transfer from oxidized dye to IrO2 occurring on the microsecond time scale. Once the interaction of the sensitizer with suitable WOCs is optimized, 1/WO3 photoanodes may hold potentialities for the straightforward building of molecular level devices for solar fuel production.

  2. Perylene bisimide dimer aggregates: fundamental insights into self-assembly by NMR and UV/Vis spectroscopy.

    PubMed

    Shao, Changzhun; Grüne, Matthias; Stolte, Matthias; Würthner, Frank

    2012-10-22

    A novel perylene bisimide (PBI) dye bearing one solubilizing dialkoxybenzyl and one bulky 2,5-di-tert-butylphenyl substituent was synthesized and its aggregation behavior was analyzed by NMR and UV/Vis spectroscopy in various chloroform/methylcyclohexane (MCH) solvent mixtures. In the presence of no less than 10 vol % chloroform, exclusive self-assembly of this PBI dye into π-stacked dimers was unambiguously confirmed by means of both concentration-dependent (1) H NMR and UV/Vis spectroscopic experiments. Based on ROESY NMR, a well-defined π-stacked dimer structure was determined and further corroborated by molecular modeling studies. By varying the solvent composition of chloroform and MCH, the solvent effects on the Gibbs free energy of PBI dimerization were elucidated and showed a pronounced nonlinearity between lower and higher MCH contents. This observation could be related to a further growth process of dimers into larger aggregates that occurs in the absence of chloroform, which is required to solvate the aromatic π surfaces. With the help of a single-crystal structure analysis for a related PBI dye, a structural model could be derived for the extended aggregates that are still composed of defined π-π-stacked PBI dimer entities.

  3. High-Performance Solution-Processed Non-Fullerene Organic Solar Cells Based on Selenophene-Containing Perylene Bisimide Acceptor.

    PubMed

    Meng, Dong; Sun, Dan; Zhong, Chengmei; Liu, Tao; Fan, Bingbing; Huo, Lijun; Li, Yan; Jiang, Wei; Choi, Hyosung; Kim, Taehyo; Kim, Jin Young; Sun, Yanming; Wang, Zhaohui; Heeger, Alan J

    2016-01-13

    Non-fullerene acceptors have recently attracted tremendous interest because of their potential as alternatives to fullerene derivatives in bulk heterojunction organic solar cells. However, the power conversion efficiencies (PCEs) have lagged far behind those of the polymer/fullerene system, mainly because of the low fill factor (FF) and photocurrent. Here we report a novel perylene bisimide (PBI) acceptor, SdiPBI-Se, in which selenium atoms were introduced into the perylene core. With a well-established wide-band-gap polymer (PDBT-T1) as the donor, a high efficiency of 8.4% with an unprecedented high FF of 70.2% is achieved for solution-processed non-fullerene organic solar cells. Efficient photon absorption, high and balanced charge carrier mobility, and ultrafast charge generation processes in PDBT-T1:SdiPBI-Se films account for the high photovoltaic performance. Our results suggest that non-fullerene acceptors have enormous potential to rival or even surpass the performance of their fullerene counterparts.

  4. Perylene Bisimide as a Promising Zinc Oxide Surface Modifier: Enhanced Interfacial Combination for Highly Efficient Inverted Polymer Solar Cells.

    PubMed

    Nian, Li; Zhang, Wenqiang; Wu, Siping; Qin, Leiqiang; Liu, Linlin; Xie, Zengqi; Wu, Hongbin; Ma, Yuguang

    2015-11-25

    We report the application of a perylene bisimide (PBI-H) as zinc oxide (ZnO) surface modifier to afford an organic-inorganic co-interlayer for highly efficient inverted organic photovoltaics (i-OPV). By thermal annealing, a N-Zn chemical bond formed between PBI-H and ZnO, inducing close organic-inorganic combination. In addition, this co-interlayer shows decreased work function and increased electron transportation and conductivity, which are benefits for the cathode to enhance charge extraction efficiency and decrease recombination losses. As a result a highly efficient i-OPV was achieved with a power conversion efficiency (PCE) of 9.43% based on this co-interlayer with PTB7:PC71BM as the active layer, which shows over 35% enhancement compared to that of the device without the PBI-H layer. Moreover, this co-interlayer was widely applicable for i-OPVs based on various material systems, such as P3HT:PC61BM and PTB7-Th:PC71BM, resulting in PCE as high as 4.78% and 10.31%, respectively.

  5. Tuning the electronic nature of mono-bay alkynyl-phenyl-substituted perylene bisimides: synthesis, structure, and photophysical properties.

    PubMed

    Mishra, Ruchika; Lim, Jong Min; Son, Minjung; Panini, Piyush; Kim, Dongho; Sankar, Jeyaraman

    2014-05-05

    Perylene bisimide (PBI) derivatives with various alkynyl-phenyl substituents at a single bay position have been synthesised by Sonogashira coupling. NMR spectroscopic studies reveal the unsymmetric nature of the dyads. All of the dyads undergo two reversible reductions, which demonstrates their structural and electrochemical rigidity. The synthesised dyads show a remarkable redshift in their absorption maxima and sharp vibronic progression. Electron-rich substituents facilitate efficient charge transfer from the substituent HOMO to the electron-deficient PBI core. The most interesting spectral signatures were exhibited by a PBI with a strongly electron-donating ethynyl(dimethylaminophenyl) substituent. The steady-state features of this PBI showed a broad absorption that covered almost the whole visible region with no emission. A twisted intramolecular charge-transfer (TICT) process, related to the rotational motion of ethynyl(dimethylaminophenyl) PBI, was also demonstrated. Computational investigations shed light on the coplanarity of the various substituents with respect to the PBI core; the PBI core itself remains flat without any noticeable deformation even after mono-functionalisation. This illustrates that mono-functionalisation exerts meagre steric hindrance on the bay positions relative to disubstituted analogues. Despite several previous reports on the structural characterisation of 1,7-disubstituted PBI derivatives, we present the first structural characterisation of a mono-bay ethynyl-phenyl substituted PBI. The solid-state structure of the phenyl derivative has a flat PBI core without any noticeable steric constraints from the substituents, as predicted. In contrast, single-crystal X-ray analysis for the mono-bromo bay-substituted PBI shows that the bromine substituent is not in the plane of the PBI core. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Self-repairing complex helical columns generated via kinetically controlled self-assembly of dendronized perylene bisimides.

    PubMed

    Percec, Virgil; Hudson, Steven D; Peterca, Mihai; Leowanawat, Pawaret; Aqad, Emad; Graf, Robert; Spiess, Hans W; Zeng, Xiangbing; Ungar, Goran; Heiney, Paul A

    2011-11-16

    The dendronized perylene 3,4:9,10-tetracarboxylic acid bisimide (PBI), (3,4,5)12G1-3-PBI, was recently reported to self-assemble in complex helical columns containing tetramers of PBI as basic repeat unit. These tetramers contain a pair of two molecules arranged side-by-side and another pair in the next stratum of the column turned upside-down and rotated around the column axis. Intra- and intertetramer rotation angles and stacking distances are different. At high temperature, (3,4,5)12G1-3-PBI self-assembles via a thermodynamically controlled process in a 2D hexagonal columnar phase while at low temperature in a 3D orthorhombic columnar array via a kinetically controlled process. Here, we report the synthesis and structural analysis, by a combination of differential scanning calorimetry, X-ray and electron diffraction, and solid-state NMR performed at different temperatures, on the supramolecular structures generated by a library of (3,4,5)nG1-3-PBI with n = 14-4. For n = 11-8, the kinetically controlled self-assembly from low temperature changes in a thermodynamically controlled process, while the orthorhombic columnar array for n = 9 and 8 transforms from the thermodynamic product into the kinetic product. The new thermodynamic product at low temperature for n = 9, 8 is a self-repaired helical column with an intra- and intertetramer distance of 3.5 Å forming a 3D monoclinic periodic array via a kinetically controlled self-assembly process. The complex dynamic process leading to this reorganization was elucidated by solid-state NMR and X-ray diffraction. This discovery is important for the field of self-assembly and for the molecular design of supramolecular electronics and solar cell.

  7. Self-assembly of ferrocene-functionalized perylene bisimide bridging ligands with PtII corner to electrochemically active molecular squares.

    PubMed

    You, Chang-Cheng; Würthner, Frank

    2003-08-13

    Ferrocenyl-substituted N,N'-di(4-pyridyl)perylene bisimide ligands have been synthesized by the coupling reaction of hydroxyphenoxy-perylene bisimides with ferrocenyl carboxylic acids. By means of metallosupramolecular self-assembly, hitherto unprecedented multiredox active dendritic molecular squares with 16 ferrocene groups positioned in the bridging ligands are prepared from the perylene bispyridyl imide ligands and [Pt(dppp)][(OTf)(2)] (dppp = 1,3-bis(diphenylphosphano)propane; OTf = trifluoromethanesulfonate) corner in high yield. The isolated metallosupramolecular squares were characterized by elemental analysis, (1)H, (31)P[(1)H] NMR, and UV/vis spectroscopy. The electrochemical properties of the ligands and squares are investigated by cyclic voltammetry as well as spectroelectrochemistry. The results obtained show that the redox behavior of ferrocene units is influenced by the square superstructure. Furthermore, redox titration of free ligand and corresponding molecular square with the one-electron oxidant thianthrenium pentachloroantimonate reveals that ferrocene groups in these structures may be oxidized completely by this oxidant, and highly charged species generated through oxidation of ferrocenyl groups in molecular square cause decomposition of the assembly due to pronounced Coulombic repulsion.

  8. Comparative analysis of the energy levels of planar and core-twisted perylene bisimides in solution and solid state by UV/VIS, CV, and UPS/IPES

    NASA Astrophysics Data System (ADS)

    Arantes, C.; Scholz, M.; Schmidt, R.; Dehm, V.; Rocco, M. L. M.; Schöll, A.; Reinert, F.; Würthner, F.

    2012-09-01

    The frontier orbital energies of four different functionalized perylene bisimide derivatives, PBI-Ph(iPr)2, PBI-H4, PBI-F2 and PBI-Cl4, were directly determined by UV-photo electron spectroscopy (UPS) and inverse photo electron spectroscopy (IPES) and are compared to the results from cyclic voltammetry (CV) and optical absorption spectroscopy (UV/VIS). The optical spectra reveal significant differences between monomeric species in solution and assembled molecules in the condensed state for the nearly planar PBI-H4 and PBI-F2, which are attributed to significant π- π stacking interactions in the condensed phase. In contrast, for PBIs with bulky substituents or twisted core, i.e. 2,6-isopropylphenyl substituents at the imide positions (PBI-Ph(iPr)2) or four chlorine substituents at perylene bay positions (PBI-Cl4), similar spectra are observed in solution and in the condensed state, which suggests the absence of strong intermolecular π- π stacking interactions. An entirely different result is obtained for the HOMO/LUMO energy values obtained from UPS/IPES and CV measurements which do not reveal a significant impact of intermolecular π- π stacking interactions. When comparing CV and UPS/IPES results, an accentuated deviation was observed for the perylene bisimide derivatives as compared to correlations found in the literature.

  9. Controlled Assembly of Rod-Like Particles

    DTIC Science & Technology

    2012-11-29

    of Turnip Yellow Mosaic Virus by Cu(I) Catalyzed Azide?Alkyne 1,3-Dipolar Cycloaddition Reaction and Its Application in Cell Binding, Bioconjugate...that investigation of two-dimensional (2D) assembly of the icosahedral turnip yellow mosaic virus (TYMV) on cationic lipid monolayers at the air

  10. Room temperature synthesis of rod-like FeC2O4·2H2O and its transition to maghemite, magnetite and hematite nanorods through controlled thermal decomposition

    NASA Astrophysics Data System (ADS)

    Zhou, Weiwei; Tang, Kaibin; Zeng, Suyuan; Qi, Yunxia

    2008-02-01

    FeC2O4·2H2O nanorods with diameter of about 50 nm and length of up to several micrometers were synthesized at room temperature in a surfactant-assisted system, which was obtained by dissolving bis(2-ethylhexyl)sodium sulfosuccinate (AOT) in a mixed solution composed of water and ethylene glycol (EG). The influence of reaction conditions on the morphology of FeC2O4·2H2O is discussed in detail. Through direct thermal decomposition of FeC2O4·2H2O under different calcination conditions, maghemite (γ-Fe2O3), magnetite (Fe3O4) and hematite (α-Fe2O3) can be selectively obtained, preserving the rod-like morphology. Transmission electron microscope (TEM) and high-resolution transmission electron microscope (HRTEM) characterizations showed that the as-obtained iron oxide nanorods were composed of fine particles with different crystal orientations. The magnetic properties of the as-obtained iron oxide nanorods were systematically investigated.

  11. Multichromophoric hybrid species made of perylene bisimide derivatives and Ru(ii) and Os(ii) polypyridine subunits.

    PubMed

    Nastasi, Francesco; La Ganga, Giuseppina; Campagna, Sebastiano; Syrgiannis, Zois; Rigodanza, Francesco; Vitale, Stefania; Licciardello, Antonino; Prato, Maurizio

    2017-05-31

    Herein, the synthesis and the photophysical and redox properties of a new perylene bisimide (PBI) species (L), bearing two 1,10-phenanthroline (phen) ligands at the two imide positions of the PBI, and its dinuclear Ru(ii) and Os(ii) complexes, [(bpy)2Ru(μ-L)Ru(bpy)2](PF6)4 (Ru2; bpy = 2,2'-bipyridine) and [(Me2-bpy)2Os(μ-L)Os(Me2-bpy)2](PF6)4 (Os2; Me2-bpy = (4,4'-dimethyl)-2,2'-bipyridine), are reported. The absorption spectra of the compounds are dominated by the structured bands of the PBI subunit due to the lowest-energy spin-allowed π-π* transition. The spin-allowed MLCT transitions in Ru2 and Os2 are inferred by the absorption at 350-470 nm, where the PBI absorption is negligible. The absorption band extends towards the red region for Os2 due to the spin-forbidden MLCT transitions, intensified by the heavy osmium center. The reduction processes of the compounds are dominated by two successive mono-electronic PBI-based processes, which in the metal complexes are slightly shifted compared to the free ligand. On oxidation, both metal complexes undergo an apparent bi-electronic process (at 1.31 V vs. SCE for Ru2 and 0.77 V for Os2), attributed to the simultaneous one-electron oxidation of the two weakly-interacting metal centers. In Ru2 and Os2, the intense fluorescence of L subunit (λmax, 535 nm; τ, 4.3 ns; Φ, 0.91) is fully quenched, mainly by photoinduced electron transfer from the metal centers, on the ps timescale (time constant, 11 ps in Ru2 and 3 ps in Os2). Such photoinduced electron transfer leads to the formation of a charge-separated state, which directly decays to the ground state in about 70 ps in Os2, but produces the triplet π-π* state of the PBI subunit in 35 ps in Ru2. The results provide information on the excited-state processes of the hybrid species combining two dominant classes of chromophore/luminophore species, the PBI and the metal polypyridine complexes, and can be used for future design on new hybrid species with made

  12. Vanadium bisimide bonding investigated by X-ray crystallography, 51V and 13C nuclear magnetic resonance spectroscopy, and V L(3,2)-edge X-ray absorption near-edge structure spectroscopy.

    PubMed

    La Pierre, Henry S; Minasian, Stefan G; Abubekerov, Mark; Kozimor, Stosh A; Shuh, David K; Tyliszczak, Tolek; Arnold, John; Bergman, Robert G; Toste, F Dean

    2013-10-07

    Syntheses of neutral halide and aryl vanadium bisimides are described. Treatment of VCl2(NtBu)[NTMS(N(t)Bu)], 2, with PMe3, PEt3, PMe2Ph, or pyridine gave vanadium bisimides via TMSCl elimination in good yield: VCl(PMe3)2(N(t)Bu)2 3, VCl(PEt3)2(N(t)Bu)2 4, VCl(PMe2Ph)2(N(t)Bu)2 5, and VCl(Py)2(N(t)Bu)2 6. The halide series (Cl-I) was synthesized by use of TMSBr and TMSI to give VBr(PMe3)2(N(t)Bu)2 7 and VI(PMe3)2(N(t)Bu)2 8. The phenyl derivative was obtained by reaction of 3 with MgPh2 to give VPh(PMe3)2(N(t)Bu)2 9. These neutral complexes are compared to the previously reported cationic bisimides [V(PMe3)3(N(t)Bu)2][Al(PFTB)4] 10, [V(PEt3)2(N(t)Bu)2][Al(PFTB)4] 11, and [V(DMAP)(PEt3)2(N(t)Bu)2][Al(PFTB)4] 12 (DMAP = dimethylaminopyridine, PFTB = perfluoro-tert-butoxide). Characterization of the complexes by X-ray diffraction, (13)C NMR, (51)V NMR, and V L(3,2)-edge X-ray absorption near-edge structure (XANES) spectroscopy provides a description of the electronic structure in comparison to group 6 bisimides and the bent metallocene analogues. The electronic structure is dominated by π bonding to the imides, and localization of electron density at the nitrogen atoms of the imides is dictated by the cone angle and donating ability of the axial neutral supporting ligands. This phenomenon is clearly seen in the sensitivity of (51)V NMR shift, (13)C NMR Δδ(αβ), and L3-edge energy to the nature of the supporting phosphine ligand, which defines the parameters for designing cationic group 5 bisimides that would be capable of breaking stronger σ bonds. Conversely, all three methods show little dependence on the variable equatorial halide ligand. Furthermore, this analysis allows for quantification of the electronic differences between vanadium bisimides and the structurally analogous mixed Cp/imide system CpV(N(t)Bu)X2 (Cp = C5H5(1-)).

  13. Structure and magnetic properties evolution of rod-like Co0.5Ni0.25Zn0.25DyxFe2-xO4 synthesized by solvothermal method

    NASA Astrophysics Data System (ADS)

    Chen, Wen; Liu, Dongsheng; Wu, Wenwei; Zhang, Huaxin; Wu, Juan

    2017-01-01

    A series of Dy3+ doped Co-Ni-Zn ferrites with the formula Co0.5Ni0.25Zn0.25DyxFe2-xO4 0≤x≤0.24) have been successfully synthesized using the solvothermal method. X-ray diffraction and scanning electron microscope examinations indicate that a highly-crystallized cubic Co0.5Ni0.25Zn0.25DyxFe2-xO4 with rod-like morphology is obtained when the precursor is calcined at 1000 °C in air for 3 h. Single phase Co0.5Ni0.25Zn0.25Fe2O4 is obtained at 650 °C, but all samples consist of the main spinel phase in combination of a small amount of a foreign Dy2O3 phase after doping Dy. When the precursor is calcined at 1000 °C, the lattice parameter of the ferrites initially increase after doping Dy, but then become smaller with increasing Dy content. The addition of Dy content results in a reduction of crystallite size, attributed that the binding energy of Dy3+-O2- is larger than that of Fe3+-O2-. Dy3+ substitution can decrease the remanence (Mr) and coercivity (Hc) of Co0.5Ni0.25Zn0.25DyxFe2-xO4 samples, which are very desirable characteristics for high density data storage devices.

  14. Preparation of the rod-like {beta}-Si{sub 3}N{sub 4} particles favoring the self-reinforcing Si{sub 3}N{sub 4} ceramics

    SciTech Connect

    Dai Jinhui; Li Jianbao; Chen Yongjun; Yang Liu; Sun Geliang

    2003-03-24

    The {beta}-Si{sub 3}N{sub 4} particles were prepared by heating original {alpha}-Si{sub 3}N{sub 4} powder with rare earth oxide Nd{sub 2}O{sub 3} or Yb{sub 2}O{sub 3} additives at 1600-1700 deg. C for 1.5 h. The transformation ratio of {alpha}-Si{sub 3}N{sub 4} was also investigated by XRD. The results showed that Yb{sub 2}O{sub 3} could accelerate the transformation of Si{sub 3}N{sub 4} more effectively than Nd{sub 2}O{sub 3} and the powder heated at 1700 deg. C with over 4 wt.% Yb{sub 2}O{sub 3} has a high transformation ratio of over 98%. The morphologies of the heated powders were observed by scanning electron microscopy. The results showed that the powder heated at 1700 deg. C with 4 wt.% Yb{sub 2}O{sub 3} had ideal {beta}-Si{sub 3}N{sub 4} rod-like morphology particles. This heated powder was used as a seed by adding it to the original {alpha}-Si{sub 3}N{sub 4} powder to prepare self-reinforced Si{sub 3}N{sub 4} ceramic by hot-pressed sintering. The fracture toughness of the seeded Si{sub 3}N{sub 4} ceramics increased to 9.1 MPa m{sup 1/2} from 7.6 MPa m{sup 1/2} of the unseeded Si{sub 3}N{sub 4} ceramics, while the high value of strength was still kept at 1200 deg. C.

  15. Molecular size, shape, and electric charges: essential for perylene bisimide-based DNA intercalator to localize in cell nuclei and inhibit cancer cell growth.

    PubMed

    Xu, Zejun; Cheng, Wenyu; Guo, Kunru; Yu, Jieshi; Shen, Jie; Tang, Jun; Yang, Wantai; Yin, Meizhen

    2015-05-13

    The molecular properties concerning size, shape, and electric charges of the planar aromatic DNA intercalators are still poorly understood. Herein, a series of water-soluble perylene bisimide (PBI) derivatives containing a rigid and planar aromatic nanoscaffold with different size, shape, and electric charges were synthesized. Using histochemistry and cell viability assays on animal tissues and cancer cells, we revealed the molecular properties required for successful DNA intercalators to localize in cell nuclei and inhibit cancer cells. Small molecular size and the strong polarity of hydrophilic substituents are prerequisites for PBI-based DNA intercalators. A large number of charges facilitate the nucleic accumulation of these DNA intercalators, while fewer charges and planar aromatic nanoscaffold more efficiently inhibit cancer cell growth.

  16. A novel water-soluble fluorescent polymer based on perylene bisimides dyes: one-pot preparation and its bio-imaging.

    PubMed

    Tan, Haijian; Liu, Hongmei; Liu, Yaojun; Duan, Wenfeng; Yi, Xuegang; Wu, Yonggang; Zhao, Hongchi; Bai, Libin

    2016-01-01

    Perylene bisimides dye-based water-soluble fluorescent polymer P3, N,N'-bis(3-amyl)-1-bromo-7-{4'-[3''-(S-poly(N-acryloyl ethylene diamine hydrochloride)-2'''-methyl propionic acid)propionyloxy hexyloxy]phenyl} perylene-3,4:9,10-tetracarboxylic bisimides, was synthesized with polyelectrolyte modification via one-pot reaction (the reduction reaction of trithioester and click reaction between the thiol group and carbon-carbon double bond were simultaneously conducted in one pot with high conversion). One-pot method can overcome the limitation that usual click reaction between thiol and other groups has low conversion because thiol group is subject to rapid oxidation during purification and storage. Chemical, structural, and optical properties of P3 and intermediate products were fully characterized by nuclear magnetic resonance spectroscopy, Fourier transform infrared, gel permeation chromatograph, UV-vis spectra, and fluorescence spectra, respectively. The results revealed that P3 displayed excellent water solubility and not only exhibited red strong fluorescence emission band in water but also had the similar photoluminescent spectra to those of intermediate products (M4 and P2) in chloroform. Allowing for the potential application in biological detection field, cell viability and live cell imaging with the presence of P3 were further investigated with Hela cells. The results showed that P3 had low cytotoxicity with strong intracellular fluorescence entry. Meanwhile, with the augment of concentration of P3 (0-0.500 mg mL(-1)), the cell uptake and accumulation of P3 increased and thereby result in enhancement of the intracellular fluorescence. These experiment results suggested that P3 had enormous potential as a fluorescence probe to be an important component in biological detection field.

  17. Differential self-assembly and tunable emission of aromatic peptide bola-amphiphiles containing perylene bisimide in polar solvents including water.

    PubMed

    Bai, Shuo; Debnath, Sisir; Javid, Nadeem; Frederix, Pim W J M; Fleming, Scott; Pappas, Charalampos; Ulijn, Rein V

    2014-07-01

    We demonstrate the self-assembly of bola-amphiphile-type conjugates of dipeptides and perylene bisimide (PBI) in water and other polar solvents. Depending on the nature of the peptide used (glycine-tyrosine, GY, or glycine-aspartic acid, GD), the balance between H-bonding and aromatic stacking can be tailored. In aqueous buffer, PBI-[GY]2 forms chiral nanofibers, resulting in the formation of a hydrogel, while for PBI-[GD]2 achiral spherical aggregates are formed, demonstrating that the peptide sequence has a profound effect on the structure formed. In water and a range of other polar solvents, self-assembly of these two PBI-peptides conjugates results in different nanostructures with highly tunable fluorescence performance depending on the peptide sequence employed, e.g., fluorescent emission and quantum yield. Organogels are formed for the PBI-[GD]2 derivative in DMF and DMSO while PBI-[GY]2 gels in DMF. To the best of our knowledge, this is the first successful strategy for using short peptides, specifically, their sequence/structure relationships, to manipulate the PBI nanostructure and consequent optical properties. The combination of controlled self-assembly, varied optical properties, and formation of aqueous and organic gel-phase materials may facilitate the design of devices for various applications related to light harvesting and sensing.

  18. Exciton-Vibrational Couplings in Homo- and Heterodimer Stacks of Perylene Bisimide Dyes within Cyclophanes: Studies on Absorption Properties and Theoretical Analysis.

    PubMed

    Bialas, David; Brüning, Christoph; Schlosser, Felix; Fimmel, Benjamin; Thein, Johannes; Engel, Volker; Würthner, Frank

    2016-10-10

    The optical properties of a series of three cyclophanes comprising either identical or different perylene bisimide (PBI) chromophores were studied by UV/Vis absorption spectroscopy and their distinctive spectral features were analyzed. All the investigated cyclophanes show significantly different absorption features with respect to the corresponding constituent PBI monomers indicating strong coupling interactions between the PBI units within the cyclophanes. DFT calculations suggest a π-stacked arrangement of the PBI units at close van der Waals distance in the cyclophanes with rotational displacement. Simulations of the absorption spectra based on time-dependent quantum mechanics properly reproduced the experimental spectra, revealing exciton-vibrational coupling between the chromophores both in homo- and heterodimer stacks. The PBI cyclophane comprising two different PBI chromophores represents the first example of a PBI heterodimer stack for which the exciton coupling has been investigated. The quantum dynamics analysis reveals that exciton coupling in heteroaggregates is indeed of similar strength as for homoaggregates. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Perylene Bisimide Cyclophanes with High Binding Affinity for Large Planar Polycyclic Aromatic Hydrocarbons: Host-Guest Complexation versus Self-Encapsulation of Side Arms.

    PubMed

    Spenst, Peter; Sieblist, Andreas; Würthner, Frank

    2017-01-31

    Binding of guest molecules with high affinity and selectivity requires well-designed hosts to provide optimized interactions in the host-guest complexes. Herein we report the design and synthesis of new cyclophanes 2PBI(2,6-iPr)2 and 2PBI(2,6-Ph)2 based on core-disubstituted perylene bisimide (PBI) chromophores bearing two phenoxy bay-substituents that evoke almost planar PBI scaffolds. This strategy afforded the new cyclophanes with conformationally rigid cavities to ensure strong binding to stiff planar polycyclic aromatic hydrocarbons (PAHs). Our detailed host-guest binding studies with different PAHs by UV/Vis and fluorescence titration experiments revealed record binding strengths for PAHs with binding constants of up to 1.6×10(6)  m(-1) in chloroform at room temperature. One- and two-dimensional NMR experiments and solvent-dependent titration studies revealed self-encapsulation of the side arms of PBI bay-substituents into the cavities that attained high fluorescence quantum yields of these cyclophanes close to unity by preventing the interaction of PBI subunits in the excited states. The binding constants and Gibbs free energies of host-guest complexations disclosed significant effects of PBI bay-substituents and core twist on the binding affinity of the cyclophanes.

  20. Transformation from kinetically into thermodynamically controlled self-organization of complex helical columns with 3D periodicity assembled from dendronized perylene bisimides.

    PubMed

    Percec, Virgil; Sun, Hao-Jan; Leowanawat, Pawaret; Peterca, Mihai; Graf, Robert; Spiess, Hans W; Zeng, Xiangbing; Ungar, Goran; Heiney, Paul A

    2013-03-13

    The dendronized perylene 3,4:9,10-tetracarboxylic acid bisimide (PBI), (3,4,5)12G1-1-PBI, was reported by our laboratory to self-assemble into complex helical columns containing dimers of dendronized PBI with one molecule in each stratum, with different intra- and interdimer rotation angles but identical intra- and interdimer distance of 3.5 Å, exhibiting a four-strata 2(1) helical repeat. A thermodynamically controlled 2D columnar hexagonal phase with short-range intracolumnar order represents the thermodynamic product at high temperature, while a kinetically controlled monoclinic columnar array with 3D periodicity is the thermodynamic product at low temperature. With heating and cooling rates higher than 10 °C/min to 1 °C/min, at low temperature the 2D columnar periodic array is the kinetic product for this dendronized PBI. Here the synthesis and structural analysis of a library of (3,4,5)nG1-m-PBI with n = 12 to 6 and m = 1 are reported. A combination of differential scanning calorimetry, X-ray diffraction on powder and orientated fibers, including pattern simulation and electron density map reconstruction, and solid-state NMR, all as a function of temperature and heating and cooling rate, was employed for their structural analysis. It was discovered that at low temperature the as-prepared n = 12 to 10 exhibit a 3D layered array that transforms irreversibly into columnar periodicities during heating and cooling. Also the kinetically controlled 3D columnar phase of n = 12 becomes thermodynamically controlled for n = 10, 9, 8, 7, and 6. This unprecedented transformation is expected to facilitate the design of functions from dendronized PBI and other self-assembling building blocks.

  1. Increasing 3D Supramolecular Order by Decreasing Molecular Order. A Comparative Study of Helical Assemblies of Dendronized Nonchlorinated and Tetrachlorinated Perylene Bisimides.

    PubMed

    Partridge, Benjamin E; Leowanawat, Pawaret; Aqad, Emad; Imam, Mohammad R; Sun, Hao-Jan; Peterca, Mihai; Heiney, Paul A; Graf, Robert; Spiess, Hans W; Zeng, Xiangbing; Ungar, Goran; Percec, Virgil

    2015-04-22

    A nonplanar, twisted, and flexible tetrachlorinated perylene bisimide (Cl4PBI) was functionalized with two AB3 minidendrons containing hydrogenated or semifluorinated dodecyl groups. The hydrogenated dendron was attached to the imide groups of Cl4PBI via m = 0, 1, and 2 methylenic units, whereas the dendron containing semifluorinated groups was attached via m = 3 or a di(ethylene oxide) linker (m = 2EO). The supramolecular structures of these compounds, determined by a combination of differential scanning calorimetry, X-ray diffraction, and solid-state NMR, were compared with those of nonchlorinated planar and rigid PBI reported previously, which demonstrated the thermodynamically controlled formation of 2D periodic arrays at high temperatures and 3D arrays at low temperatures. The molecularly less ordered Cl4PBI containing hydrogenated dendrons self-organize into exclusively 3D crystalline periodic arrays under thermodynamic control for m = 0 and 2, while the more highly molecularly ordered PBI produced less stable and ordered 3D crystals and also 2D assemblies. This induction of a higher degree of 3D order in supramolecular assemblies of the less well-ordered molecular building blocks was unanticipated. The semifluorinated dendronized Cl4PBI with m = 3 formed a 2D columnar hexagonal array under kinetic control, whereas the compound with m = 2EO formed an unusual 2D honeycomb-like hexagonal phase under thermodynamic control. These Cl4PBI compounds provide a new route to stable crystalline assemblies via thermodynamic control at lower temperatures than previously obtained with PBI, thus generating 3D order in an accessible range of temperature of interest for structural analysis and for technological applications.

  2. Phenylene ethynylene-tethered perylene bisimide folda-dimer and folda-trimer: investigations on folding features in ground and excited states.

    PubMed

    Fimmel, Benjamin; Son, Minjung; Sung, Young Mo; Grüne, Matthias; Engels, Bernd; Kim, Dongho; Würthner, Frank

    2015-01-07

    In this work, we have elucidated in detail the folding properties of two perylene bisimide (PBI) foldamers composed of two and three PBI units, respectively, attached to a phenylene ethynylene backbone. The folding behaviors of these new PBI folda-dimer and trimer have been studied by solvent-dependent UV/Vis absorption and 1D and 2D NMR spectroscopy, revealing facile folding of both systems in tetrahydrofuran (THF). In CHCl3 the dimer exists in extended (unfolded) conformation, whereas partially folded conformations are observed in the trimer. Temperature-dependent (1) H NMR spectroscopic studies in [D8 ]THF revealed intramolecular dynamic processes for both PBI foldamers due to, on the one hand, hindered rotation around CN imide bonds and, on the other hand, backbone flapping; the latter process being energetically more demanding as it was observed only at elevated temperature. The structural features of folded conformations of the dimer and trimer have been elucidated by different 2D-NMR spectroscopy (e.g., ROESY and DOSY) in [D8 ]THF. The energetics of folding processes for the PBI dimer and trimer have been assessed by calculations applying various methods, particularly the semiempirical PM6-DH2 and the more sophisticated B97D approach, in which relevant dispersion corrections are included. These calculations corroborate the results of NMR spectroscopic studies. Folding features in the excited states of these PBI foldamers have been characterized by using time-resolved fluorescence and transient absorption spectroscopy in THF and CHCl3 , exhibiting similar solvent-dependent behavior as observed for the ground state. Interestingly, photoinduced electron transfer (PET) process from electron-donating backbone to electron-deficient PBI core for extended, but not for folded, conformations was observed, which can be explained by a fast relaxation of excited PBI stacks in the folded conformation into fluorescent excimer states. © 2015 WILEY-VCH Verlag GmbH & Co

  3. Naphthalene bisimides asymmetrically and symmetrically N-substituted with triarylamine--comparison of spectroscopic, electrochemical, electronic and self-assembly properties.

    PubMed

    Rybakiewicz, Renata; Zapala, Joanna; Djurado, David; Nowakowski, Robert; Toman, Petr; Pfleger, Jiri; Verilhac, Jean-Marie; Zagorska, Malgorzata; Pron, Adam

    2013-02-07

    Two semiconducting naphthalene bisimides were comparatively studied: NBI-(TAA)(2), symmetrically N-substituted with triaryl amine and asymmetric NBI-TAA-Oc with triaryl amine and octyl N-substituents. Both compounds show very similar spectroscopic and redox properties but differ in their supramolecular organization. As evidenced by STM, in monolayers on HOPG they form ordered 2D structures, however of different packing patterns. NBI-(TAA)(2) does not form ordered 3D structures, yielding amorphous thin films whereas films of NBI-TAA-Oc are highly crystalline. DFT calculations predict the ionization potential (IP) of 5.22 eV and 5.18 eV for NBI-TAA-Oc and NBI-(TAA)(2), respectively, as well as the electron affinity values (EA) of -3.25 eV and -3.22 eV. These results are consistent with the cyclic voltammetry data which yield similar values of IP (5.20 eV and 5.19 eV) and somehow different values of EA (-3.80 eV and -3.83 eV). As judged from these data, both semiconductors should exhibit ambipolar behavior. Indeed, NBI-TAA-Oc is ambipolar, showing hole and electron mobilities of 4.5 × 10(-5) cm(2)/(V s) and of 2.6 × 10(-4) cm(2)/(V s), respectively, in the field effect transistor configuration. NBI-(TAA)(2) is not ambipolar and yields field effect only in the p-channel configuration. This different behavior is rationalized on the basis of structural factors.

  4. Nonfullerene-Acceptor All-Small-Molecule Organic Solar Cells Based on Highly Twisted Perylene Bisimide with an Efficiency of over 6.

    PubMed

    Xin, Rui; Feng, Jiajing; Zeng, Cheng; Jiang, Wei; Zhang, Lei; Meng, Dong; Ren, Zhongjie; Wang, Zhaohui; Yan, Shouke

    2017-01-25

    Two twisted singly linked perylene bisimide (PBI) dimers with chalcogen bridges in the PBI cores, named C4,4-SdiPBI-S and C4,4-SdiPBI-Se, were synthesized as acceptors for nonfullerene all-small-molecule organic solar cells (NF all-SMSCs). A moderate-band-gap small-molecule DR3TBDTT used as the electron donor displayed complementary absorption with C4,4-SdiPBI-S and C4,4-SdiPBI-Se. It was found that solvent-vapor annealing (SVA) played a critical role in the photovoltaic performance in NF all-SMSCs, which improves the crystallinity of the donor and acceptors, promotes the proper phase segregation domain size, and therefore enhances charge transport. The power conversion efficiencies (PCEs) of NF all-SMSC devices based on DR3TBDTT/C4,4-SdiPBI-S and DR3TBDTT/C4,4-SdiPBI-Se increased from 2.52% to 5.81% (JSC = 11.12 mA cm(-2), VOC = 0.91 V, and FF = 57.32%) and from 2.65% to 6.22% (JSC = 11.55 mA cm(-2), VOC = 0.92 V, and FF = 58.72%), respectively, after exposure to chloroform vapor. The best efficiency of 6.22% is one of the highest PCEs for NF all-SMSC-based PBI acceptors so far. The studies illustrate that highly efficient NF all-SMSCs can be achieved by using a PBI acceptor with a suitable SVA process.

  5. A new tunable light-emitting and π-stacked hexa-ethyleneglycol naphthalene-bisimide oligomer: synthesis, photophysics and electrochemical properties.

    PubMed

    Bodapati, Jagadeesh B; Icil, Huriye

    2011-08-01

    An oligomer (3) containing flexible hydrophilic hexa(ethylene glycol) and hydrophobic naphthalene-bisimide chromophores has been synthesized by a one-step condensation reaction and its photophysical and electrochemical properties were investigated. 3 was characterized through the data from NMR, IR, UV-vis, GPC, DSC, TGA, elemental analysis and cyclic voltammetry. The average molecular weight (M(w)) of 3 was 4430 g mol(-1). Intrinsic viscosity was measured as 0.28 dL g(-1) in m-cresol at 25 °C. It has high thermal stability (T(d) = 325 °C). Interestingly, compound 3 shows excimer-like emission in all kinds of solvents. The band gap energy (E(g)), LUMO and HOMO energy values in nonpolar and polar protic solvents were 2.71 eV/3.12 eV, -3.69 eV/-3.88 eV and -6.40 eV/-7.00 eV for 3, respectively. The oligomer showed concentration and solvent dependent fluorescent color tunability. Remarkably, the fluorescent colors of the excimer emissions at 10(-6) M concentration in CHCl(3), DMF and MeOH are light yellow, light blue-yellow and strong blue, respectively, and become more intense at higher concentrations. The excimer emission color in CHCl(3) and DMF is fluorescent yellow and changed to green in MeOH at 10(-4) M concentration. 3 shows two reversible reduction steps at -1.103 and -1.457 V (vs. ferrocene/ferrocenium) in nonpolar solvent CH(2)Cl(2) and only one at -0.917 V in (50:50) CH(3)OH-CH(3)CN binary solvent mixture with higher reversibility. Strong blue-shifts of emission band were noted in protic solvents, which confirm the existence of a negative solvatochromism probably due to protonation. The strong solvent-dependent photophysical and electrochemical properties, including the large shift of excimer emission maximum reflecting self-assembly mediated through hydrogen bonding and π-stacking interactions, make the oligomer a potential candidate for various photo-sensing applications.

  6. Bright Fluorescence and Host-Guest Sensing with a Nanoscale M₄L₆ Tetrahedron Accessed by Self-Assembly of Zinc-Imine Chelate Vertices and Perylene Bisimide Edges.

    PubMed

    Frischmann, Peter D; Kunz, Valentin; Würthner, Frank

    2015-06-15

    A highly luminescent Zn4L6 tetrahedron is reported with 3.8 nm perylene bisimide edges and hexadentate Zn(II)-imine chelate vertices. Replacing Fe(II) and monoamines commonly utilized in subcomponent self-assembly with Zn(II) and tris(2-aminoethyl)amine provides access to a metallosupramolecular host with the rare combination of structural integrity at concentrations <10(-7) mol L(-1) and an exceptionally high fluorescence quantum yield of Φ(em) =0.67. Encapsulation of multiple perylene or coronene guest molecules is accompanied by strong luminescence quenching. We anticipate this self-assembly strategy may be generalized to improve access to brightly fluorescent coordination cages tailored for host-guest light-harvesting, photocatalysis, and sensing.

  7. Frictionless Packings of Rod-like Granular Materials

    NASA Astrophysics Data System (ADS)

    Franklin, Scott

    2010-03-01

    Piles of large aspect ratio granular materials are known to form solid plugs significantly more rigid than piles of ordinary sand or rice. We create random, jammed packings of spherocylinders --- cylinders with hemispherical endcaps --- using energy minimization techniques. The packing fraction at high aspect ratios agrees with a mean-field model that scales as the inverse of excluded volume, implying that that contact number is constant even for very long, thin particles. This is confirmed by a direct analysis of the average contact number at large aspect ratios. The structure of the jammed state can be investigated through the dynamical matrix of elastic modes. In contrast with other work on ellipsoids, our packings show low energy translational modes and higher energy rotational modes, which we explain as resulting due to the absence of particle curvature.

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

    PubMed Central

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

    2016-01-01

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

  9. An ambient stable core-substituted perylene bisimide dianion: isolation and single crystal structure analysis† †Electronic supplementary information (ESI) available: Synthesis, spectroelectrochemistry, UV-vis, electrochemistry, X-ray diffraction, NMR and mass spectra. CCDC 1032959. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4sc03671a Click here for additional data file. Click here for additional data file.

    PubMed Central

    Seifert, Sabine; Schmidt, David

    2015-01-01

    Here we report the first example of an isolable, ambient stable perylene bisimide (PBI) dianion which was synthesized by catalytic reduction of a highly electron deficient PBI derivative. The remarkable stability of this unprecedented dianion in air for months facilitated its complete characterization by different methods, including single crystal X-ray analysis. Furthermore, solvent dependent cyclic and square wave voltammetry studies revealed that the formation of PBI dianions is preferred in more polar solvents, whereas the generation of PBI radical anions should be favoured in less polar solvents. PMID:28717450

  10. Anti-cooperative supramolecular polymerization: a new K 2–K model applied to the self-assembly of perylene bisimide dye proceeding via well-defined hydrogen-bonded dimers† †Electronic supplementary information (ESI) available: Synthesis and characterization, NMR and UV/Vis experiments, VPO and ITC measurements, derivation of the K 2–K model. See DOI: 10.1039/c5sc03759j Click here for additional data file.

    PubMed Central

    Gershberg, Jana; Fennel, Franziska; Rehm, Thomas H.; Lochbrunner, Stefan

    2016-01-01

    A perylene bisimide dye bearing amide functionalities at the imide positions derived from amino acid l-alanine and a dialkoxy-substituted benzyl amine self-assembles into tightly bound dimers by π–π-stacking and hydrogen bonding in chloroform. In less polar or unpolar solvents like toluene and methylcyclohexane, and in their mixtures, these dimers further self-assemble into extended oligomeric aggregates in an anti-cooperative process in which even numbered aggregates are highly favoured. The stepwise transition from dimers into oligomers can not be properly described by conventional K 2–K model, and thus a new K 2–K aggregation model has been developed, which interpretes the present anti-cooperative supramolecular polymerization more appropriately. The newly developed K 2–K model will be useful to describe self-assembly processes of a plethora of other π-conjugated molecules that are characterized by a favored dimer species. PMID:28966774

  11. Geometric model and analysis of rod-like large space structures

    NASA Technical Reports Server (NTRS)

    Nayfeh, A. H.; Hefney, M. S.

    1978-01-01

    The application of geometrical schemes to large sphere antenna reflectors was investigated. The purpose of these studies is to determine the shape and size of flat segmented surfaces which approximate general shells of revolution and in particular spherical and paraboloidal reflective surfaces. The extensive mathematical and computational geometry analyses of the reflector resulted in the development of a general purpose computer program. This program is capable of generating the complete design parameters of the dish and can meet stringent accuracy requirements. The computer program also includes a graphical self contained subroutine which graphically displays the required design.

  12. Curvature-driven capillary migration and assembly of rod-like particles.

    PubMed

    Cavallaro, Marcello; Botto, Lorenzo; Lewandowski, Eric P; Wang, Marisa; Stebe, Kathleen J

    2011-12-27

    Capillarity can be used to direct anisotropic colloidal particles to precise locations and to orient them by using interface curvature as an applied field. We show this in experiments in which the shape of the interface is molded by pinning to vertical pillars of different cross-sections. These interfaces present well-defined curvature fields that orient and steer particles along complex trajectories. Trajectories and orientations are predicted by a theoretical model in which capillary forces and torques are related to Gaussian curvature gradients and angular deviations from principal directions of curvature. Interface curvature diverges near sharp boundaries, similar to an electric field near a pointed conductor. We exploit this feature to induce migration and assembly at preferred locations, and to create complex structures. We also report a repulsive interaction, in which microparticles move away from planar bounding walls along curvature gradient contours. These phenomena should be widely useful in the directed assembly of micro- and nanoparticles with potential application in the fabrication of materials with tunable mechanical or electronic properties, in emulsion production, and in encapsulation.

  13. Thermotropic rod-like mesogens as stabilizers for polyolefins and polyvinyl chloride

    NASA Astrophysics Data System (ADS)

    Burmistrov, V. A.; Kuvshinova, S. A.; Koifman, O. I.

    2016-02-01

    The main approaches to stabilization of polymers and requirements to anti-ageing agents are discussed. Considerable attention is paid to the progress in the studies of the stabilizing activity of various substances in polyolefin- and polyvinyl chloride-based compositions. Particular demand for environmentally benign organic heat stabilizers and antioxidants is noted. The so-called mesogenic structures serving as effective light and heat stabilizers for polymer composites are presented. The effects of mesogens on the supramolecular structure of polyethylene, deformation and relaxation properties and thermal parameters as well as melt flow index, tribological properties and other properties of polymer materials are discussed. The bibliography includes 112 references.

  14. On the nucleation and initial film growth of rod-like organic molecules

    PubMed Central

    Winkler, Adolf

    2016-01-01

    In this article, some fundamental topics related to the initial steps of organic film growth are reviewed. General conclusions will be drawn based on experimental results obtained for the film formation of oligophenylene and pentacene molecules on gold and mica substrates. Thin films were prepared via physical vapor deposition under ultrahigh-vacuum conditions and characterized in-situ mainly by thermal desorption spectroscopy, and ex-situ by X-ray diffraction and atomic force microscopy. In this short review article the following topics will be discussed: What are the necessary conditions to form island-like films which are either composed of flat-lying or of standing molecules? Does a wetting layer exist below and in between the islands? What is the reason behind the occasionally observed bimodal island size distribution? Can one describe the nucleation process with the diffusion-limited aggregation model? Do the impinging molecules directly adsorb on the surface or rather via a hot-precursor state? Finally, it will be described how the critical island size can be determined by an independent measurement of the deposition rate dependence of the island density and the capture-zone distribution via a universal relationship. PMID:27482122

  15. A generalized Oldroyd model for a suspension of rod-like or disk-like particles

    NASA Astrophysics Data System (ADS)

    Davis, Robert; Martin, Richard; Zinchenko, Alexander

    2014-11-01

    Early work on emulsion rheology was performed by Frankel and Acrivos [J. Fluid Mech. 44, 65 (1970)] for dilute emulsions of drops with small deformations. Martin, Zinchenko and Davis [J. Rheol. 58, 759 (2014)] developed a more general approach, valid for larger deformations and based on a 5-parameter Oldroyd model with variable coefficients found from fitting the equation to three viscometric and two extensiometric functions in simple shear and hyperbolic flow, respectively, at arbitrary flow intensities. The method was validated with the Frankel-Acrivos small-deformation theory. We have extended the method to ellipsoidal particles subject to Brownian rotations. The viscometric and extensiometric functions were obtained by numerically solving the Fokker-Planck equation for the particle orientation distribution function through expansions into spherical harmonics. The results compare well with the interpolation models of Hinch and Leal [J. Fluid Mech. 76, 187 (1976)] between the limits of weak and strong flows. A benefit of our general approach to constitutive modeling is that it can be applied to concentrated systems (suspensions, emulsions, etc.), while the prior models are limited to dilute systems of non-interacting particles or drops.

  16. Obstruction enhances the diffusivity of self-propelled rod-like particles.

    PubMed

    Khalilian, Hamidreza; Fazli, Hossein

    2016-10-28

    Diffusion of self-propelled particles in the presence of randomly distributed obstacles is studied in three dimensions (3D) using Langevin dynamics simulations. It is found that depending on the magnitude of the propelling force and the particle aspect ratio, the diffusion coefficient can be a monotonically decreasing or a non-monotonic concave function of the obstructed volume fraction. Counterintuitive enhancement of the particle diffusivity with increasing the obstacle crowd is shown to be resulted from interplay of self-propulsion and anisotropy in the particle shape. On the propelling force-aspect ratio plane, regions that correspond to monotonic and non-monotonic dependence of the diffusivity on obstacle density are specified using the simulation results and the boundary between the two regions is described.

  17. Chiral twist drives raft formation and organization in membranes composed of rod-like particles.

    PubMed

    Kang, Louis; Lubensky, Tom C

    2017-01-03

    Lipid rafts are hypothesized to facilitate protein interaction, tension regulation, and trafficking in biological membranes, but the mechanisms responsible for their formation and maintenance are not clear. Insights into many other condensed matter phenomena have come from colloidal systems, whose micron-scale particles mimic basic properties of atoms and molecules but permit dynamic visualization with single-particle resolution. Recently, experiments showed that bidisperse mixtures of filamentous viruses can self-assemble into colloidal monolayers with thermodynamically stable rafts exhibiting chiral structure and repulsive interactions. We quantitatively explain these observations by modeling the membrane particles as chiral liquid crystals. Chiral twist promotes the formation of finite-sized rafts and mediates a repulsion that distributes them evenly throughout the membrane. Although this system is composed of filamentous viruses whose aggregation is entropically driven by dextran depletants instead of phospholipids and cholesterol with prominent electrostatic interactions, colloidal and biological membranes share many of the same physical symmetries. Chiral twist can contribute to the behavior of both systems and may account for certain stereospecific effects observed in molecular membranes.

  18. Combustion synthesized rod-like nanostructure hematite with enhanced lithium storage properties

    SciTech Connect

    Xiong, Q.Q.; Shi, S.J.; Tang, H.; Wang, X.L.; Gu, C.D.; Tu, J.P.

    2015-01-15

    Graphical abstract: Fe{sub 2}O{sub 3} nanorods are synthesized by combustion method using alcohol as both solvent and fuel. As an anode material for lithium-ion batteries, the Fe{sub 2}O{sub 3} nanorod electrode delivers good electrochemical performance. - Highlights: • We prepared Fe{sub 2}O{sub 3} nanorod by a facile and powerful combustion method. • The Fe{sub 2}O{sub 3} nanorod shows high capacity, good cycle stability, and rate performance. • Combustion saves time and energy to meet the demand of green and sustainable industry. - Abstract: Fe{sub 2}O{sub 3} nanorods are synthesized by combustion method using alcohol as both solvent and fuel, which is a facile and effective strategy for the large-scale and inexpensive fabrication. The Fe{sub 2}O{sub 3} nanorods are with the well distributed diameters of 20–30 nm and length ranging from 80 to 100 nm. As an anode material for lithium-ion batteries, the Fe{sub 2}O{sub 3} nanorod electrode delivers a high discharge capacity of 761.7 mA h g{sup −1} after 60 cycles at 500 mA g{sup −1}, and 727.2 mA h g{sup −1} at a high current density of 2000 mA g{sup −1}. The good electrochemical performance is attributed to the sufficient contact of active material and electrolyte, large surface area, and short diffusion length of Li{sup +}.

  19. Curvature-driven capillary migration and assembly of rod-like particles

    PubMed Central

    Cavallaro, Marcello; Botto, Lorenzo; Lewandowski, Eric P.; Wang, Marisa; Stebe, Kathleen J.

    2011-01-01

    Capillarity can be used to direct anisotropic colloidal particles to precise locations and to orient them by using interface curvature as an applied field. We show this in experiments in which the shape of the interface is molded by pinning to vertical pillars of different cross-sections. These interfaces present well-defined curvature fields that orient and steer particles along complex trajectories. Trajectories and orientations are predicted by a theoretical model in which capillary forces and torques are related to Gaussian curvature gradients and angular deviations from principal directions of curvature. Interface curvature diverges near sharp boundaries, similar to an electric field near a pointed conductor. We exploit this feature to induce migration and assembly at preferred locations, and to create complex structures. We also report a repulsive interaction, in which microparticles move away from planar bounding walls along curvature gradient contours. These phenomena should be widely useful in the directed assembly of micro- and nanoparticles with potential application in the fabrication of materials with tunable mechanical or electronic properties, in emulsion production, and in encapsulation. PMID:22184218

  20. Nanomechanical characterization of rod-like superlattice assembled from tobacco mosaic viruses

    NASA Astrophysics Data System (ADS)

    Wang, Haoran; Wang, Xinnan; Li, Tao; Lee, Byeongdu

    2013-01-01

    Tobacco mosaic virus (TMV) and TMV-derived materials have demonstrated their great potential in biomedical applications, where the mechanical properties are determining factors for their proper functionalities and structural integrity. Recently, it has been found that a superlattice structure can be formed by two-dimensional hexagonal packing TMV self-assembly in Barium ions solution. In parallel to the exploration of possible applications of TMV superlattice, the mechanical properties were characterized by the atomic force microscopy based nanoindentation. The elastic modulus of 2.14 GPa was obtained by application of the extended Johnson-Kendall-Roberts (JKR) model with the force vs sample deformation data. The adhesion force was taken into consideration, and an easy-to-implement approach of using the extended JKR model was proposed by processing both the theoretical model and the experimental data. Finite element analysis was conducted to evaluate the reinforcing effect of the like-charge forces between the TMVs and the mechanical properties of the TMV superlattice. Using the Halpin-Tsai model, the transverse elastic modulus of the superlattice sample varied within 2.00-4.38 GPa, depending on the indentation locations. Attraction-repulsion equilibrium was found to maintain the packing of TMVs. This provides useful information to address the sources of the attraction and repulsion forces to control the TMV assembly.

  1. Nematic Ordering in a Population of Growing and Dividing Rod-like Cells

    NASA Astrophysics Data System (ADS)

    Tsimring, Lev

    2007-03-01

    Morphogenesis is one of the most important themes in biology, and it is also central to nonequilibrium physics. The fundamental issue is to understand how local interactions of elementary components lead to collective behavior and the formation of a highly organized system. In nature this self-organization is found on many different scales, from single cells to schools of fish and herds of animals. Collective behavior leads to significant selective advantages for living organisms. At low density, communication among cells occurs mainly due to chemotaxis, the mechanical response of cell to the gradients of chemicals emitted by other cells. At higher densities, steric exclusion effects may strongly affect their collective behavior. In this work we focus on the mechanical interaction among non-motile bacteria in engineered biofilms. These biofilms are formed by growing two-dimensional bacterial colonies in a highly controlled microfluidic environment. We combine experimental observations and analysis with discrete-element molecular dynamics simulations and theoretical modeling to provide mesoscopic description of the biofilm growth. Our results reveal how cell growth and colony expansion trigger the formation of the orientational (nematic) order in the biofilms.

  2. Synthesis and ESR studies of 2'-deoxyuridines tethered with alkynyl, rod-like linkages#

    PubMed Central

    Sniady, Adam; Sevilla, Michael D.; Meneni, Srinivasarao; Lis, Tadeusz; Szafert, Slawomir; Khanduri, Deepthi; Finke, John M.; Dembinski, Roman

    2015-01-01

    Sonogashira coupling of diacetyl 5-ethynyl-2'-deoxyuridine with diacetyl 5-iodo-2'-deoxyuridine gave the acylated ethynediyl-linked 2'-deoxyuridine dimer (3b) (63%) that was deprotected with ammonia/methanol to ethynediyl-linked 2'-deoxyuridines (3a) (79%). Reaction of 5-ethynyl-2'-deoxyuridine (1a) with 5-iodo-2'-deoxyuridine gave the furopyrimidine linked to 2'-deoxyuridine (78%). Catalytic oxidative coupling of 1a (O2, CuI, Pd/C, DMF) gave the butadiynediyl-linked 2'-deoxyuridines (4) (84%). Double Sonogashira coupling of 5-iodo-2'-deoxyuridine with 1,4-bis(ethynyl)benzene gave 1,4-phenylenediethyne-bridged 5-ethynyl-2'-deoxyuridines (5, 83%). Cu-catalyzed cycloisomerization of dimers 4 and 5 gave their furopyrimidine derivatives. One electron addition to 1a, 3a and 4 gave the anion radical whose ESR spectra showed the unpaired electron largely localized at C6 of one uracil ring (17 G doublet) at 77 K. For the ethynediyl- and butadiynyl-linked uridines 3a and 4 the ESR spectra of their one electron oxidized species at 77 K showed that the unpaired electron is delocalized over both rings. Thus structures 3a and 4 provide an efficient electronic link for hole conduction between the uracil rings. However, for the excess electron, an activation barrier prevents coupling to both rings. These dimeric structures could provide a gate that could separate hole transfer from electron transport between strands in DNA systems. In the crystal structure of acylated dimer 3b the bases were found in the anti position to each other across the ethynyl link. Similar anti conformation was preserved in the derived furopyrimidine–deoxyuridine dinucleoside. PMID:19609983

  3. On the nucleation and initial film growth of rod-like organic molecules

    NASA Astrophysics Data System (ADS)

    Winkler, Adolf

    2016-10-01

    In this article, some fundamental topics related to the initial steps of organic film growth are reviewed. General conclusions will be drawn based on experimental results obtained for the film formation of oligophenylene and pentacene molecules on gold and mica substrates. Thin films were prepared via physical vapor deposition under ultrahigh-vacuum conditions and characterized in-situ mainly by thermal desorption spectroscopy, and ex-situ by X-ray diffraction and atomic force microscopy. In this short review article the following topics will be discussed: What are the necessary conditions to form island-like films which are either composed of flat-lying or of standing molecules? Does a wetting layer exist below and in between the islands? What is the reason behind the occasionally observed bimodal island size distribution? Can one describe the nucleation process with the diffusion-limited aggregation model? Do the impinging molecules directly adsorb on the surface or rather via a hot-precursor state? Finally, it will be described how the critical island size can be determined by an independent measurement of the deposition rate dependence of the island density and the capture-zone distribution via a universal relationship.

  4. Chiral twist drives raft formation and organization in membranes composed of rod-like particles

    PubMed Central

    Lubensky, Tom C.

    2017-01-01

    Lipid rafts are hypothesized to facilitate protein interaction, tension regulation, and trafficking in biological membranes, but the mechanisms responsible for their formation and maintenance are not clear. Insights into many other condensed matter phenomena have come from colloidal systems, whose micron-scale particles mimic basic properties of atoms and molecules but permit dynamic visualization with single-particle resolution. Recently, experiments showed that bidisperse mixtures of filamentous viruses can self-assemble into colloidal monolayers with thermodynamically stable rafts exhibiting chiral structure and repulsive interactions. We quantitatively explain these observations by modeling the membrane particles as chiral liquid crystals. Chiral twist promotes the formation of finite-sized rafts and mediates a repulsion that distributes them evenly throughout the membrane. Although this system is composed of filamentous viruses whose aggregation is entropically driven by dextran depletants instead of phospholipids and cholesterol with prominent electrostatic interactions, colloidal and biological membranes share many of the same physical symmetries. Chiral twist can contribute to the behavior of both systems and may account for certain stereospecific effects observed in molecular membranes. PMID:27999184

  5. Rod-like plasmonic nanoparticles as optical building blocks: how differences in particle shape and structural geometry influence optical signal

    SciTech Connect

    Stender, Anthony

    2013-01-01

    Gold nanoparticles, particularly those with an anisotropic shape, have become a popular optical probe for experiments involving work on the nanoscale. However, to carry out such delicate and intricate experiments, it is first necessary to understand the detailed behavior of individual nanoparticles. In this series of experiments, optical and electron microscopy were utilized for the characterization of individual nanoparticles and small assemblies of nanoparticles. In the first experiment, gold nanorods were investigated. Single, isolated nanorods exhibit two maxima of localized surface plasmon resonance (LSPR), which are associated with the two nanorod axes. Upon the physical rotation of a nanorod at one of its LSPR wavelengths under polarized illumination, the optical behavior varies in a sinusoidal fashion. A dimer of nanorods exhibits optical behavior quite similar to a nanorod, except the LSPR maxima are shifted and broader. Under differential interference contrast (DIC) microscopy, a pair of nanorods separated by a distance below the diffraction limit can be distinguished from a single nanorod due to its optical behavior upon rotation. Dark field microscopy is unable to distinguish the two geometries. For the second set of experiments, the optical behavior of single gold nanorods at non-plasmonic wavelengths was investigated. The same nanorod was rotated with respect to a polarized light source under DIC, dark field, and polarized light microscopy. DIC microscopy was found to produce diffraction pattern peaks at non-plasmonic wavelengths, which could be altered by adjusting the setting of the polarizer. In the third set of experiments, the optical behavior of a single gold dumbbell and several simple dumbbell geometries were investigated with microscopy and simulations. The single dumbbell displayed behavior quite similar to that of a nanorod, but dumbbells exhibit a shift in both LSPR wavebands. Moreover, the shape of dumbbell particles allows them to interlock with one another quite easily. The dimers that form as a result display optical behavior that differs from what has been previously reported about nanorod dimers. Simulated surface charge density patterns reveal that hybridization of LSPR modes occurs readily along the lobes of individual dumbbells in some situations. A pentamer of dumbbells also displays hybridization of modes, and “hot spots” are observed at junctions between pairings of dumbbells. In the final set of experiments, the assembly behavior of nanoparticles in solution was observed in real time. In general, large assemblies of nanoparticles display backbone-like rigidity, but an interesting variety of movements is permitted within the larger structures.

  6. Experimental and theoretical study of the silica particle interactions in the presence of multivalent rod-like ions.

    PubMed

    Reščič, Jurij; Kovačević, Davor; Tomšič, Matija; Jamnik, Andrej; Ahualli, Silvia; Bohinc, Klemen

    2014-08-19

    The silica particle interactions in the presence of spermidine were systematically investigated both from experimental and theoretical points of view. The hydrodynamic radii and the corresponding polydispersity indices of the colloidal silica particles were determined by dynamic light scattering (DLS) as a function of spermidine concentration. Whereas the effective size of the silica particles increases with increasing spermidine concentration (pointing to the particle aggregation), the polydispersity index first increases reaches a maximum and then further decreases with the increasing spermidine concentration. From the mobility measurements it was concluded that the increase in spermidine concentration causes less negative values of zeta potential, meaning that the adsorption of spermidine leads to the less negative silica surface. Moreover, Monte Carlo (MC) simulations also confirmed that the addition of spermidine reduces the repulsion between silica particles. The MC concentration profiles of spermidine close to the charged silica particle are in a very good agreement with the results obtained by theory. An important motivation for our study is the effectiveness of multivalent ions to coagulate colloidal suspensions; e.g., the multivalent ions are exploited in the water purification process.

  7. Electrophysiological evidence for rod-like receptors in the gray squirrel, ground squirrel and prairie dog retinas.

    PubMed

    Green, D G; Dowling, J E

    1975-02-15

    Spectral sensitivities of the gray squirrel, Mexican and 13-line ground squirrel and prairie dog were determined by electroretinography under both dark- and light-adapted conditions. The dark-adapted spectral sensitivity function obtained from intact eyes of these species peaks between 515-525 nm; however, when corrected for lens absorption or recorded from the lensless eye, it peaks near 500 nm and closely matches in shape a rhodopsin nomogram curve (lambda max equals 502 nm). Upon light adaptation all these retinas become relatively more sensitive to long-wave stimuli (i.e., they show a small Purkinje shift). The light-adapted spectral sensitivity function is broader than that obtained from the dark-adapted eye, especially toward the longer wavelengths. Weconclude that in all these species the dark-adapted spectral sensitivity is mediated by a single, rhodopsin-like photopigment and that light-adapted sensitivity is mediated by two (or more) photopigments.

  8. Controlled synthesis of novel rod-like Cu1.81S nanostructures and field emission properties

    NASA Astrophysics Data System (ADS)

    Song, Changqing; Yu, Ke; Li, Shouchuan; Yin, Haihong; zhang, Ning; Zhao, Bin; Zhu, Ziqiang

    2014-10-01

    Three flower-like and one rod-shape cubic Cu2S nanostructures were successfully synthesized from a facile hydrothermal method employing CuCl2·2H2O and thiourea as Cu and S source with different volume ratio of ethanol and distilled water, respectively. Hexadecyl trimethyl ammonium Bromide (CTAB) plays an important role in forming the nanorod. After thermal annealing treatment, tetragonal Cu1.81S nanoflower and nanorod were obtained for the first time. Field emission (FE) properties of these nanostructures were investigated for the first time. The results indicated that the tetragonal Cu1.81S nanorods had excellent field emission performance with turn-on field of ∼2.2 V μm-1, threshold field of ∼5.1 V μm-1 and enhancement factor of 1532. It showed that the tetragonal Cu1.81S nanostructures were competitive material in field emission applications.

  9. RGD-conjugated rod-like viral nanoparticles on 2D scaffold improved bone differentiation of mesenchymal stem cells

    NASA Astrophysics Data System (ADS)

    Wang, Qian; Pongkwan, Sitasuwan; Lee, L.; Li, Kai; Nguyen, Huong

    2014-05-01

    Viral nanoparticles have uniform and well-defined nano-structures and can be produced in large quantities. Several plant viral nanoparticles have been tested in biomedical applications due to the lack of mammalian cell infectivity. We are particularly interested in using Tobacco mosaic virus (TMV), which has been demonstrated to enhance bone tissue regeneration, as a tuneable nanoscale building block for biomaterials development. Unmodified TMV particles have been shown to accelerate osteogenic differentiation of adult stem cells by synergistically upregulating BMP2 and IBSP expression with dexamethasone. However, the lack of affinity to mammalian cell surface resulted in low initial cell adhesion. In this study, to increase cell binding capacity of TMV based material the chemical functionalization of TMV with arginine-glycine-aspartic acid (RGD) peptide was explored. An azide-derivatized RGD peptide was “clicked” to tyrosine residues on TMV outer surface via an efficient copper(I) catalysed azide-alkyne cycloaddition reaction. The ligand spacing is calculated to be 2-4 nm, which could offer a polyvalent ligand clustering effect for enhanced cell receptor signalling, further promoting the proliferation and osteogenic differentiation of bone marrow derived mesenchymal stem cells.

  10. Formation and stability of twisted ribbons in mixtures of rod-like fd-virus and non-adsorbing polymer

    NASA Astrophysics Data System (ADS)

    Dogic, Z.; Didonna, B.; Bryning, M.; Lubensky, T. C.; Yodh, A. G.; Janmey, P. A.

    2003-03-01

    We are investigating the behavior of mixtures of monodisperse fd-virus rods and non-adsorbing polymer. We observe the formation of isolated smectic disks. The single smectic disk is of a monolayer of aligned rods while its thickness equal to the length of a single rod. As disks coalesce they undergo shape transformations from flat structures to elongated twisted ribbons. A theoretical model is formulated wherein the chirality of the molecule favors the formation of the elongated ribbon structure while the line tension favors formation of untwisted disks. To check the validity of the theoretical model line tension and twist constants are experimentally measured. The line tension is deduced from thermal fluctuations of the interface. The twist constant is determined by unwinding the twisted ribbons using optical tweezers. This work is partially supported by NSF grants DMR-0203378, the PENN MRSEC, DMR-0079909, and NASA grant NAG8-2172.

  11. RGD-conjugated rod-like viral nanoparticles on 2D scaffold improve bone differentiation of mesenchymal stem cells

    PubMed Central

    Sitasuwan, Pongkwan; Lee, L. Andrew; Li, Kai; Nguyen, Huong Giang; Wang, Qian

    2014-01-01

    Viral nanoparticles have uniform and well-defined nano-structures and can be produced in large quantities. Several plant viral nanoparticles have been tested in biomedical applications due to the lack of mammalian cell infectivity. We are particularly interested in using Tobacco mosaic virus (TMV), which has been demonstrated to enhance bone tissue regeneration, as a tunable nanoscale building block for biomaterials development. Unmodified TMV particles have been shown to accelerate osteogenic differentiation of adult stem cells by synergistically upregulating bone morphogenetic protein 2 (BMP2) and integrin-binding bone sialoprotein (IBSP) expression with dexamethasone. However, their lack of affinity to mammalian cell surface resulted in low initial cell adhesion. In this study, to increase cell binding capacity of TMV based material the chemical functionalization of TMV with arginine-glycine-aspartic acid (RGD) peptide was explored. An azide-derivatized RGD peptide was “clicked” to tyrosine residues on TMV outer surface via an efficient copper(I) catalyzed azide-alkyne cycloaddition (CuAAC) reaction. The ligand spacing is calculated to be 2–4 nm, which could offer a polyvalent ligand clustering effect for enhanced cell receptor signaling, further promoting the proliferation and osteogenic differentiation of bone marrow-derived mesenchymal stem cells (BMSCs). PMID:24904922

  12. short stop is allelic to kakapo, and encodes rod-like cytoskeletal-associated proteins required for axon extension.

    PubMed

    Lee, S; Harris, K L; Whitington, P M; Kolodziej, P A

    2000-02-01

    short stop (shot) is required for sensory and motor axons to reach their targets in the Drosophila embryo. Growth cones in shot mutants initiate at the normal times, and they appear normal with respect to overall morphology and their abilities to orient and fasciculate. However, sensory axons are unable to extend beyond a short distance from the cell body, and motor axons are unable to reach target muscles. The shot gene encodes novel actin binding proteins that are related to plakins and dystrophin and expressed in axons during development. The longer isoforms identified are predicted to contain an N-terminal actin binding domain, a long central triple helical coiled-coil domain, and a C-terminal domain that contains two EF-hand Ca(2+) binding motifs and a short stretch of homology to the growth arrest-specific 2 protein. Other isoforms lack all or part of the actin binding domains or are truncated and contain a different C-terminal domain. Only the isoforms containing full-length actin binding domains are detectably expressed in the nervous system. shot is allelic to kakapo, a gene that may function in integrin-mediated adhesion in the wing and embryo. We propose that Shot's interactions with the actin cytoskeleton allow sensory and motor axons to extend.

  13. Rich polymorphism of a rod-like liquid crystal (8CB) confined in two types of unidirectional nanopores.

    PubMed

    Guégan, R; Morineau, D; Lefort, R; Béziel, W; Guendouz, M; Noirez, L; Henschel, A; Huber, P

    2008-07-01

    We present a neutron and X-rays scattering study of the phase transitions of 4-n-octyl-4' -cyanobiphenyl (8CB) confined in unidirectional nanopores of porous alumina and porous silicon (PSi) membranes with an average diameter of 30 nm. Spatial confinement reveals a rich polymorphism, with at least four different low temperature phases in addition to the smectic A phase. The structural study as a function of thermal treatments and conditions of spatial confinement allows us to get insights into the formation of these phases and their relative stability. It gives the first description of the complete phase behavior of 8CB confined in PSi and provides a direct comparison with results obtained in bulk conditions and in similar geometric conditions of confinement but with reduced quenched disorder effects using alumina anopore membranes.

  14. Mechanoresponsive change in photoluminescent color of rod-like liquid-crystalline compounds and control of molecular orientation on photoaligned layer

    NASA Astrophysics Data System (ADS)

    Kondo, Mizuho; Miura, Seiya; Okumoto, Kentaro; Hashimoto, Mayuko; Fukae, Ryohei; Kawatsuki, Nobuhiro

    2014-10-01

    In this paper, we reported novel liquid-crystalline luminophore that switches its photoluminescent color by mechanically grinding. Mechanochromic luminescence (MCL) is expected for mechanical sensor, cellular imaging, detection of microenvironmental changes, and optical memory. In this work, we focused on liquid-crystalline MCL compounds on alignment layer. Controlling the molecular alignment of MCL compounds with photoalignment layer have potential to succeed in functional MCL film such as polarized micropatterned MCL and directional detection of mechanical stimuli. Herein, we prepared asymmetric rodlike MCL compounds containing cyano- and pyridyl molecular terminal and explored their photoluminescence behavior under mechanical stimulus. The cyano terminated compound showed a nematic phase and tuned its photoluminescent color from green to yellow upon grinding, while the pyridyl-terminated compounds that show no mesophase changed its photoluminescent color from blue to green and reverted to its initial color by heating above its melting point. The cyano-terminated MCL was aligned along the orientation direction of photoalignment layer and pyridyl-terminated MCL exhibited uniaxial alignment when it coated on photoaligned film containing carboxylic acid.

  15. Fabrication of the C-N co-doped rod-like TiO{sub 2} photocatalyst with visible-light responsive photocatalytic activity

    SciTech Connect

    Li, Liang-Hai; Lu, Juan; Wang, Zuo-Shan; Yang, Lu; Zhou, Xiu-Feng; Han, Lu

    2012-06-15

    Highlights: ► Novel synthesis of C-N co-doped TiO{sub 2}. ► Self-assembly of C-N co-doped TiO{sub 2} nanorods by nanoparticles. ► Excellent photocatalytic efficiency. -- Abstract: The C-N co-doped TiO{sub 2} nanorods were synthesized by the vapor transport method of water molecules, and urea was used as the carbon and nitrogen source. The samples were characterized by X-ray diffraction and photoelectron spectroscopy analysis. The scanning electron microscope images showed that as-prepared TiO{sub 2} powders were nanorods, which were formed by the stacking of nanoparticles with a uniform size around 40 nm. The degradation of methylene blue with the prepared nanorods demonstrated the photocatalytic activities of TiO{sub 2} under visible light are improved by doping with C and N elements. The main reasons were discussed: doping with C and N elements could enhance the corresponding visible-light absorption of TiO{sub 2}. On the other hand, doping C and N could create more oxygen vacancies in the TiO{sub 2} crystals, which could capture the photogenerated electrons more effectively. Thus, more photogenerated holes could be left to improve the photocatalytic activity of TiO{sub 2}.

  16. Fluorescent labelling of DNA on superparamagnetic nanoparticles by a perylene bisimide derivative for cell imaging.

    PubMed

    Maltas, Esra; Malkondu, Sait; Uyar, Pembegul; Ozmen, Mustafa

    2015-03-01

    N,N'-Bis[tris-(2-aminoethyl) amine]-3,4,9,10-perylenetetracarboxylic diimide (PBI-TRIS), nonfluorescent dye was used to fluorescent labelling of DNA. For this aim, (3-aminopropyl) triethoxysilane (APTS) modified superparamagnetic iron oxide nanoparticles (SPIONs) were synthesized to provide a suitable surface for binding of DNA. Amine functionalized nanoparticles showed a high immobilization capacity (82.70%) at 25mg of nanoparticle concentration for Calf thymus DNA. Binding capacity of PBI-TRIS to DNA-SPION was also found as 1.93μM on 25mg of nanoparticles by using UV-vis spectroscopy. Binding of PBI-TRIS to DNA onto nanoparticles was also characterized by scanning electron microscopy and infrared spectroscopy. The confocal images of PBI-TRIS labelled DNA-SPION and breast cells were taken at 488 and 561.7nm of excitation wavelengths. Cell image was also compared with a commercial dye, DAPI at 403.7nm of excitation wavelength. Results showed that PBI-TRIS can be used for cell staining. Copyright © 2014 Elsevier B.V. All rights reserved.

  17. Laminate comprising fibers embedded in cured amine terminated bis-imide

    NASA Technical Reports Server (NTRS)

    Kumar, D. (Inventor); Fohlen, G. M. (Inventor); Parker, J. A. (Inventor)

    1986-01-01

    Amine terminated bisaspartimides are prepared by a Michael type reaction of an aromatic bismaleimide and an aromatic diamine in an aprotic solvent. These bisaspartimides are thermally polymerized to yield tough, resinous polymers crosslinked through -NH- groups. Such polymers are useful in applications requiring materials with resistance to change at elevated temperatures.

  18. Assemblies based on the directing effect of non-classical W{sub 18} anionic clusters and the rod-like trans-1,2-di-(4-pyridyl)-ethylen (bpe)

    SciTech Connect

    Han, Zhangang; Wang, Yanna; Song, Xuejun; Huang, Jiao; Zhai, Xueliang

    2011-03-15

    Two polyoxometalate (POM) supramolecular assemblies based on W{sub 18} clusters and the rigid organic trans-1,2-di-(4-pyridyl)-ethylen (bpe) have been synthesized and fully characterized, namely (H{sub 2}bpe)3.5H{sub 2}[SbW{sub 18}O{sub 60}].5H{sub 2}O (1), and (H{sub 2}bpe)5[Ni{sub 4}(AsW{sub 9}O{sub 34}){sub 2}(H{sub 2}O){sub 2}].3H2O (2). Compounds 1-2 are formed from organic bpe cations and different polytungstate anions: pseudo-Dawson-type [SbW{sub 18}O{sub 60}]{sup 9-} in 1 and sandwich-type [Ni{sub 4}(H{sub 2}O){sub 2}(AsW{sub 9}O{sub 34}){sub 2}]{sup 10-} in 2. Both of compounds 1-2 crystallize in a low-symmetrical space group of P-1 and consist of a complicated supramolecular network based on non-covalent intermolecular weak interactions, including hydrogen bonding and {pi}...{pi} stacking. The multipoint hydrogen bonding interactions constitute the structural feature in two supramolecular frameworks. The UV-vis, fluorescence and electrochemistry properties are also studied. -- Graphical abstract: Two polyoxometalate-based supramolecular assemblies built upon W{sub 18} clusters and the rigid organic trans-1,2-di-(4-pyridyl)-ethylen (bpe) have been synthesized and characterized. Research highlights: > Sb{sup 3+} has a larger ionic radius to prevent the formation of the sandwich-type polyoxometalate cluster. > Non-covalent interactions play important roles in the self-organization process. > Polyanion can structure the conjugated organic molecule into a parallel and ordered arrangement. > Polyanion-based hybrid is a potential candidate in the modified material for electrode.

  19. Assemblies based on the directing effect of non-classical W 18 anionic clusters and the rod-like trans-1,2-di-(4-pyridyl)-ethylen (bpe)

    NASA Astrophysics Data System (ADS)

    Han, Zhangang; Wang, Yanna; Song, Xuejun; Huang, Jiao; Zhai, Xueliang

    2011-03-01

    Two polyoxometalate (POM) supramolecular assemblies based on W 18 clusters and the rigid organic trans-1,2-di-(4-pyridyl)-ethylen (bpe) have been synthesized and fully characterized, namely (H 2bpe)3.5H 2[SbW 18O 60]·5H 2O ( 1), and (H 2bpe)5[Ni 4(AsW 9O 34) 2(H 2O) 2]·3H2O ( 2). Compounds 1- 2 are formed from organic bpe cations and different polytungstate anions: pseudo-Dawson-type [SbW 18O 60] 9- in 1 and sandwich-type [Ni 4(H 2O) 2(AsW 9O 34) 2] 10- in 2. Both of compounds 1- 2 crystallize in a low-symmetrical space group of P-1 and consist of a complicated supramolecular network based on non-covalent intermolecular weak interactions, including hydrogen bonding and π··· π stacking. The multipoint hydrogen bonding interactions constitute the structural feature in two supramolecular frameworks. The UV-vis, fluorescence and electrochemistry properties are also studied.

  20. Synthesis, photophysics of two new perylene bisimides and their photovoltaic performances in quasi solid state dye sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Mikroyannidis, John A.; Stylianakis, Minas M.; Roy, M. S.; Suresh, P.; Sharma, G. D.

    Two new symmetrical compounds A and P based on perylene-anthracene and perylene-pyrene, respectively, were synthesized and characterized by FT-IR, 1H NMR, TGA and TMA. These compounds contained tert-butyl groups which enhanced their solubility, decomposed above 400 °C and gave char yields of 46-65% at 800 °C in N 2. Compound A showed significantly higher glass transition temperature (124 °C) than P (75 °C). Their absorption spectra were broad with longer wavelength absorption at 467-525 nm and optical band gap of 2.05 eV. The solutions of the compounds emitted green-yellow light with maximum at 555 nm, while their films were not photoluminescent. The compound A shows better photovoltaic response than compound P. Quasi solid state dye sensitized solar cells (DSSCs) have been fabricated employing compound A as sensitizer and polymer sol gel as electrolyte and characterized through the current-voltage characteristics in dark as well as under illumination and electrochemical impedance spectra. We found that the Al 2O 3 modification of TiO 2 layer significantly improves the dye absorption resulting in enhancement of power conversion efficiency (PCE) (from 1.15 to 2.13%) which is attributed to the increase in electron lifetime and reduction in back transfer of electrons. Finally, the TiO 2 has been incorporated into the polymer electrolyte gel to improve the power conversion efficiency (3.42%) of the quasi solid state DSSC. The faster electron diffusion in the device, the high ionic conductivity and the low activation energy of the polymer electrolyte are also responsible for enhanced PCE, when TiO 2 nano-particles are incorporated in the polymer electrolyte.

  1. Optical gating with organic building blocks. A quantitative model for the fluorescence modulation of photochromic perylene bisimide dithienylcyclopentene triads

    PubMed Central

    Pärs, Martti; Gradmann, Michael; Gräf, Katja; Bauer, Peter; Thelakkat, Mukundan; Köhler, Jürgen

    2014-01-01

    We investigated the capability of molecular triads, consisting of two strong fluorophores that were covalently linked to a photochromic molecule, for optical gating. Therefore we monitored the fluorescence intensity of the fluorophores as a function of the isomeric state of the photoswitch. From the analysis of our data we develop a kinetic model that allows us to predict quantitatively the degree of the fluorescence modulation as a function of the mutual intensities of the lasers that are used to induce the fluorescence and the switching of the photochromic unit. We find that the achievable contrast for the modulation of the fluorescence depends mainly on the intensity ratio of the two light beams and appears to be very robust against absolute changes of these intensities. The latter result provides valuable information for the development of all-optical circuits which would require to handle different signal strengths for the input and output levels. PMID:24614963

  2. Synthesis and Luminescent Chemosensory Behavior of N,N'-bis(p-aminophenyl)-1,5-bis(p-(tetraethyleneglycoloxy)phenyl)anthracene-2,3,6,7-tetracarboxyl bisimide

    NASA Technical Reports Server (NTRS)

    Ilhan, Faysal; Tyson, Daniel S.; Meador, Michael A.

    2004-01-01

    We have utilized the photoenolization reaction of a dibenzoyl-p-xylene derivative to synthesize two new, highly substituted anthracene-based molecules. ABI-NO2 and ABI-NH2 maintained photostability with longer wavelength absorption and emission spectra as compared to unsubstituted anthracene. Conversion of the periphery nitro groups to amines created an internal photoinduced electron transfer scenario that quenched the luminescence of ABI-NH2. Reversible or irreversible reaction of the attached amines resulted in fluorescence recovery. Sensitivity, of ABI-NH2 and other potential derivatives, to toxic chemicals may prove useful for early detection systems.

  3. High-Performance Non-Fullerene Organic Solar Cells Based on a Selenium-Containing Polymer Donor and a Twisted Perylene Bisimide Acceptor

    SciTech Connect

    Liu, Tao; Meng, Dong; Cai, Yunhao; Sun, Xiaobo; Li, Yan; Huo, Lijun; Liu, Feng; Wang, Zhaohui; Russell, Thomas P.; Sun, Yanming

    2016-04-23

    A novel polymer donor (PBDTS-Se) is designed to match with a non-fullerene acceptor (SdiPBI-S). The corresponding solar cells show a high efficiency of 8.22%, which result from synergetic improvements of light harvesting, charge carrier transport and collection, and morphology. The results indicate that rational design of novel donor materials is important for non-fullerene organic solar cells.

  4. High-Performance Non-Fullerene Organic Solar Cells Based on a Selenium-Containing Polymer Donor and a Twisted Perylene Bisimide Acceptor.

    PubMed

    Liu, Tao; Meng, Dong; Cai, Yunhao; Sun, Xiaobo; Li, Yan; Huo, Lijun; Liu, Feng; Wang, Zhaohui; Russell, Thomas P; Sun, Yanming

    2016-09-01

    A novel polymer donor (PBDTS-Se) is designed to match with a non-fullerene acceptor (SdiPBI-S). The corresponding solar cells show a high efficiency of 8.22%, which result from synergetic improvements of light harvesting, charge carrier transport and collection, and morphology. The results indicate that rational design of novel donor materials is important for non-fullerene organic solar cells.

  5. Critical Processing Conditions of a Specific Ternary System-Molecular Composite

    DTIC Science & Technology

    1981-02-01

    amorphous coil-like polymers-have been [2]investigated. A pair of polymers, rod-like poly-para-phenylene benzothiazole (PBT) - with its improved thermo...polymers have been. [2]investigated. A pair of polymers, rod-like poly-para-phenylene benzothiazole (PBT) - with its improved thermo-oxidative

  6. A unique perylene-based DNA intercalator: localization in cell nuclei and inhibition of cancer cells and tumors.

    PubMed

    Xu, Zejun; Guo, Kunru; Yu, Jieshi; Sun, Haili; Tang, Jun; Shen, Jie; Müllen, Klaus; Yang, Wantai; Yin, Meizhen

    2014-10-29

    To date, perylene derivatives have not been explored as DNA intercalator to inhibit cancer cells by intercalating into the base pairs of DNA. Herein, a water-soluble perylene bisimide (PBDI) that efficiently intercalates into the base pairs of DNA is synthesized. Excitingly, PBDI is superior to the commercial DNA intercalator, amonafide, for specific nuclear accumulation and effective suppression of cancer cells and tumors.

  7. Nanoassemblies Based on Semiconductor Quantum Dots and Dye Molecules:. Single Objects Detection and Related Interface Dynamics

    NASA Astrophysics Data System (ADS)

    Zenkevich, E.; von Borczyskowski, C.; Kowerko, D.

    2013-05-01

    Single molecule spectroscopy of QD-dye nanoassemblies is shown that single functionalized dye molecules (perylene-bisimides and meso-pyridyl porphyrins) can be considered as extremely sensitive probes for studying exciton and relaxation processes in semiconductor CdSe/ZnS quantum dots.

  8. A Low Reabsorbing Luminescent Solar Concentrator Employing π-Conjugated Polymers.

    PubMed

    Gutierrez, Gregory D; Coropceanu, Igor; Bawendi, Moungi G; Swager, Timothy M

    2016-01-20

    A highly efficient thin-film luminescent solar concentrator (LSC) utilizing two π-conjugated polymers as antennae for small amounts of the valued perylene bisimide Lumogen F Red 305 is presented. The LSC exhibits high photoluminescence quantum yield, low reabsorption, and relatively low refractive indices for waveguide matching. A Monte Carlo simulation predicts the LSC to possess exceptionally high optical efficiencies on large scales. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Trapping on demand: External regulation of excitation energy transfer in a photoswitchable smart matrix

    NASA Astrophysics Data System (ADS)

    Schmidt, R.; Pärs, M.; Weller, T.; Thelakkat, M.; Köhler, J.

    2014-01-01

    A thin film of polystyrene has been doped with small amounts of dithienylcyclopentene (DCP) based molecular switches and perylene bisimide (PBI) chromophores to obtain a photoswitchable smart matrix. The photochromic DCP can be converted by light between two bistable conformations and thereby changes the energetic position of its lowest excited singlet state. We exploit this feature to regulate the transfer of excitation energy between PBI and DCP as a function of the externally controllable illumination conditions in such a blend.

  10. Fire- and Heat-Resistant Laminating Resins

    NASA Technical Reports Server (NTRS)

    Kourtides, Demetrius A.; Mikroyannidis, John A.

    1987-01-01

    Imide compounds containing phosphourus thermally polymerized. New maleimido- or citraconimido-end-capped monomers, have relatively low melting temperatures, polymerized at moderate temperatures to rigid bisimide resins without elimination of volatiles. Monomers dissolve in such solvents as methyl ethyl ketone, acetone, and tetrahydrofuran, suitable and perferred as "varnish solvents" for composite fabrication. Low melting points of these componds allow use as adhesives without addition of solvents.

  11. Fire- and Heat-Resistant Laminating Resins

    NASA Technical Reports Server (NTRS)

    Kourtides, Demetrius A.; Mikroyannidis, John A.

    1987-01-01

    Imide compounds containing phosphourus thermally polymerized. New maleimido- or citraconimido-end-capped monomers, have relatively low melting temperatures, polymerized at moderate temperatures to rigid bisimide resins without elimination of volatiles. Monomers dissolve in such solvents as methyl ethyl ketone, acetone, and tetrahydrofuran, suitable and perferred as "varnish solvents" for composite fabrication. Low melting points of these componds allow use as adhesives without addition of solvents.

  12. Imide modified epoxy matrix resins

    NASA Technical Reports Server (NTRS)

    Scola, D. A.

    1984-01-01

    The results of a program designed to develop tough imide modified epoxy resins cured by bisimide amine (BIA) hardeners are described. State-of-the-art epoxides MY720 and DER383 were used, and four bismide amines were evaluated. These were the BIA's derived from the 6F anhydride (4,4'-(hexafluoroisopropylidene) bis(phthalic anhydride) and the diamines 3,3'-diaminodiphynyl sulfone, 4,4'-oxygianiline, 4,4'-methylene dianiline, and 1,12-dodecane diamine. A key intermediate, designated 6F anhydride, is required for the synthesis of the bisimide amines. Reaction parameters to synthesize a precursor to the 6F anhydride (6FHC) in high yields were investigated. The catalyst trifluoromethane sulfonic acid was studied. Although small scale runs yielded the 6FHC in 50 percent yield, efforts to ranslate these results to a larger scale synthesis gave the 6FHC in only 9 percent yield. Results show that the concept of using bisimide amine as curing agents to improve the toughness properties of epoxies is valid.

  13. A supramolecular helix that disregards chirality.

    PubMed

    Roche, Cécile; Sun, Hao-Jan; Leowanawat, Pawaret; Araoka, Fumito; Partridge, Benjamin E; Peterca, Mihai; Wilson, Daniela A; Prendergast, Margaret E; Heiney, Paul A; Graf, Robert; Spiess, Hans W; Zeng, Xiangbing; Ungar, Goran; Percec, Virgil

    2016-01-01

    The functions of complex crystalline systems derived from supramolecular biological and non-biological assemblies typically emerge from homochiral programmed primary structures via first principles involving secondary, tertiary and quaternary structures. In contrast, heterochiral and racemic compounds yield disordered crystals, amorphous solids or liquids. Here, we report the self-assembly of perylene bisimide derivatives in a supramolecular helix that in turn self-organizes in columnar hexagonal crystalline domains regardless of the enantiomeric purity of the perylene bisimide. We show that both homochiral and racemic perylene bisimide compounds, including a mixture of 21 diastereomers that cannot be deracemized at the molecular level, self-organize to form single-handed helical assemblies with identical single-crystal-like order. We propose that this high crystalline order is generated via a cogwheel mechanism that disregards the chirality of the self-assembling building blocks. We anticipate that this mechanism will facilitate access to previously inaccessible complex crystalline systems from racemic and homochiral building blocks.

  14. Imide modified epoxy matrix resins

    NASA Technical Reports Server (NTRS)

    Scola, D. A.; Pater, R. H.

    1981-01-01

    High char yield epoxy using novel bisimide amines (BIA's) as curing agents with a state of the art epoxy resin was developed. Stoichiometric quantities of the epoxy resin and the BIA's were studied to determine the cure cycle required for preparation of resin specimens. The bisimide cured epoxies were designated IME's (imide modified epoxy). The physical, thermal and mechanical properties of these novel resins were determined. The levels of moisture absorption exhibited by the bisimide amine cured expoxies (IME's) were considerably lower than the state of the art epoxies. The strain-to-failure of the control resin system was improved 25% by replacement of DDS with 6F-DDS. Each BIA containing resin exhibited twice the char yield of the control resin MY 720/DDS. Graphite fiber reinforced control (C) and IME resins were fabricated and characterized. Two of the composite systems showed superior properties compared to the other Celion 6000/IME composite systems and state of the art graphite epoxy systems. The two systems exhibited excellent wet shear and flexural strengths and moduli at 300 and 350 F.

  15. Fluorinated polymides for interlayer dielectric applications: Tailoring of properties via copolymerization

    SciTech Connect

    Auman, B.C.; McKerrow, A.J.; Ho, P.S.

    1996-10-01

    Over the past several years DuPont has been exploring new, rod-like fluorinated polyimides for interlayer dielectric (ILD) applications. It has been shown that copolymerization is a versatile method for tailoring properties of these rigid polyimides. Initial product offerings from DuPont showed an excellent balance of properties for ILD applications. These materials, however, due to their highly rod-like structure and very low in-plane coefficient of thermal expansion (CTE), actually yielded negative thermal stresses on silicon at the 1 {mu}m thicknesses typical of interlayer dielectrics. More flexible materials with higher CTE typically yield positive stress values which can be undesirably quite high. The dielectric constant of these highly rod-like fluorinated polyimides was also somewhat anisotropic, again due to the rod-like nature and resulting high in-plane orientation of these polyimides. Since a thermal stress on silicon near zero and a more isotropic dielectric constant are likely the most desirable states for an ILD, the highly rod-like polyimide was further optimized by incorporation of a more flexible fluorinated comonomer, 6FDA, at various levels to increase CTE and balance dielectric constant. The various properties of this series of fluorinated polyimides were investigated. The results have shown that it is indeed possible to obtain near zero stress on silicon while attaining more isotropic dielectric constant via structure optimization.

  16. Eutectic pattern transition under different temperature gradients: A phase field study coupled with the parallel adaptive-mesh-refinement algorithm

    NASA Astrophysics Data System (ADS)

    Zhang, A.; Guo, Z.; Xiong, S.-M.

    2017-03-01

    Eutectic pattern transition under an externally imposed temperature gradient was studied using the phase field method coupled with a novel parallel adaptive-mesh-refinement (Para-AMR) algorithm. Numerical tests revealed that the Para-AMR algorithm could improve the computational efficiency by two orders of magnitude and thus made it possible to perform large-scale simulations without any compromising accuracy. Results showed that the direction of the temperature gradient played a crucial role in determining the eutectic patterns during solidification, which agreed well with experimental observations. In particular, the presence of the transverse temperature gradient could tilt the eutectic patterns, and in 3D simulations, the eutectic microstructure would alter from lamellar to rod-like and/or from rod-like to dumbbell-shaped. Furthermore, under a radial temperature gradient, the eutectic would evolve from a dumbbell-shaped or clover-shaped pattern to an isolated rod-like pattern.

  17. Faraday polarization fluctuations of satellite beacon signals

    NASA Technical Reports Server (NTRS)

    Lee, M. C.; Klobuchar, J. A.

    1988-01-01

    The anisotropic effects of random density irregularities in causing Faraday polarization fluctuations of VHF radio signals are examined, taking both rod-like and sheet-like irregularities into consideration. It is found that the variance of Faraday polarization fluctuations depends on the ratio of perpendicular to parallel correlation lengths. The anisotropic effect of rod-like ionospheric irregularities are shown to be most appreciable for longitudinal propagation. The anisotropic effect of sheet-like ionospheric irregularities, however, is not strongly dependent on the radio propagation angle. During transionospheric propagation at large angles with respect to the geomagnetic field, sheet-like irregularities may cause greater Faraday polarization fluctuations than rod-like irregularities.

  18. ETTF - Apt inserts sample into experiment in Spacehab

    NASA Image and Video Library

    1996-09-17

    STS79-E-5018 (17 September 1996) --- Astronaut Jerome (Jay) Apt prepares experiment, a rod-like device for insertion into Extreme Temperature Translation Furnace (ETTF) in STS-79-E-5019, during early mission chores aboard Spacehab in the Space Shuttle Atlantis cargo bay, on Flight Day 2.

  19. Evidence for rod-shaped DNA-stabilized silver nanocluster emitters.

    PubMed

    Schultz, Danielle; Gardner, Kira; Oemrawsingh, Sumant S R; Markešević, Nemanja; Olsson, Kevin; Debord, Mark; Bouwmeester, Dirk; Gwinn, Elisabeth

    2013-05-28

    Fluorescent DNA-stabilized silver nanoclusters contain both cationic and neutral silver atoms. The absorbance spectra of compositionally pure solutions follow the trend expected for rod-shaped silver clusters, consistent with the polarized emission measured from individual nanoclusters. The data suggest a rod-like assembly of silver atoms, with silver cations mediating attachment to the bases.

  20. Study and Characterization of Tobacco Mosaic Virus Head-to-tail Assembly Assisted by Aniline Polymerization

    SciTech Connect

    Niu,Z.; Bruckman, M.; Kotakadi, V.; He, J.; Emrick, T.; Russell, T.; Yang, L.; Wang, Q.

    2006-01-01

    One-dimensional composite nanofibres with narrow dispersity, high aspect ratio and high processibility have been fabricated by head-to-tail self-assembly of rod-like tobacco mosaic virus assisted by aniline polymerization, which can promote many potential applications including electronics, optics, sensing and biomedical engineering.

  1. Study of Chromosomes: Its Vital Importance in Agriculture, Biology, and Medicine

    USDA-ARS?s Scientific Manuscript database

    Chromosomes are rod-like structures in the nuclei of eukaryotic cells. DNA, the blueprint of life, combined with proteins (histones) is packaged into these dense string-like structures. Thus, chromosomes constitute an assembly of DNA and histones by which the genetic information is transmitted accu...

  2. APPARATUS FOR SHEARING TUBULAR JACKETS

    DOEpatents

    Simon, J.P.

    1962-09-01

    A machine is designed for removing the jacket from the core of a used rod-like fuel element by shearing the jacket into a spiral ribbon. Three skewed rolls move the fuel element axially and rotatively, and a tool cooperates with one of the rolls to carry out the shearing action. (AEC)

  3. Preparation and characterization of homogeneous chitosan-polylactic acid/hydroxyapatite nanocomposite for bone tissue engineering and evaluation of its mechanical properties.

    PubMed

    Cai, Xuan; Tong, Hua; Shen, Xinyu; Chen, Weixuan; Yan, Juan; Hu, Jiming

    2009-09-01

    Homogeneous nanocomposites composed of hydroxyapatite and chitosan in the presence of polylactic acid were synthesized by a novel in situ precipitation method. The morphological and compositional properties of composites were investigated. Hydroxyapatite nanoparticles in a special rod-like shape with a diameter of about 50nm and a length of about 300nm were distributed homogeneously within the chitosan-polylactic acid matrix. The interaction between the organic matrix and the inorganic crystallite and the formation mechanism of the rod-like nanoparticles were also studied. The results suggested that the formation of the special rod-like nanoparticles could be controlled by a multiple-order template effect. High-resolution images showed that the rod-like inorganic particles were composed of randomly orientated subparticles about 10nm in diameter. The mechanical properties of the composites were evaluated by measuring their compressive strength and elastic modulus. The data indicated that the addition of polylactic acid can make homogeneous composites scaffold resist significantly higher stress. The elastic modulus of the composites was also improved by the addition of polylactic acid, which can make them more beneficial for surgical applications.

  4. Morphological influence of cellulose nanoparticles (CNs) from cottonseed hulls on rheological properties of polyvinyl alcohol/CN suspensions

    USDA-ARS?s Scientific Manuscript database

    This work aims to extract and characterize fibrous, rod-like and spherical cellulose nanoparticles (CNs) from cottonseed hull and to investigate the structure-morphology-rheology relationships. The rheological behavior of poly(vinyl alcohol) (PVA)/CNs suspensions was also examined to guide the solve...

  5. Method for preparing spherical thermoplastic particles of uniform size

    DOEpatents

    Day, J.R.

    1975-11-17

    Spherical particles of thermoplastic material of virtually uniform roundness and diameter are prepared by cutting monofilaments of a selected diameter into rod-like segments of a selected uniform length which are then heated in a viscous liquid to effect the formation of the spherical particles.

  6. Molecular Composites from the Phase Separation at Low Temperatures of Kevlar and Diaminophenylindane Polyimide in Sulfuric Acid

    DTIC Science & Technology

    1988-09-30

    Pat. Appl. 902525, (1978). 2. Jackson, C. L., Samulski, E. T. and Shaw, M. T., "Foams from Rod-like Molecules", ACS PMSE Division Proceeding, Vol. 57...107 (1987). 3. Alonso, M. A. and Shaw, M. T., "Isotropic Kevlar and PBA (poly 1.4 benzamide) Reinforcements from Composites", ACS PMSE Toronto, Canada

  7. Novel DNA nanoparticles and networks.

    PubMed

    Seela, Frank; Jawalekar, Anup M; Sirivolu, Venkata R; Rosemeyer, Helmut; He, Yang; Leonard, Peter

    2005-01-01

    Joining the thrombin-binding aptamer 5-d(GGTTGGTGTGGTTGG) and the minihairpin 5-d(GCGAAGC) leads to new DNA nanoparticles, which are different from rod-like helical double-stranded DNA. Covalent interstrand cross-links in DNA duplexes generated by bifunctional alkadiyne chains were used to build-up the DNA networks.

  8. The enhanced MR performance of dimorphic MR suspensions containing either magnetic rods or their non-magnetic analogs

    NASA Astrophysics Data System (ADS)

    Plachy, Tomas; Cvek, Martin; Kozakova, Zuzana; Sedlacik, Michal; Moucka, Robert

    2017-02-01

    A co-precipitation method was used to prepare non-magnetic rod-like ferrous oxalate dihydrate (Fe2CO4 · 2H2O) particles that were further turned into iron oxide (Fe3O4) magnetic rod-like particles. A simple precursor-assisted thermal decomposition technique enabled the preservation of the morphology and size of the precursor ferrous oxalate dihydrate particles, thus allowing their magnetic analogs to be obtained. Both types of rod-like particles were used as an additive together with spherical carbonyl iron (CI) particles in novel dimorphic magnetorheological (MR) suspensions. Controlled shear rate mode experiments were performed using a rotational rheometer with a source of an external magnetic field in order to investigate their MR behavior. Moreover, the properties of the novel prepared dimorphic MR (DMR) suspensions were compared with conventional MR suspensions based on spherical CI microparticles. It was found that the DMR suspensions exhibit enhanced MR performance as well as enhanced sedimentation stability in comparison with the MR suspension based on pure CI. The dimorphic suspensions containing magnetic rod-like additives further exhibited significant MR hardening at low shear rates. The properties of CI-based suspensions can be thus optimized by using various additive substances.

  9. A bolaamphiphilic amino acid appended photo-switching supramolecular gel and tuning of photo-switching behaviour.

    PubMed

    Roy, Subhasish; Maiti, Dibakar Kumar; Panigrahi, Shrabani; Basak, Durga; Banerjee, Arindam

    2014-04-07

    Self-assembled bolaamphiphilic perylene bisimide (PBI) containing an amino acid appended fluorescent semiconducting soft material (hydrogel) has been discovered at physiological pH. This new organic material based on self-assembled perylene bisimide appended amino acid-based bolaamphiphile (PBI-C11-Y) has been well characterized using various techniques including UV-Vis, fluorescence, X-ray diffraction, FT-IR, transmission electron microscopic (TEM) and atomic force microscopic (AFM) studies. Interestingly, the UV-Vis absorption properties of the soft-material are dependent on the pH of the medium. This PBI-conjugated amino acid appended gelator molecule contains a centrally located perylene bisimide moiety as well as an aromatic amino acid l-tyrosine at the side chains, which are extremely useful for interacting with the delocalized large π-surface of GO (graphene oxide) or RGO (reduced graphene oxide) to form a GO/RGO containing hybrid hydrogel. Graphene oxide and reduced graphene oxide have been successfully incorporated into the nanofibrillar network structure of the PBI-C11-Y based gel to make nanohybrid systems. The I-V profile of the semiconducting photo-responsive soft-material of the PBI-C11-Y has been successfully tuned upon the incorporation of GO and RGO within the gel-based soft material. This PBI-C11-Y xerogel based structure shows photo-switching behaviour upon exposure to white light. The ON/OFF ratio of the PBI-C11-Y can be modulated upon the inclusion of GO and RGO within the hydrogel matrix. Furthermore, the OFF state stability of the PBI-C11-Y xerogel material has been increased upon the inclusion of RGO. Regulation of the photo-switching behaviour of the PBI-C11-Y based xerogel holds promise for making PBI-containing amino acid appended biomaterials with interesting properties in future.

  10. Perylene Derivatives As Useful SERRS Reporters, Including Multiplexing Analysis.

    PubMed

    Tenori, Eleonora; Colusso, Andrea; Syrgiannis, Zois; Bonasera, Aurelio; Osella, Silvio; Ostric, Adrian; Lazzaroni, Roberto; Meneghetti, Moreno; Prato, Maurizio

    2015-12-30

    Five perylene bisimide (PBI) derivatives were designed and synthesized, on the basis of quantum-chemical calculations. The influence of halogen substituents on the shape and energy of the frontier orbitals and the Raman spectra were calculated, in the prospect use in surface-enhanced resonance Raman scattering (SERRS) studies. The corresponding experiments confirmed a very strong SERRS response in the presence of pristine (i.e., uncoated) gold nanoparticles. These spectra can be used for multiplexing measurements, namely measurements in which, by using a single laser excitation, one can recognize the simultaneous presence of several analytes.

  11. Redox-Active Supramolecular Polymer Binders for Lithium–Sulfur Batteries That Adapt Their Transport Properties in Operando

    SciTech Connect

    Frischmann, Peter D.; Hwa, Yoon; Cairns, Elton J.; Helms, Brett A.

    2016-10-25

    π-Stacked perylene bisimide (PBI) molecules are implemented here as highly networked, redox-active supramolecular polymer binders in sulfur cathodes for lightweight and energy-dense Li-S batteries. We show that the in operando reduction and lithiation of these PBI binders sustainably reduces Li-S cell impedance relative to nonredox active conventional polymer binders. This lower impedance enables high-rate cycling in Li-S cells with excellent durability, a critical step toward unlocking the full potential of Li-S batteries for electric vehicles and aviation.

  12. Controllable Self-Assembly of Amphiphilic Zwitterionic PBI Towards Tunable Surface Wettability of the Nanostructures.

    PubMed

    Ye, Yong; Lü, Baozhong; Cheng, Wenyu; Wu, Zhen; Wei, Jie; Yin, Meizhen

    2017-05-04

    Amphiphilic molecules have received wide attention as they possess both hydrophobic and hydrophilic properties, and can form diverse nanostructures in selective solvents. Herein, we report an asymmetric amphiphilic zwitterionic perylene bisimide (AZP) with an octyl chain and a zwitterionic group on the opposite imide positions of perylene tetracarboxylic dianhydride. The controllable nanostructures of AZP with tunable hydrophilic/hydrophobic surface have been investigated through solvent-dependent amphiphilic self-assembly as confirmed by SEM, TEM, and contact angle measurements. The planar perylene core of AZP contributes to strong π-π stacking, while the amphiphilic balance of asymmetric AZP adjusts the self-assembly property. Additionally, due to intermolecular π-π stacking and solvent-solute interactions, AZP could self-assemble into hydrophilic microtubes in a polar solvent (acetone) and hydrophobic nanofibers in an apolar solvent (hexane). This facile method provides a new pathway for controlling the surface properties based on an asymmetric amphiphilic zwitterionic perylene bisimide. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Modification of MnO2 nanoparticles with rutin synthesized by Triton X-100 aggregations' template

    NASA Astrophysics Data System (ADS)

    Wang, Yi; Zhu, Jun; Han, Jie; Guo, Rong

    2008-10-01

    Manganese dioxide (MnO2) nanoparticles have been prepared through the redox reaction between KMnO4 and the nonionic surfactant Triton X-100 with the aid of rod-like micelles, hexagonal liquid crystals and reverse micelle templates, in which Triton X-100 acts both as template and reductant. MnO2 nanorods (20 50 nm in diameter) can be obtained in rod-like micelles and hexagonal liquid crystals, whereas MnO2 nanospheres (about 85 nm in diameter) are formed in reverse micelles. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) are used to characterize the products. Modification of MnO2 nanoparticles by rutin has been discussed using fluorescence spectra and UV vis spectra, and the free radical eliminating investigations of surface-modified MnO2 nanoparticles with rutin show that MnO2 nanoparticles can improve the free-radical-scavenging activity of rutin.

  14. Geometrical design of self-phoretic colloids

    NASA Astrophysics Data System (ADS)

    Nourhani, Amir; Lammert, Paul E.

    Within a unified formalism we study the generic properties of self-phoretic particles for source-or-sink (such as self-diffusiophoresis and self-thermophoresis) and sink-and-source (such as self-electrophoresis) flux distribution across a continuous range of geometries from disk-like to sphere to rod-like shapes. We obtain new insights into the performance of self-phoretic particles as a function of the distribution of surface flux and their shape. Surprisingly, upon varying the geometry between the sphere and rod-like shape, the velocity is not simply an interpolation, but has a nonmonotonic dependent on particle geometry. This work was supported by the NSF under Grants No. DMR-0820404 and DMR-1420620 through the Penn State Center for Nanoscale Science.

  15. A green chemical approach for synthesis of shape anisotropic gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Kalyan Kamal, S. S.; Vimala, J.; Sahoo, P. K.; Ghosal, P.; Ram, S.; Durai, L.

    2014-06-01

    A complete green chemical reaction between aurochloric acid and tea polyphenols resulted in the reduction of Au3+ → Au0. The reaction was carried out in a Teflon-coated bomb digestion vessel at 200 °C. It was observed that with increasing the reaction time from 1 to 5 h, the shape of the nanoparticles changed from spherical- to rod-like structures. The reaction was followed with the help of UV-vis spectrometer, which showed a single absorption peak at 548 nm for 1-h reaction product and two peaks for a 5-h reaction product at 533 and 745 nm corresponding to the transverse and longitudinal surface plasmon resonance bands. Microstructures obtained from transmission electron microscope revealed that the samples obtained after 1-h reaction are predominantly spherical in shape with an average size of 15 nm. Whereas samples obtained after 5 h of reaction exhibited rod-like structures with an average size of 45 nm.

  16. Thin film growth and Zn doping of h-MoO3 hexagonal rods by hydrothermal technique

    NASA Astrophysics Data System (ADS)

    Mousavi-Zadeh, Seyyed Hamid; Rahmani, Mohammad Bagher

    2016-12-01

    In this research, rod-like undoped and Zn doped h-MoO3 thin films were grown on top of MoO3 seed layers, using hydrothermal technique without adding any surfactant. Seed layers of MoO3 were coated on top of glass substrates using spray pyrolysis technique. Structural, morphological and optical properties of thin films were examined. XRD pattern analysis showed that the seed layer has orthorhombic crystal structure. Also, it confirms the formation of hexagonal structure for thin films grown by hydrothermal. FESEM images show the formation of long, well-shaped hexagonal rod-likes. UV-Vis spectroscopy reveals band gap increasing from 3.2 eV to 3.54 eV, by increasing Zn.

  17. Fluorinated and nonfluorinated polyimides based on 4,4{double_prime}-diamino-p-terphenyl

    SciTech Connect

    Auman, B.C.

    1993-12-31

    The synthesis of stiff, rod-like polyimides based on rod-like 4,4{double_prime}-diamino-p-terphenyl (DATP) is described. Both fluorinated and nonfluorinated materials were prepared. Polyimide films based on DATP and standard dianhydrides, pyromellitic dianhydride and biphenyl tetracarboyxlic dianhydride, exhibited remarkably low moisture absorption; while those based on DATP and rigid, fluorinated dianhydrides, 9,9-bis(trifluoromethyl)- and 9-phenyl-9-trifluoromethyl-xanthene-2,3,6,7-tetracarboxylic dianhydrides showed low dielectric constant, but were higher in moisture absorption than expected. All four structures studied showed very low CTE typical of very stiff, rodlike materials. These materials have potential uses in electronics applications in which low CTE (for less stress), low moisture and low dielectric constant are important. Other potential uses include fibers, resins, coatings and composites.

  18. Influence of convection on rod spacing of eutectics

    NASA Technical Reports Server (NTRS)

    Caram, R.; Chandrasekhar, S.; Wilcox, W. R.

    1990-01-01

    This paper describes a three-dimensional numerical model to study the influence of convection on the rod-like microstructure of an eutectic system. This model is based on a central finite difference approach. By applying it, the average concentration near the solid/liquid interface of a growing rod-like eutectic was determined for eutectic compositions C(e) of 0.03, 0.05, and 0.10. Following Jackson and Hunt (1966), the average interfacial composition was converted to a change of undercooling at the interface and, finally, to spacing between the rods. The change in rod spacing with increasing intensity of convection was calculated assuming the eutectic grows at minimum interfacial undercooling. It was confirmed that an increase in convection should coarsen the microstructure (i.e., the rod spacing increases with increasing intensity of stirring).

  19. Influence of processing parameters on spherulite formation and crystallization behaviour of polypropylene

    NASA Astrophysics Data System (ADS)

    Ariff, Zulkifli Mohamad; Loon, Chan Kai; Zakaria, Zunaida

    2017-04-01

    The effects of different parameters on polypropylene crystallization behavior were investigated using a constant stress capillary rheometer. Morphology changes of polypropylene spherulite were characterized using polarized light optical microscope and relationship between growth rate of spherulite, Avrami exponent with respect to the processing effects were evaluated. The result indicates that increasing pressure has pronounced effect on spherulite orientation which changes the spherulite shape from round or disc to rod-like shape. Corresponding to the changes of spherulite shape to rod-like, the value of Avrami exponent was decreased and approaching the value of 1. On the other hand, processing temperature influenced the stress relaxation process that encouraged the spherulite to have more rounded or disc shape. The influence can be quatitatively assessed thorugh increment of Avrami exponent nearing to the value of 2 indicating that the growth was in two dimensions.

  20. Simultaneous polymerization-induced self-assembly (PISA) and guest molecule encapsulation.

    PubMed

    Karagoz, Bunyamin; Boyer, Cyrille; Davis, Thomas P

    2014-02-01

    Nanoparticles with various morphologies such as micelles, worm-like/rod-like and spherical vesicles are made using a polymerization-induced self-assembly (PISA) approach via a one-pot RAFT dispersion polymerization. On polymerization/self-assembly, we report a concurrent highly efficient loading of guest molecules within the nanoparticle structures. Different nanoparticle morphologies, such as spherical micelles, worm-like, rod-like, and spherical vesicles, are achieved by gradually increasing the number-average degree of polymerization (DPn) of the PST block via increasing polymerization times (in a poor solvent) as determined by transmission electron microscopy (TEM) and dynamic light scattering (DLS) measurements. In parallel, a guest molecule (Nile Red) is encapsulated during the polymerization without disturbing the morphology or the polymerization kinetics.

  1. The effect of solvent on the morphology of ZnO nanostructure assembly by dielectrophoresis and its device applications.

    PubMed

    La Ferrara, Vera; Pacheri Madathil, Aneesh; De Girolamo Del Mauro, Anna; Massera, Ettore; Polichetti, Tiziana; Rametta, Gabriella

    2012-07-01

    Different zinc oxide nanostructured morphologies were grown on photolithographically patterned silicon/silicon dioxide substrates by dielectrophoresis technique using different solvents, such as water and ethanol, obtaining rod-like and net-like nanostructures, respectively. The formation of continuous nanostructures was confirmed by scanning electron microscopic, atomic force microscopic images, and electrical characterizations. The rod-like zinc oxide nanostructures were observed in the 10 μm gap between the fingers in the pattern, whereas net-like nanostructures were formed independently of microgap. A qualitative study about the mechanism for the assembly of zinc oxide continuous nanostructures was presented. Devices were electrically characterized, at room temperature, in controlled environment to measure the conductance behavior in ultraviolet and humidity environment. Devices based on zinc oxide nanostructures grown in ethanol medium show better responses under both ultraviolet and humidity, because of the net-like structure with high surface-to-volume ratio.

  2. Incorporating headgroup structure into the Poisson-Boltzmann model of charged lipid membranes

    NASA Astrophysics Data System (ADS)

    Wang, Muyang; Chen, Er-Qiang; Yang, Shuang; May, Sylvio

    2013-07-01

    Charged lipids often possess a complex headgroup structure with several spatially separated charges and internal conformational degrees of freedom. We propose a headgroup model consisting of two rod-like segments of the same length that form a flexible joint, with three charges of arbitrary sign and valence located at the joint and the two terminal positions. One terminal charge is firmly anchored at the polar-apolar interface of the lipid layer whereas the other two benefit from the orientational degrees of freedom of the two headgroup segments. This headgroup model is incorporated into the mean-field continuum Poisson-Boltzmann formalism of the electric double layer. For sufficiently small lengths of the two rod-like segments a closed-form expression of the charging free energy is calculated. For three specific examples—a zwitterionic headgroup with conformational freedom and two headgroups that carry an excess charge—we analyze and discuss conformational properties and electrostatic free energies.

  3. Nanonewton force measurement using a modified Michelson interferometer

    NASA Astrophysics Data System (ADS)

    Tahviliyan, Masoud; Charsooghi, Mohammad A.; Akhlaghi, Ehsan A.; Taghi Tavassoly, Mohammad

    2017-04-01

    In this paper, we introduce a new method to measure forces in the nanonewton range. The method is based on modification of a Michelson interferometer in which the rigid mirrors are replaced with two thin rod-like mirrors. One of the rod-like mirrors is fixed at both ends and the other has one free end. As the mirror with free end deflects in response to an applied force the spatial interference pattern is changed. Analysis of the interference fringes provides a readout of the rod deflection and thereby the applied force. The device is calibrated by applying known forces to the mirror with a free end and measuring the resulting displacement. Two different methods, mechanical and electrostatic, are used for calibration. The precision of the measurements and the propagation of the calibration uncertainty are investigated. The results show that this optical method is a good candidate for detecting small forces in the nanonewton range.

  4. The self-assembly of a macroion with anisotropic surface charge density distribution.

    PubMed

    Haso, Fadi; Fang, Xikui; Yin, Panchao; Li, Dong; Ross, Jennifer L; Liu, Tianbo

    2013-01-21

    A macroion, having anisotropic surface charge density distribution, shows unique self-assembly behaviour in polar solvents. Regular "blackberry"-like assemblies form in methanol-water mixtures due to counter-ion mediated attraction and the strong contribution of hydrogen bonding. However, rod-like assemblies form in acetone-water mixtures as the charge inhomogeneity effect overcomes the non-directional hydrogen bonding.

  5. Biomimetic Polyaminoacids as Precursors for Optical-Active Intelligent Materials

    DTIC Science & Technology

    2003-06-17

    University of Chemical Technology , Moscow, Russia Abstract Three main types of light-sensitive polyaminoacids (PAA) such as: rod-like dyes... Technology , Moscow, Russia 8. PERFORMING ORGANIZATION REPORT NUMBER 9. SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSOR/MONITOR’S...taining 0.25% mol of dye and 33% molar % fluorescein, but last compound detected weak absorbtion 499nm, fig. 3(a). Strong splitting was detected for n-Glu

  6. Process for forming shaped group III-V semiconductor nanocrystals, and product formed using process

    DOEpatents

    Alivisatos, A. Paul; Peng, Xiaogang; Manna, Liberato

    2001-01-01

    A process for the formation of shaped Group III-V semiconductor nanocrystals comprises contacting the semiconductor nanocrystal precursors with a liquid media comprising a binary mixture of phosphorus-containing organic surfactants capable of promoting the growth of either spherical semiconductor nanocrystals or rod-like semiconductor nanocrystals, whereby the shape of the semiconductor nanocrystals formed in said binary mixture of surfactants is controlled by adjusting the ratio of the surfactants in the binary mixture.

  7. Characterizing trace metal impurities in optical waveguide materials using x-ray absorption

    SciTech Connect

    Citrin, P.H.; Northrup, P.A.; Atkins, R.M.; Niu, L.; Marcus, M.A.; Jacobson, D.C.; Glodis, P.F.

    1998-12-31

    X-ray absorption measurements are described for identifying metal impurities in silica preforms, the rod-like starting materials from which hair-like optical fibers are drawn. The results demonstrate the effectiveness of this approach as a non-destructive, quantitative, element-selective, position-sensitive, and chemical-state-specific means for characterizing transition metals in the concentration regime of parts per billion.

  8. Interaction of Electromagnetic Fields with Biosynthetic Processes in Connective Tissue Cells

    DTIC Science & Technology

    1989-12-01

    induced by retinol ) which may resemble that which occurs in vivo in early stages of osteoarthritis. Possible therapeutic agents such as anti-invasion...Poisson- Boltzmann equation. The highest level of tractable compl,xity is that of a rod-like polyelectrolyte, representing a cross section of a...incorporation (Fig. 5) reflects the rate of synthesis of pro- 1-ri~ans and total protein, respectively. Sulfate and proline incorporation levels il aeqarose

  9. Observations on glial inclusion bodies in a case of acute disseminated sclerosis

    PubMed Central

    Field, E. J.; Miller, Henry; Russell, Dorothy S.

    1962-01-01

    An unusual rod-like structure enclosed within a vacuole is described as occurring in enlarged glial cells associated with the lesions encountered in an uncommonly acute case of multiple sclerosis apparently heralded by an attack of `viral encephalitis'. Similar bodies were not found in a variety of other enlarged glial cells. An encapsulated `grape-fruit' like structure was also seen. Images PMID:13892761

  10. Fluorinated Polyhedral Oligomeric Silsesquioxanes (F-POSS)

    DTIC Science & Technology

    2008-01-01

    Both FH and FD are triclinic (P1) showing the presence of one and two crystallographically independent “half” molecules in the asymmetric unit...conformations. The molecular structure of F-POSS contains rigid, rod-like fluoroalkyl chains, which are attached to the silicon atoms of the POSS cage...may also contribute to surface properties, including hydrophobicity. The crystal structures of FH and FD showed a near-parallel arrangement of the

  11. Tunable Composite Metamaterials with Imbedded Coherently Controllable Atomic or Molecular Materials

    DTIC Science & Technology

    2010-10-07

    control attained in this system is It is noted that the rod-like metamaterials considered here are already fabricated by electrodeposition processes...PMMA 330-385nm 470-490nm 510-550nm. 20 nm Blue Green Red [2] Solution casting technique for preparation Offers the possibility of Polychromatic...filter 36 nm 358 nm (strong) 591 nm (weak) 336 nm (Strong) 402 nm (weak) 60 nm [3] Ultra short pulse Ti: Saphire laser (50 fs pulse at a

  12. Synthesis and Characterization of Unique Liquid Crystalline Block Copolyesters. A Proposal for a Polymer Research Center at the Atlanta University.

    DTIC Science & Technology

    1984-10-01

    active 2-phenylsulfonylbicyclo- [2.2.21octane can be effected. B. Use of 1,2-Bia( phenylthio )ethylene Catalyzed (AICi3) and uncatalyzed reactions of...spun from rod-like thermotropic polymers generally have high - melting points. Although a high melting temperature is important for many end- use ...block copolymer. morphology. The objectives of the Polk and Bota research team were to use cyclohexane derivatives as the sof t blocks and benzene

  13. Process for forming shaped group II-VI semiconductor nanocrystals, and product formed using process

    DOEpatents

    Alivisatos, A. Paul; Peng, Xiaogang; Manna, Liberato

    2001-01-01

    A process for the formation of shaped Group II-VI semiconductor nanocrystals comprises contacting the semiconductor nanocrystal precursors with a liquid media comprising a binary mixture of phosphorus-containing organic surfactants capable of promoting the growth of either spherical semiconductor nanocrystals or rod-like semiconductor nanocrystals, whereby the shape of the semiconductor nanocrystals formed in said binary mixture of surfactants is controlled by adjusting the ratio of the surfactants in the binary mixture.

  14. [Development cycles of coryneform and Nocardia-like bacteria].

    PubMed

    Nesterenko, O A; Nogina, T M; Kvasnikov, E I

    1980-01-01

    The growth cycles and the types of cell separation were studied in a microchamber with the collection strains of Brevibacterium ammoniagenes ATTC 6871, B. helvolum ATCC 19239, B. linens CCM 47 and ATCC 9174, B. maris VKM B-464 and B. stationis ATCC 14403, as well as with the strains of the genus Rhodococcus isolated from soils, viz. R. maris sp. nov. IMB 283 and R. luteus sp. nov. IMB 385. According to the increasing complexity of cellular morphological transformation in the life cycle, the organisms may be arranged in a series: R. maris -- B. ammoniagenes -- B. stationis -- B. linens -- B. helvolum -- R. luteus. The first three organisms are characterized by the snapping type of separation of short rod-like daughter cells. The cells of B. linens separate by both the snapping and bending types. The coccoid cells of B. helvolum ATCC 19239 produce many buds which are transformed into rod-like cells in the course of growth. In the log phase of growth, both true and false branching of the cells is observed; the latter is the result of a peculiar growth of the ends in the separated cells of B. helvolum. The cells of R. luteus form a rudimentary, rapidly fragmenting mycelium whose rod-like elements divide then by binary fission; the daughter cells separate the bending and snapping types.

  15. Morphological Effect of Non-targeted Biomolecule-Modified MNPs on Reticuloendothelial System

    NASA Astrophysics Data System (ADS)

    Li, Xiao; Hu, Yan; Xiao, Jie; Cheng, Dengfeng; Xiu, Yan; Shi, Hongcheng

    2015-09-01

    Magnetic nanoparticles (MNPs) with special morphology were commonly used as biomaterials, while morphological effects of non-targeted biomolecule-modified MNPs on biological behaviors were still unclear. In this research, spherical and rod-like Fe3O4 in a comparable size were synthesized and then surface-modified by bovine serum albumin (BSA) as a model of non-targeted biomolecule-modified MNPs. Morphological effects were featured by TEM and quantification of in vitro phagocytic uptake, as well as the in vivo quantification of particles in reticuloendothelial system (RES)-related organs of normal Kunming mice. For these non-targeted BSA-modified MNPs, intracellular distributions were the same, but the rod-like MNPs were more likely to be uptake by macrophages; furthermore, the BSA-modified MNPs gathered in RES-related organs soon after intravenous injection, but the rod-like ones were expelled from the lung more quickly and expelled from the spleen more slowly. These preliminary results may be referable if MNPs or other similar biomolecule-modified nanoparticles were used.

  16. Crystallization-Driven Self-Assembly of Rod-Coil-Rod Pseudopolyrotaxanes into Spherical Micelles, Nanorods, and Nanorings in Aqueous Solutions.

    PubMed

    Qi, Rui; Jin, Yong; Cheng, Xinfeng; Fan, Baozhu; Sun, Tongbing; Peng, Shaojun; Li, Hanping

    2015-08-01

    A novel rod-containing block copolymer is constructed by supramacromolecular self-assembly of α-cyclodextrin and a triblock copolymer with methoxy polyethylene glycol as the flanking chains and the midterm block alternately connected by 2,2-dimethylolbutyric acid and isophorone diisocyanate. The assembled rod-containing block copolymer shows an exciting phenomenon of concentration- and pH-dependent morphological switching of well-defined nanostructures. In the solutions at pH 9.2, spherical micelles, rod-like micelles, and hydrogel are observed successively with an increase of the concentration. Notably, the rod-like micelles are composed of spherical segments due to the combination of the crystalline cores of the spherical micelles. In addition, 1D nanostructures with different curvatures from linear rod-like micelles (pH 9.2) to ring-shaped micelles (pH 7.5) can be obtained by controlling the pH values of the assembled systems.

  17. Simulation study of proton transport in ionomers

    NASA Astrophysics Data System (ADS)

    Taylor, Philip; Allahyarov, Elshad

    2008-03-01

    Coarse-grained molecular-dynamics simulations were used to study the morphological changes induced in a Nafion-like ionomer by the imposition of a strong electric field. We observe that proton transport through this polymer electrolyte membrane is accompanied by morphological changes that include the formation of structures aligned along the direction of the applied field. The polar head groups of the ionomer side chains assemble into clusters, which then form rod-like formations, and these cylindrical structures then assemble into a hexagonally ordered array aligned with the direction of current flow. For dry ionomers, at current densities in excess of 1 A/cm^2 these rod-like clusters undergo an inner micro-phase separation, in which distinct wire-like lines of sulfonate head groups are accompanied by similar wire-like alignments of bound protons. The clusters appear to be of two types. If there are two, four, or five lines of sulfonates then there is an equal number of lines of protons, but if there are three lines of sulfonates then they are accompanied by four lines of protons. Occasionally these lines of sulfonates and protons form a helical structure. Upon removal of the electric field, the hexagonal array of rod-like structures remains, but the microphase separation disappears below the threshold current of 1 A/cm^2.

  18. Nucleation and morphology of sodium metaborate dihydrate from NaOH solution

    NASA Astrophysics Data System (ADS)

    Qin, Shiyue; Zhang, Yifei; Zhang, Yi

    2016-01-01

    Szaibelyite ore is an important boron mineral used for producing boron compounds. Sodium metaborate dihydrate can be prepared through leaching of the szaibelyite ore in NaOH solution and the leaching liquor mainly consists of NaBO2 and NaOH. In this work, the induction time for sodium metaborate dihydrate crystallized in NaOH solution from 30 to 50 °C was systematically investigated. The primary nucleation and growth mechanism were determined on the basis of the induction time measurements. The crystals of various morphologies under different crystallization conditions were obtained: the rod-like crystals preferred to form at low temperature, while the plate-like crystals formed at high temperature; when the crystallization temperature was 30 °C, the flat rod-like crystals formed at low supersaturation, while the slim rod-like crystals formed at high supersaturation. Finally, the growth mechanism of the sodium metaborate dihydrate was identified with various models and the 2D nucleation-mediated model gave satisfactory fitting results.

  19. Effects of neutrino trapping on thermodynamic properties of nuclear ``pasta''

    NASA Astrophysics Data System (ADS)

    Watanabe, G.; Iida, K.; Sato, K.

    2001-05-01

    Geometrical structure of matter at subnuclear densities is investigated in the presence of a degenerate gas of neutrinos as encountered in stellar collapse. The crystalline phases with spherical, cylindrical and planar nuclei as well as with spherical and cylindrical nuclear bubbles are considered by using a compressible liquid-drop model. This model allows for uncertainties in the lepton fraction YL in addition to those in the nuclear surface tension Esurf and in the proton chemical potential in bulk neutron matter μp(0). The phase diagrams obtained at zero temperature show that only the phases with rod-like and slab-like nuclei occur at typical values of YL, Esurf and μp(0), whereas the bubble phases, especially with spherical bubbles, are at best expected at hypothetically low values of YL and/or Esurf. For the rod-like and slab-like nuclei, thermally induced displacements are calculated from their respective elastic constants. It is found that at temperatures appropriate to supernova cores, thermal fluctuations would destroy a layered lattice of slab-like nuclei rather than a triangular lattice of rod-like nuclei, almost independently of the nuclear models and of the degree of the neutrino degeneracy.

  20. Morphology and crystal phase evolution of GeO 2 in liquid phase deposition process

    NASA Astrophysics Data System (ADS)

    Jing, Chengbin; Sun, Wei; Wang, Wei; Li, Yi; Chu, Junhao

    2012-01-01

    Morphology and crystal phase evolution of GeO 2 in liquid phase deposition (LPD) process is investigated. Rod-like solid phases precipitate out of solution ahead of truncated cube-like phases. SEM, XRD and TEM analyses reveal that the two sorts of solid phases are tetragonal GeO 2 and hexagonal GeO 2, respectively. The tetragonal GeO 2 phases start to experience a re-dissolving process as soon as the hexagonal phases come into being. The prior precipitation of the rod-like phase arises from a relatively low solute saturation of tetragonal GeO 2. Fast growth of a tetragonal GeO 2 phase along [111] direction leads to development of a rod-like shape. The re-dissolving phenomenon does not agree with the classic growth kinetics of crystals but is strongly favored by our calculations based on thermodynamics. The GeO 2 solutes are released in a fluctuant way by germanate ions, which promotes the occurrence of the re-dissolution phenomenon. The current researches open a door for room-temperature LPD growth of not only the hexagonal GeO 2 particles and film but also the one-dimensional tetragonal GeO 2 product.

  1. Controlled Isotropic and Anisotropic Shell Growth in β-NaLnF4 Nanocrystals Induced by Precursor Injection Rate.

    PubMed

    Fischer, Stefan; Swabeck, Joseph K; Alivisatos, A Paul

    2017-09-06

    Precise morphology and composition control is vital for designing multifunctional lanthanide-doped core/shell nanocrystals. Herein, we report controlled isotropic and anisotropic shell growth techniques in hexagonal sodium rare-earth tetrafluoride (β-NaLnF4) nanocrystals by exploiting the kinetics of the shell growth. A drastic change of the shell morphology was observed by changing the injection rate of the shell precursors while keeping all other reaction conditions constant. We obtained isotropic shell growth for fast sequential injection and a preferred growth of the shell layers along the crystal's c-axis [001] for slow dropwise injection. Using this slow shell growth technique, we have grown rod-like shells around different almost spherical core nanocrystals. Bright and efficient upconversion was measured for both isotropic and rod-like shells around β-NaYF4 nanocrystals doped with Yb(3+)/Er(3+) and Yb(3+)/Tm(3+). Photoluminescence upconversion quantum yield and lifetime measurements reveal the high quality of the core/shell nanocrystal. Furthermore, multishell rod-like nanostructures have been prepared with optically active cores and tips separated by an inert intermediate shell layer. The controlled anisotropic shell growth allows the design of new core/multishell nanostructures and enables independent investigations of the chemistry and physics of different nanocrystal facets.

  2. Mesoscale Simulation of Asphaltene Aggregation.

    PubMed

    Wang, Jiang; Ferguson, Andrew L

    2016-08-18

    Asphaltenes constitute a heavy aromatic crude oil fraction with a propensity to aggregate and precipitate out of solution during petroleum processing. Aggregation is thought to proceed according to the Yen-Mullins hierarchy, but the molecular mechanisms underlying mesoscopic assembly remain poorly understood. By combining coarse-grained molecular models parametrized using all-atom data with high-performance GPU hardware, we have performed molecular dynamics simulations of the aggregation of hundreds of asphaltenes over microsecond time scales. Our simulations reveal a hierarchical self-assembly mechanism consistent with the Yen-Mullins model, but the details are sensitive and depend on asphaltene chemistry and environment. At low concentrations asphaltenes exist predominantly as dispersed monomers. Upon increasing concentration, we first observe parallel stacking into 1D rod-like nanoaggregates, followed by the formation of clusters of nanoaggregates associated by offset, T-shaped, and edge-edge stacking. Asphaltenes possessing long aliphatic side chains cannot form nanoaggregate clusters due to steric repulsions between their aliphatic coronae. At very high concentrations, we observe a porous percolating network of rod-like nanoaggregates suspended in a sea of interpenetrating aliphatic side chains with a fractal dimension of ∼2. The lifetime of the rod-like aggregates is described by an exponential distribution reflecting a dynamic equilibrium between coagulation and fragmentation.

  3. De novo morphogenesis in L-forms via geometric control of cell growth

    PubMed Central

    Billings, Gabriel; Ouzounov, Nikolay; Ursell, Tristan; Desmarais, Samantha M.; Shaevitz, Joshua; Gitai, Zemer; Huang, Kerwyn Casey

    2015-01-01

    Summary In virtually all bacteria, the cell wall is crucial for mechanical integrity and for determining cell shape. Escherichia coli’s rod-like shape is maintained via the spatiotemporal patterning of cell-wall synthesis by the actin homologue MreB. Here, we transiently inhibited cell-wall synthesis in E. coli to generate cell-wall-deficient, spherical L-forms, and found that they robustly reverted to a rod-like shape within several generations after inhibition cessation. The chemical composition of the cell wall remained essentially unchanged during this process, as indicated by liquid chromatography. Throughout reversion, MreB localized to inwardly curved regions of the cell, and fluorescent cell wall labelling revealed that MreB targets synthesistothose regions. When exposed to the MreB inhibitor A22, reverting cells regrew a cell wall but failed to recover a rod-like shape. Our results suggest that MreB provides the geometric measure that allows E. coli to actively establish and regulate its morphology. PMID:24995493

  4. In situ synthesis carbonated hydroxyapatite layers on enamel slices with acidic amino acids by a novel two-step method.

    PubMed

    Wu, Xiaoguang; Zhao, Xu; Li, Yi; Yang, Tao; Yan, Xiujuan; Wang, Ke

    2015-09-01

    In situ fabrication of carbonated hydroxyapatite (CHA) remineralization layer on an enamel slice was completed in a novel, biomimetic two-step method. First, a CaCO3 layer was synthesized on the surface of demineralized enamel using an acidic amino acid (aspartic acid or glutamate acid) as a soft template. Second, at the same concentration of the acidic amino acid, rod-like carbonated hydroxyapatite was produced with the CaCO3 layer as a sacrificial template and a reactant. The morphology, crystallinity and other physicochemical properties of the crystals were characterized using field emission scanning electron microscopy (FESEM), Fourier transform infrared spectrometry (FTIR), X-ray diffraction (XRD) and energy-dispersive X-ray analysis (EDAX), respectively. Acidic amino acid could promote the uniform deposition of hydroxyapatite with rod-like crystals via absorption of phosphate and carbonate ions from the reaction solution. Moreover, compared with hydroxyapatite crystals coated on the enamel when synthesized by a one-step method, the CaCO3 coating that was synthesized in the first step acted as an active bridge layer and sacrificial template. It played a vital role in orienting the artificial coating layer through the template effect. The results show that the rod-like carbonated hydroxyapatite crystals grow into bundles, which are similar in size and appearance to prisms in human enamel, when using the two-step method with either aspartic acid or acidic glutamate (20.00 mmol/L).

  5. Morphological Effect of Non-targeted Biomolecule-Modified MNPs on Reticuloendothelial System.

    PubMed

    Li, Xiao; Hu, Yan; Xiao, Jie; Cheng, Dengfeng; Xiu, Yan; Shi, Hongcheng

    2015-12-01

    Magnetic nanoparticles (MNPs) with special morphology were commonly used as biomaterials, while morphological effects of non-targeted biomolecule-modified MNPs on biological behaviors were still unclear. In this research, spherical and rod-like Fe3O4 in a comparable size were synthesized and then surface-modified by bovine serum albumin (BSA) as a model of non-targeted biomolecule-modified MNPs. Morphological effects were featured by TEM and quantification of in vitro phagocytic uptake, as well as the in vivo quantification of particles in reticuloendothelial system (RES)-related organs of normal Kunming mice. For these non-targeted BSA-modified MNPs, intracellular distributions were the same, but the rod-like MNPs were more likely to be uptake by macrophages; furthermore, the BSA-modified MNPs gathered in RES-related organs soon after intravenous injection, but the rod-like ones were expelled from the lung more quickly and expelled from the spleen more slowly. These preliminary results may be referable if MNPs or other similar biomolecule-modified nanoparticles were used.

  6. Liquid crystalline phase transitions in virus and virus/polymer suspensions

    NASA Astrophysics Data System (ADS)

    Dogic, Zvonimir

    Using experimental, theoretical, and simulation methods, we investigate the relationship between the intermolecular interactions of rod-like colloids and the resulting liquid crystalline phase diagrams. As a model system of rod-like particles we use bacteriophage fd, which is a charge stabilized colloid. We are able to engineer complex attractive and repulsive intermolecular interactions by changing the ionic strengths of the suspensions, attaching covalently bound polymers and adding nonadsorbing polymers. Using standard molecular cloning techniques it is also shown that the aspect ratio of the rod-like particle can be manipulated. In the limit of high ionic strength the fd virus quantitatively agrees with the Onsager theory for the isotropic-nematic (I-N) phase transition in hard rods. The role of attractive interaction on the nature of the I-N phase transition is investigated. As the strength of the attraction is increased we observe isotropic-smectic (I-S) phase transitions. Using an optical microscope we follow the kinetics of the I-S phase transition and observe a wide range of novel structures of unexpected complexity. We also investigate the influence of adding hard spheres, or polymers on the nematic-smectic phase transition. We conclude that adding small spheres stabilizes the smectic phase and destabilizes the nematic phase.

  7. Fluidization of spherocylindrical particles

    NASA Astrophysics Data System (ADS)

    Mahajan, Vinay V.; Nijssen, Tim M. J.; Fitzgerald, Barry W.; Hofman, Jeroen; Kuipers, Hans; Padding, Johan T.

    2017-06-01

    Multiphase (gas-solid) flows are encountered in numerous industrial applications such as pharmaceutical, food, agricultural processing and energy generation. A coupled computational fluid dynamics (CFD) and discrete element method (DEM) approach is a popular way to study such flows at a particle scale. However, most of these studies deal with spherical particles while in reality, the particles are rarely spherical. The particle shape can have significant effect on hydrodynamics in a fluidized bed. Moreover, most studies in literature use inaccurate drag laws because accurate laws are not readily available. The drag force acting on a non-spherical particle can vary considerably with particle shape, orientation with the flow, Reynolds number and packing fraction. In this work, the CFD-DEM approach is extended to model a laboratory scale fluidized bed of spherocylinder (rod-like) particles. These rod-like particles can be classified as Geldart D particles and have an aspect ratio of 4. Experiments are performed to study the particle flow behavior in a quasi-2D fluidized bed. Numerically obtained results for pressure drop and bed height are compared with experiments. The capability of CFD-DEM approach to efficiently describe the global bed dynamics for fluidized bed of rod-like particles is demonstrated.

  8. Bismaleimides and related maleimido polymers as matrix resins

    NASA Technical Reports Server (NTRS)

    Parker, J. A.; Kourtides, D. A.; Fohlen, G. M.

    1985-01-01

    Significant processing and property improvements can be achieved by copolymerization of state-of-the-art bisimides with various vinyl stilbazole derivatives to give both fire resistance and high-temperature properties from hot-melt compositions. Significant improvement in mechanical properties is achieved through these modifications, which may make these new matrix resins ideal candidates for fireworthy secondary graphite composite structures. Phosphorous modifications of maleimido polymers through phosphonate structure and tricyclophosphazene derivatives provide families of new matrix resins for short-time applications in severe thermo-oxidative environments. With further research these may provide matrix resins for long-term thermo-oxidative stability of advanced composites at temperatures up to 400 to 500 C.

  9. Photoconductive Cathode Interlayer for Highly Efficient Inverted Polymer Solar Cells.

    PubMed

    Nian, Li; Zhang, Wenqiang; Zhu, Na; Liu, Linlin; Xie, Zengqi; Wu, Hongbin; Würthner, Frank; Ma, Yuguang

    2015-06-10

    A highly photoconductive cathode interlayer was achieved by doping a 1 wt % light absorber, such as perylene bisimide, into a ZnO thin film, which absorbs a very small amount of light but shows highly increased conductivity of 4.50 × 10(-3) S/m under sunlight. Photovoltaic devices based on this kind of photoactive cathode interlayer exhibit significantly improved device performance, which is rather insensitive to the thickness of the cathode interlayer over a broad range. Moreover, a power conversion efficiency as high as 10.5% was obtained by incorporation of our photoconductive cathode interlayer with the PTB7-Th:PC71BM active layer, which is one of the best results for single-junction polymer solar cells.

  10. Triplet formation by charge recombination in thin film blends of perylene red and pyrene: developing a target model for the photophysics of organic photovoltaic materials.

    PubMed

    Williams, René M; Vân Anh, Nguyễn; van Stokkum, Ivo H M

    2013-09-26

    Photoinduced charge separation in a mixture of Perylene Red (N,N'-bis(2,6-di-isopropylphenyl)-1,6,7,12-tetraphenoxyperylene-3,4:9,10-tetracarboxylic acid bis-imide) and pyrene, organized in thin solid film on quartz, was studied by means of steady-state absorption and emission spectroscopy and by femtosecond transient absorption spectroscopy. Steady state spectroscopy shows substantial interaction between the two chromophores in the ground and excited states. Luminescence quenching indicates charge transfer interaction. Global and target analysis of the transient absorption data indicates a complex photophysical behavior with the formation of long-lived charges (free charge carriers) and of a triplet excited state species (with rates of ∼10.4 × 10(9) and 72.1 × 10(6) s(-1)) via charge recombination pathways from charged states. A generally applicable target model for the analysis of photophysical data of photovoltaic blends is developed.

  11. Noncovalent functionalization and charge transfer in antimonene.

    PubMed

    Abellán, Gonzalo; Ares, Pablo; Wild, Stefan; Nuin, Edurne; Neiss, Christian; Rodriguez-San Miguel, David; Segovia, Pilar; Gibaja, Carlos; Michel, Enrique G; Görling, Andreas; Hauke, Frank; Gómez-Herrero, Julio; Hirsch, Andreas; Zamora, Félix

    2017-09-25

    Antimonene, a novel group-15 2D material, is functionalized with a tailor-made perylene bisimide through strong van-der-Waals interactions. The functionalization process leads to a dramatic quenching of the perylene fluorescence, which surpasses that observed for graphene or black phosphorus, allowing a straightforward characterization of the flakes by scanning Raman microscopy. Furthermore, scanning photoelectron microscopy studies and theoretical calculations reveal a remarkable charge transfer behavior, being twice that of black phosphorus. Moreover, the excellent stability under environmental conditions of pristine antimonene has been tackled, pointing towards the spontaneous formation of a sub-nanometric oxide passivation layer. DFT calculations revealed that the noncovalent functionalization of antimonene results in a charge transfer band gap of 1.1 eV. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Deliberate Switching of Single Photochromic Triads

    NASA Astrophysics Data System (ADS)

    Maier, Johannes; Pärs, Martti; Weller, Tina; Thelakkat, Mukundan; Köhler, Jürgen

    2017-01-01

    Photochromic molecules can be reversibly converted between two bistable conformations by light, and are considered as promising building blocks in novel macromolecular structures for sensing and imaging techniques. We have studied individual molecular triads consisting of two strong fluorophores (perylene bisimide) that are covalently linked via a photochromic unit (dithienylcyclopentene) and distinguished between deliberate switching and spontaneous blinking. It was verified that the probability for observing deliberate light-induced switching of a single triad (rather than stochastic blinking) amounts to 0.8 ± 0.1. In a few exceptional cases this probability can exceed 0.95. These numbers are sufficiently large for application in sensitive biosensing, and super-resolution imaging. This opens the possibility to develop devices that can be controlled by an external optical stimulus on a truly molecular length scale.

  13. Deliberate Switching of Single Photochromic Triads

    PubMed Central

    Maier, Johannes; Pärs, Martti; Weller, Tina; Thelakkat, Mukundan; Köhler, Jürgen

    2017-01-01

    Photochromic molecules can be reversibly converted between two bistable conformations by light, and are considered as promising building blocks in novel macromolecular structures for sensing and imaging techniques. We have studied individual molecular triads consisting of two strong fluorophores (perylene bisimide) that are covalently linked via a photochromic unit (dithienylcyclopentene) and distinguished between deliberate switching and spontaneous blinking. It was verified that the probability for observing deliberate light-induced switching of a single triad (rather than stochastic blinking) amounts to 0.8 ± 0.1. In a few exceptional cases this probability can exceed 0.95. These numbers are sufficiently large for application in sensitive biosensing, and super-resolution imaging. This opens the possibility to develop devices that can be controlled by an external optical stimulus on a truly molecular length scale. PMID:28139764

  14. Deliberate Switching of Single Photochromic Triads.

    PubMed

    Maier, Johannes; Pärs, Martti; Weller, Tina; Thelakkat, Mukundan; Köhler, Jürgen

    2017-01-31

    Photochromic molecules can be reversibly converted between two bistable conformations by light, and are considered as promising building blocks in novel macromolecular structures for sensing and imaging techniques. We have studied individual molecular triads consisting of two strong fluorophores (perylene bisimide) that are covalently linked via a photochromic unit (dithienylcyclopentene) and distinguished between deliberate switching and spontaneous blinking. It was verified that the probability for observing deliberate light-induced switching of a single triad (rather than stochastic blinking) amounts to 0.8 ± 0.1. In a few exceptional cases this probability can exceed 0.95. These numbers are sufficiently large for application in sensitive biosensing, and super-resolution imaging. This opens the possibility to develop devices that can be controlled by an external optical stimulus on a truly molecular length scale.

  15. Fire and heat resistant laminating resins based on maleimido and citraconimido substituted 1-(diorgano oxyphosphonyl) methyl -2,4- and -2,6- diaminobenzenes

    NASA Technical Reports Server (NTRS)

    Mikroyannidis, John A. (Inventor); Kourtides, Demetrius A. (Inventor)

    1987-01-01

    A class of fire and heat resistant bisimide resins prepared by thermal polymerization of maleimido or citraconimido substituted 1-((dialkoxyphosphonyl) methyl)-2-4 and -2,6-diaminobenzenes are described. The polymer precursors are prepared by reacting 1-((diorganooxyphosphonyl) methyl)-2-4 and -2,6-diaminobenzenes with maleic anhydride or citraconic anhydride in a mole ratio 1:2. Chain extension of the monomers is achieved by reacting the mono-N-maleimido derivatives of 1-((diorganooxyphosphonyl) methyl)-2,4 and -2,6-diaminobenzenes with aryl tetracarboxylic dianhydrides, such as benzophenone tetracarbocylic dianhydride, or aryl diisocyanates, such as methylenebis (4-phenylisocyanate), in a mole ratio 2:1. The polymerization of the monomers is studied by differential scanning calorimetry (DSC) and the thermal stability of the polymers is ascertained by thermogravimetric analysis (TGA).

  16. Non-Fullerene-Acceptor-Based Bulk-Heterojunction Organic Solar Cells with Efficiency over 7.

    PubMed

    Sun, Dan; Meng, Dong; Cai, Yunhao; Fan, Bingbing; Li, Yan; Jiang, Wei; Huo, Lijun; Sun, Yanming; Wang, Zhaohui

    2015-09-02

    A novel perylene bisimide (PBI) dimer-based acceptor material, SdiPBI-S, was developed. Conventional bulk-heterojunction (BHJ) solar cells based on SdiPBI-S and the wide-band-gap polymer PDBT-T1 show a high power conversion efficiency (PCE) of 7.16% with a high open-circuit voltage of 0.90 V, a high short-circuit current density of 11.98 mA/cm(2), and an impressive fill factor of 66.1%. Favorable phase separation and balanced carrier mobilites in the BHJ films account for the high photovoltaic performance. The results demonstrate that fine-tuning of PBI-based materials is a promising way to improve the PCEs of non-fullerene BHJ organic solar cells.

  17. Rigid Nonfullerene Acceptors Based on Triptycene-Perylene Dye for Organic Solar Cells.

    PubMed

    Meng, Dong; Fu, Huiting; Fan, Bingbing; Zhang, Jianqi; Li, Yan; Sun, Yanming; Wang, Zhaohui

    2017-06-19

    Three kinds of nonconjugated rigid perylene bisimide (PBI) derivatives based on a triptycene core were designed, synthesized and characterized. The unique three-dimensional (3D) conformation of triptycene could enable formation of polymer with the favorable morphology for organic polymer solar cells (PSCs) by relieving the self-aggregation of rigid PBI units. The low-lying LUMO energy levels of these compounds demonstrated that they are very suitable for use as acceptors in organic solar cells. A higher power conversion efficiency (PCE) of 6.15 % was obtained for the blend film using the compound with two PBI units (T-2) as the acceptor and commercial poly[[4,8-bis[5-(2-ethylhexyl)thiophene-2-yl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)-carbonyl]thieno[3,4-b]thiophenediyl

  18. Azomethine diimides end-capped with anthracene moieties: Experimental and theoretical investigations

    NASA Astrophysics Data System (ADS)

    Schab-Balcerzak, Ewa; Grucela, Marzena; Malecki, Grzegorz; Kotowicz, Sonia; Siwy, Mariola; Janeczek, Henryk; Golba, Sylwia; Praski, Aleksander

    2017-01-01

    New arylene bisimide derivatives containing imine linkages and anthracene units were synthesized. Azomethine diimides were prepared via condensation reaction of 9-anthracenecarboxaldehyde and diamines with phthalic diimide or naphthalene diimide core and Schiff base linkers. They were characterized by FTIR spectroscopy, elemental analysis and mass spectrometry (MALDI-TOF-MS). The synthesized compounds exhibited high resistance against thermal decomposition up to 400 °C. Investigated compounds are electrochemically active and undergo reversible electrochemical reduction and irreversible oxidation processes as was found in cyclic voltammetry studies. The photoluminescence measurements of synthesized compounds in solid state as thin film on glass substrate revealed their ability to emission of the blue light with quantum yield efficiency about 2%. The electronic structure and spectroscopic properties of prepared azomethine diimides were also calculated by the density functional theory (DFT). The electrical properties of the diimide derivatives were preliminary investigated by current-voltage measurements.

  19. Glyconanosomes: disk-shaped nanomaterials for the water solubilization and delivery of hydrophobic molecules.

    PubMed

    Assali, Mohyeddin; Cid, Juan-José; Pernía-Leal, Manuel; Muñoz-Bravo, Miguel; Fernández, Inmaculada; Wellinger, Ralf E; Khiar, Noureddine

    2013-03-26

    Herein, we describe the first report on a new class of disk-shaped and quite monodisperse water-soluble nanomaterials that we named glyconanosomes (GNS). GNSs were obtained by sliding out the cylindrical structures formed upon self-organization and photopolymerization of glycolipid 1 on single-walled carbon nanotube (SWCNT) sidewalls. GNSs present a sheltered hydrophobic inner cavity formed by the carbonated tails, surrounded by PEG and lactose moieties. The amphiphilic character of GNSs allows the water solubility of insoluble hydrophobic cargos such as a perylene-bisimide derivative, [60]fullerene, or the anti-carcinogenic drug camptothecin (CPT). GNS/C60 inclusion complexes are able to establish specific interactions between peanut agglutinin (PNA) lectin and the lactose moiety surrounding the complexes, while CPT solubilized by GNS shows higher cytotoxicity toward MCF7-type breast cancer cells than CPT alone. Thus, GNS represents an attractive extension of nanoparticle-based drug delivery systems.

  20. Fire and heat resistant laminating resins based on malemeido and citraconimido substituted 1 -2,4- and -2,6- diaminobenzenes

    NASA Technical Reports Server (NTRS)

    Mikroyannidis, John A.; Kourtides, Demetrius A. (Inventor)

    1987-01-01

    A novel class of fire and heat resistant bisimide resins prepared by thermal polymerization of maleimido or citraconimido substituted 1-(dialkox phosphonyl) methyl-2-4 and -2,6-diamino benzenes was presented. The polymer precursors are prepared by reacting 1-(diorgano oxyphosphonyl) methyl-2-4- and -2,6-diamino benzenes with maliec anhydride or citraconic anhydride in a mole ratio 1:2. Chain extension of the monomers is achieved by reacting the mono-N-maleimido derivaties of 1 (diorgano oxyphosphonyl) methyl -2,4- and -2,6-diamino benzenes with aryl tetracarboxylic dianhydrides, such as benzophenone tetracarboxylic dianhydride, or aryl diisocyanates, such as methylene bis(4-phenyl isocyanate), in a mole ratio 2:1. The polymerization of the monomers is studied by diferential scanning calorimetry and the thermal stability of the polymers is ascertained by thermogravimetric analysis.

  1. Adsorption and desorption behavior of asphaltene on polymer-brush-immobilized surfaces.

    PubMed

    Higaki, Yuji; Hatae, Kaoru; Ishikawa, Tatsuya; Takanohashi, Toshimasa; Hayashi, Jun-ichiro; Takahara, Atsushi

    2014-11-26

    The adsorption behavior of a model compound for surface-active component of asphaltenes, N-(1-hexylheptyl)-N'-(12-carboxylicdodecyl) perylene-3,4,9,10-tetracarboxylic bisimide (C5Pe), and detachment behavior of asphaltene deposit films for high-density polymer brushes were investigated. Zwitterionic poly(3-(N-2-methacryloyloxyethyl-N,N-dimethyl)ammonatopropanesulfonate (PMAPS) brushes and hydrophobic poly(n-hexyl methacrylate) (PHMA) brushes exhibit less C5Pe adsorption than poly(methyl methacrylate) (PMMA). The asphaltene deposit films on the PHMA brush detached in a model oil (toluene/n-heptane=1/4 (v/v)), and the asphaltene films on the PMAPS brush detached in water. The antifouling character was explained by the interface free energy for the polymer-brush/asphaltenes (γSA) and polymer-brush/toluene (γSO).

  2. Delayed cure bismaleimide resins

    DOEpatents

    Adams, Johnnie E.; Jamieson, Donald R.

    1984-08-07

    Polybismaleimides prepared by delayed curing of bis-imides having the formula ##STR1## wherein R.sub.1 and R.sub.2 each independently is H, C.sub.1-4 -alkyl, C.sub.1-4 -alkoxy, Cl or Br, or R.sub.1 and R.sub.2 together form a fused 6-membered hydrocarbon aromatic ring, with the proviso that R.sub.1 and R.sub.2 are not t-butyl or t-butoxy; X is O, S or Se; n is 1-3; and the --(CH.sub.2).sub.n -- group, optionally, is substituted by 1-3 methyl groups or by fluorine.

  3. Structure, morphology, and assembly behavior of kafirin

    DOE PAGES

    Xiao, Jie; Li, Yunqi; Li, Ji; ...

    2014-12-15

    Prolamins from grains have attracted intensive attention in recent years due to their potential in satisfying the demand for environmentally friendly (biodegradable), abundantly available (sustainable), and cost-effective biomaterials. However, for kafirin, the prolamin from sorghum, its composition, structure, morphology, and self-assembly behaviors have not been fully characterized. In this paper, kafirin was extracted from the whole sorghum grain and found to contain 68, 14, 6, and 12% of α-, β-, and γ-fractions and cross-linked kafirin, respectively. Freeze-dried kafirin contained ~49% α-helix in the solid state. When dissolved in 65% (v/v) isopropanol, 60% (v/v) tert-butanol, and 85% (v/v) ethanol aqueous solvents,more » the relative α-helix content in kafirin increased with the decrease of solvent polarity. Structural analysis using small-angle X-ray scattering (SAXS) indicated that kafirin (2 mg/mL) took stretched and extended conformations with dimensions of 118 × 15 × 15 and 100 × 11 × 11 Å in 60% tert-butanol and 65% isopropanol, respectively. More elongated conformation of individual kafirin with high-order assembly was observed in 85% ethanol. Protein aggregation occurred as protein concentration increased in its good solvent. The morphology of kafirin assemblies captured by atomic force microscopy (AFM) revealed that kafirin protein took uniform particle morphology at low concentration, and disk-like or rod-like structures resulting from solvent evaporation induced particle interactions emerged at high concentrations. Lastly, these results suggest that both protein concentration and solvent polarity can effectively regulate kafirin assemblies from thick rod-like to slim rod-like structures, a convenient way to tune the fibrillation of prolamin-based biomaterials.« less

  4. Structure, morphology, and assembly behavior of kafirin

    SciTech Connect

    Xiao, Jie; Li, Yunqi; Li, Ji; Gonzalez, Alejandro Perez; Xia, Qiuyang; Huang, Qingrong

    2014-12-15

    Prolamins from grains have attracted intensive attention in recent years due to their potential in satisfying the demand for environmentally friendly (biodegradable), abundantly available (sustainable), and cost-effective biomaterials. However, for kafirin, the prolamin from sorghum, its composition, structure, morphology, and self-assembly behaviors have not been fully characterized. In this paper, kafirin was extracted from the whole sorghum grain and found to contain 68, 14, 6, and 12% of α-, β-, and γ-fractions and cross-linked kafirin, respectively. Freeze-dried kafirin contained ~49% α-helix in the solid state. When dissolved in 65% (v/v) isopropanol, 60% (v/v) tert-butanol, and 85% (v/v) ethanol aqueous solvents, the relative α-helix content in kafirin increased with the decrease of solvent polarity. Structural analysis using small-angle X-ray scattering (SAXS) indicated that kafirin (2 mg/mL) took stretched and extended conformations with dimensions of 118 × 15 × 15 and 100 × 11 × 11 Å in 60% tert-butanol and 65% isopropanol, respectively. More elongated conformation of individual kafirin with high-order assembly was observed in 85% ethanol. Protein aggregation occurred as protein concentration increased in its good solvent. The morphology of kafirin assemblies captured by atomic force microscopy (AFM) revealed that kafirin protein took uniform particle morphology at low concentration, and disk-like or rod-like structures resulting from solvent evaporation induced particle interactions emerged at high concentrations. Lastly, these results suggest that both protein concentration and solvent polarity can effectively regulate kafirin assemblies from thick rod-like to slim rod-like structures, a convenient way to tune the fibrillation of prolamin-based biomaterials.

  5. Effects of trabecular type and orientation on microdamage susceptibility in trabecular bone.

    PubMed

    Shi, Xiutao; Liu, X Sherry; Wang, Xiang; Guo, X Edward; Niebur, Glen L

    2010-05-01

    Trabecular architecture becomes more rod-like and anisotropic in osteoporotic and aging trabecular bone. In order to address the effects of trabecular type and orientation on trabecular bone damage mechanics, microstructural finite element modeling was used to identify the yielded tissue in ten bovine tibial trabecular bone samples compressed to 1.2% on-axis apparent strain. The yielded tissue was mapped onto individual trabeculae identified by an Individual Trabeculae Segmentation (ITS) technique, and the distribution of the predicted yielding among trabecular types and orientations was compared to the experimentally measured microdamage. Although most of the predicted yielded tissue was found in longitudinal plates (73+/-11%), the measured microcrack density was positively correlated with the proportion of the yielded tissue in longitudinal rods (R(2)=0.52, p=0.02), but not in rods of other directions or plates. The overall fraction of rods and the fractions of rods along the longitudinal and transverse axes were also correlated with the measured microcrack density. In contrast, diffuse damage area did not correlate with any of these quantities. These results agree with the findings that both in vitro and in vivo microcrack densities are correlated with Structure Model Index (SMI), and are also consistent with decreased energy to failure in more rod-like trabecular bone. Together the results suggest that bending or buckling deformations of rod-like trabeculae may make trabecular structures more susceptible to microdamage formation. Moreover, while simple strain-based tissue yield criteria may account for macroscopic yielding, they may not be suitable for identifying damage.

  6. Manganese oxides with rod-, wire-, tube-, and flower-like morphologies: highly effective catalysts for the removal of toluene.

    PubMed

    Wang, Fang; Dai, Hongxing; Deng, Jiguang; Bai, Guangmei; Ji, Kemeng; Liu, Yuxi

    2012-04-03

    Nanosized rod-like, wire-like, and tubular α-MnO(2) and flower-like spherical Mn(2)O(3) have been prepared via the hydrothermal method and the CCl(4) solution method, respectively. The physicochemical properties of the materials were characterized using numerous analytical techniques. The catalytic activities of the catalysts were evaluated for toluene oxidation. It is shown that α-MnO(2) nanorods, nanowires, and nanotubes with a surface area of 45-83 m(2)/g were tetragonal in crystal structure, whereas flower-like spherical Mn(2)O(3) with a surface area of 162 m(2)/g was of cubic crystal structure. There were the presence of surface Mn ions in multiple oxidation states (e.g., Mn(3+), Mn(4+), or even Mn(2+)) and the formation of surface oxygen vacancies. The oxygen adspecies concentration and low-temperature reducibility decreased in the order of rod-like α-MnO(2) > tube-like α-MnO(2) > flower-like Mn(2)O(3) > wire-like α-MnO(2), in good agreement with the sequence of the catalytic performance of these samples. The best-performing rod-like α-MnO(2) catalyst could effectively catalyze the total oxidation of toluene at lower temperatures (T(50%) = 210 °C and T(90%) = 225 °C at space velocity = 20,000 mL/(g h)). It is concluded that the excellent catalytic performance of α-MnO(2) nanorods might be associated with the high oxygen adspecies concentration and good low-temperature reducibility. We are sure that such one-dimensional well-defined morphological manganese oxides are promising materials for the catalytic elimination of air pollutants.

  7. Structure, Morphology, and Assembly Behavior of Kafirin

    PubMed Central

    2015-01-01

    Prolamins from grains have attracted intensive attention in recent years due to their potential in satisfying the demand for environmentally friendly (biodegradable), abundantly available (sustainable), and cost-effective biomaterials. However, for kafirin, the prolamin from sorghum, its composition, structure, morphology, and self-assembly behaviors have not been fully characterized. In this paper, kafirin was extracted from the whole sorghum grain and found to contain 68, 14, 6, and 12% of α-, β-, and γ-fractions and cross-linked kafirin, respectively. Freeze-dried kafirin contained ∼49% α-helix in the solid state. When dissolved in 65% (v/v) isopropanol, 60% (v/v) tert-butanol, and 85% (v/v) ethanol aqueous solvents, the relative α-helix content in kafirin increased with the decrease of solvent polarity. Structural analysis using small-angle X-ray scattering (SAXS) indicated that kafirin (2 mg/mL) took stretched and extended conformations with dimensions of 118 × 15 × 15 and 100 × 11 × 11 Å in 60% tert-butanol and 65% isopropanol, respectively. More elongated conformation of individual kafirin with high-order assembly was observed in 85% ethanol. Protein aggregation occurred as protein concentration increased in its good solvent. The morphology of kafirin assemblies captured by atomic force microscopy (AFM) revealed that kafirin protein took uniform particle morphology at low concentration, and disk-like or rod-like structures resulting from solvent evaporation induced particle interactions emerged at high concentrations. These results suggest that both protein concentration and solvent polarity can effectively regulate kafirin assemblies from thick rod-like to slim rod-like structures, a convenient way to tune the fibrillation of prolamin-based biomaterials. PMID:25510968

  8. Structure, Morphology, and Assembly Behavior of Kafirin

    SciTech Connect

    Xiao, Jie; Li, Yunqi; Li, Ji; Gonzalez, Alejandro Perez; Xia, Qiuyang; Huang, Qingrong

    2015-01-14

    Prolamins from grains have attracted intensive attention in recent years due to their potential in satisfying the demand for environmentally friendly (biodegradable), abundantly available (sustainable), and cost-effective biomaterials. However, for kafirin, the prolamin from sorghum, its composition, structure, morphology, and self-assembly behaviors have not been fully characterized. In this paper, kafirin was extracted from the whole sorghum grain and found to contain 68, 14, 6, and 12% of α-, β-, and γ-fractions and cross-linked kafirin, respectively. Freeze-dried kafirin contained ~49% α-helix in the solid state. When dissolved in 65% (v/v) isopropanol, 60% (v/v) tert-butanol, and 85% (v/v) ethanol aqueous solvents, the relative α-helix content in kafirin increased with the decrease of solvent polarity. Structural analysis using small-angle X-ray scattering (SAXS) indicated that kafirin (2 mg/mL) took stretched and extended conformations with dimensions of 118 × 15 × 15 and 100 × 11 × 11 Å in 60% tert-butanol and 65% isopropanol, respectively. More elongated conformation of individual kafirin with high-order assembly was observed in 85% ethanol. Protein aggregation occurred as protein concentration increased in its good solvent. The morphology of kafirin assemblies captured by atomic force microscopy (AFM) revealed that kafirin protein took uniform particle morphology at low concentration, and disk-like or rod-like structures resulting from solvent evaporation induced particle interactions emerged at high concentrations. These results suggest that both protein concentration and solvent polarity can effectively regulate kafirin assemblies from thick rod-like to slim rod-like structures, a convenient way to tune the fibrillation of prolamin-based biomaterials.

  9. Meso/macroporous {gamma}-Al{sub 2}O{sub 3} fabricated by thermal decomposition of nanorods ammonium aluminium carbonate hydroxide

    SciTech Connect

    Li, Guang-Ci; Liu, Yun-Qi; Guan, Li-Li; Hu, Xiao-Fu; Liu, Chen-Guang

    2012-04-15

    Highlights: Black-Right-Pointing-Pointer Rod-like AACH were synthesized by a hydrothermal treatment. Black-Right-Pointing-Pointer AACH was formed via a Al(OH){sub 3} {yields} (NH{sub 4}){sub 2}Al{sub 6}(CO{sub 3}){sub 3}(OH){sub 14}{center_dot}xH{sub 2}O {yields} NH{sub 4}Al(OH){sub 2}CO{sub 3}{center_dot}H{sub 2}O {yields} NH{sub 4}Al(OH){sub 2}CO{sub 3} path. Black-Right-Pointing-Pointer Alumina derived from AACH has a good thermal stability. Black-Right-Pointing-Pointer The obtained alumina possesses large pore volume and bimodal porosity. -- Abstract: Through exploring the reaction parameters during the synthesis of the AACH, rod-like ammonium aluminium carbonate hydroxide (AACH) with high crystallinity has been successfully prepared via a facile hydrothermal method. The synthesis parameters like time, the molar ratio of NH{sub 4}HCO{sub 3}/Al and the properties of starting materials were systematically investigated. The structure was characterized using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), IR and transmission electron microscopy (TEM). The experimental results display that the obtained {gamma}-Al{sub 2}O{sub 3} materials possess meso/macroporosity and large pore volume, which are mainly attributed to the removal of gas molecules during the decomposition of AACH. Moreover, using the rod-like AACH as precursor, {gamma}-Al{sub 2}O{sub 3} nanorods were obtained via a low-temperature thermal decomposition method.

  10. Shape Transformation Following Reduction-Sensitive PEG Cleavage of Polymer/DNA Nanoparticles

    PubMed Central

    Williford, John-Michael; Ren, Yong; Huang, Kevin; Pan, Deng; Mao, Hai-Quan

    2014-01-01

    PEGylated polycation/DNA micellar nanoparticles have been developed that can undergo shape transformation upon cleavage of the PEG grafts in response to an environmental cue. As a proof-of-principle, DNA nanoparticles with higher PEG grafting density adopting long, worm- and rod-like morphologies, transition to more condensed nanoparticles with spherical and short-rod morphologies upon cleavage of a fraction of the PEG grafts from the copolymer. This shape transformation leads to increased surface charges, correlating with improved transfection efficiency. PMID:25530853

  11. Preparation and characterization of uniform drug particles: dehydrocholic acid.

    PubMed

    Mohamed, Amr Ali; Matijević, Egon

    2012-02-15

    Two methods for the preparation of uniform dispersions of dehydrocholic acid of different morphologies are described. In the first case, the drug was dissolved in acetone and then re-precipitated by adding a non-solvent (either water or an aqueous stabilizer solution), which yielded rod-like particles. In the second procedure, spheres, consisting of small elongated subunits, were obtained by acidification of basic aqueous solutions of the drug. The resulting particles were characterized in terms of their structure and surface charge characteristics.

  12. [The model of resting forms of mycobacteria for testing of drugs for latent forms of tuberculosis].

    PubMed

    Anuchin, A M; Goncharenko, A V; Galon, I V; Demidenok, O I; Kudykina, Iu K; Moĭsenovich, M M; Muliukin, A L; Kaprel'iants, A S

    2010-01-01

    The new model of obtaining of ovoid resting forms Mycobacterium smegmatis, which are morphologically different from vegetative (rod-like) cells, was developed. Ovoid forms were characterized by a drastically decreased level of metabolic activity, an increased stability to heat processing and antibiotics action, and also by prolonged (more than 2 months) storage time preserving colony-forming ability. Obtained resting forms of mycobacteria may be used in test-systems for checking efficiency of new medical agents against latent forms of tuberculosis and determination of role of these of those genes in entering rest state.

  13. A trabecular plate-like phenotype is overrepresented in Chinese-American versus Caucasian women.

    PubMed

    Walker, M D; Shi, S; Russo, J J; Liu, X S; Zhou, B; Zhang, C; Liu, G; McMahon, D J; Bilezikian, J P; Guo, X E

    2014-12-01

    This study used extreme phenotype selection to define two trabecular bone phenotypes in a cohort of Chinese-American and Caucasian women. A trabecular plate-predominant phenotype is more common in Chinese-Americans while the rod-predominant phenotype is more typical of Caucasians. The robustness of these phenotypic associations with respect to lifestyle factors suggests that this trait may have a genetic basis and that these phenotypes can be utilized in future genetic studies. Compared to Caucasians, Chinese-Americans have more plate-like trabecular bone when measured by individual trabecula segmentation (ITS). These findings suggest a phenotypic difference between the races, which may be amenable to genetic analysis. We sought to identify a single ITS plate trait to pursue in genetic studies by conducting an extreme phenotype selection strategy to numerically define two distinct phenotypes-plate-like and rod-like-and determine whether the selected phenotypic associations were independent of lifestyle factors in order to conduct future genetic studies. A previously described cohort of 146 Chinese-American and Caucasian women with high-resolution peripheral quantitative computed tomography imaging and ITS analyses were studied with logistic regression and receiver operator characteristic analyses. The tibial plate-to-rod (TPR) ratio was the best ITS discriminator of race. Using extreme phenotypic selection, two TPR ratio phenotypes were defined numerically: plate-like as a TPR ratio value in the highest quartile (≥1.336) and rod-like as a TPR ratio value in the lowest quartile (≤0.621). Women with a plate-like phenotype were 25.7 times more likely (95 % CI 7.3-90.1) to be Chinese-American than women with rod-like morphology. After controlling for constitutional and lifestyle covariates, women in the highest vs. lowest TPR ratio quartile were 85.0 times more likely (95 % CI 12.7-568.0) to be Chinese-American. Using extreme phenotype selection, we defined a plate

  14. Macromolecule-Induced Clustering of Hard Spheres.

    PubMed

    Chatterjee, Avik Prasun

    2001-06-01

    The connectivity Ornstein-Zernike formalism, together with the polymer reference interaction site model (PRISM), is employed to describe connectivity and network formation in mixtures of spheres and polymers. Results are presented for the percolation of spheres induced by both flexible coil-like and rigid rod-like linear polymers; the Percus-Yevick (PY) approximation is used throughout. Our results are compared with predictions based on the adhesive hard sphere (AHS) model, and correlations with the polymer-mediated second virial coefficient between spheres are discussed. Copyright 2001 Academic Press.

  15. Microwave absorption by nanoresonator vibrations tuned with surface modification

    NASA Astrophysics Data System (ADS)

    Krivosudský, Ondrej; Cifra, Michal

    2016-08-01

    Elucidating the physical and chemical parameters that govern viscous damping of nanoresonator vibrations and their coupling to electromagnetic radiation is important for understanding the behavior of matter at the nanoscale. Here we develop an analytical model of microwave absorption of a longitudinally oscillating and electrically polar rod-like nanoresonator embedded in a viscoelastic fluid. We show that the slip length, which can be tuned via surface modifications, controls the quality factor and coupling of nanoresonator vibration modes to microwave radiation. We demonstrate that the larger slip length brings the sharper frequency response of the nanoresonator vibration and electromagnetic absorption. Our findings contribute to design guidelines of fluid embedded nanoresonator devices.

  16. Numerical study of soap-film flow by nonuniform alternating electric fields

    NASA Astrophysics Data System (ADS)

    Nasiri, M.; Shirsavar, R.; Mollaei, S.; Ramos, A.

    2017-02-01

    Fluid flow of suspended liquid films induced by non-uniform alternating electric fields has been reported. The electric fields were generated by two rod-like electrodes perpendicular to the fluid surface. The observed fluid flow was explained qualitatively by considering a charge induction mechanism, where the electric field actuates on the charge induced on the film surface. In this paper we perform a numerical study of this fluid flow taking into account the charge induction mechanism. The numerical results are compared with experiments and good agreement is found. Finally, we propose the application of the device as a new kind of two dimensional fluid pump.

  17. ELECTROMAGNETIC APPARATUS FOR MOVING A ROD

    DOEpatents

    Young, J.N.

    1958-04-22

    An electromagnetic apparatus for moving a rod-like member in small steps in either direction is described. The invention has particular application in the reactor field where the reactor control rods must be moved only a small distance and where the use of mechanical couplings is impractical due to the high- pressure seals required. A neutron-absorbing rod is mounted in a housing with gripping uaits that engage the rod, and coils for magnetizing the gripping units to make them grip, shift, and release the rod are located outside the housing.

  18. A Tightly Stretched Ultralong Supramolecular Multiporphyrin Array Propagated by Double-Strand Formation.

    PubMed

    Morisue, Mitsuhiko; Hoshino, Yuki; Shimizu, Masaki; Uemura, Shinobu; Sakurai, Shinichi

    2016-09-05

    A shape-programmed linearity through supramolecular polymerization is demonstrated by a step-growth double-strand formation of a telechelic oligomeric porphyrin array in which two alternating pyridyl-porphyrin sequenced units are held together by self-complementary ligand-to-metal coordination. The stiff rod-like structure and sufficiently large binding constant of the double-strand unit considerably extended a supramolecular array in the one dimension, which produced a tightly stretched string with a length that exceeded several micrometers. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Polymer-induced phase separation in suspensions of bacteria

    NASA Astrophysics Data System (ADS)

    Schwarz-Linek, J.; Dorken, G.; Winkler, A.; Wilson, L. G.; Pham, N. T.; French, C. E.; Schilling, T.; Poon, W. C. K.

    2010-03-01

    We study phase separation in suspensions of two unrelated species of rod-like bacteria, Escherichia coli and Sinorhizobium meliloti, induced by the addition of two different anionic polyelectrolytes, sodium polystyrene sulfonate or succinoglycan, the former being synthetic and the latter of natural origin. Comparison with the known behaviour of synthetic colloid-polymer mixtures and with simulations show that "depletion" (or, equivalently, "macromolecular crowding") is the dominant mechanism: exclusion of the non-adsorbing polymer from the region between two neighbouring bacteria creates an unbalanced osmotic force pushing them together. The implications of our results for understanding phenomena such as biofilm formation are discussed.

  20. Morphology-Dependent Hardness of Cr7C3-Ni-Rich Alloy Composite vs Orientation Independent Hardness of Cr7C3 Primary Phase in a Laser Clad Microstructure

    NASA Astrophysics Data System (ADS)

    Venkatesh, Lakshmi Narayanan; Suresh Babu, Pitchuka; Gundakaram, Ravi Chandra; Doherty, Roger D.; Joshi, Shrikant V.; Samajdar, Indradev

    2017-04-01

    Microstructural evolution with superheating was studied in chromium carbide-nickel coatings deposited by laser cladding. At lower superheating, selective growth of <0001> direction from the high density of Cr7C3 grains nucleated resulted in a columnar structure with (0001) texture. Increased superheating lead to the loss of columnar structure as well as the (0001) texture. The hexagonal Cr7C3 showed an unusual isotropic nanoindentation hardness evidently correlated with its low c/ a ratio. However, the rod-like morphology of the carbide dendrites resulted in significant anisotropy in the hardness of the composite.

  1. Self-organization of OPV-PEG diblock copolymers in THF/water.

    SciTech Connect

    Jurban, V.; Littrell, K. C.; Thiyagarajan, P.; Wang, H. B.; Wang, H. H.; Yu, L.

    1999-07-02

    Oligo(phenylenevinylene)-poly(ethyleneglycol) (OPV-PEG) diblock copolymers in tetrahydrofuran (THF) solution at concentrations of 5 to 25 gl self-assemble into rod-like structures with a radius of about 80 {angstrom} for an OPV-PEG diblock copolymer comprising 13 PV and 45 EG monomers. These aggregates consist of a liquid crystalline OPV core and a PEG shell. Addition of about 10% water to the solution induces the formation of a phase of packed rods, as revealed by a sudden and dramatic transition of the scattering pattern. Further addition of water leads to swelling and at about 30% ultimately to disruption of the packed-rod phase.

  2. Voids and yolk-shells from crystals that coat particles.

    PubMed

    Sindoro, Melinda; Granick, Steve

    2014-10-01

    We investigate curvature-driven core-shell morphology that emerges when polycrystalline shells of ZIF-8 (zeolitic imidazolate framework coordination polymer) grow on colloid-sized particles. In early growth stages, the shell is continuous, but it transforms to yolk-shell, with neither sacrificial template nor core etching, because of geometrical frustration. A design rule is developed regarding how local surface curvature matters. Comparing shells grown on cubic, rod-like, and peanut-shaped hematite core particles, we validate the argument.

  3. Flipping and scooping of curved 2D rigid fibers in simple shear: the Jeffery equations

    NASA Astrophysics Data System (ADS)

    Crowdy, Darren

    2015-11-01

    The dynamical system (or ``Jeffery equations'') governing the orbits of a curved rigid two-dimensional fiber in simple shear is derived in analytical form. The study is motivated by the need to understand the dynamics of isolated non-axisymmetric rod-like particles in simple flows for use in suspension modeling. Solutions of the dynamical system are shown to display the ``flipping'' and ``scooping'' recently observed in computational studies of three-dimensional fibers using linked rigid rod and bead-shell models. Indeed the equations we derive are expected to be the same ones governing curved 3D slender fibers executing motions in the plane of shear.

  4. Simulation study of poled low-water ionomers with different architectures

    NASA Astrophysics Data System (ADS)

    Allahyarov, Elshad; Taylor, Philip L.; Löwen, Hartmut

    2011-11-01

    The role of the ionomer architecture in the formation of ordered structures in poled membranes is investigated by molecular dynamics computer simulations. It is shown that the length of the sidechain Ls controls both the areal density of cylindrical aggregates Nc and the diameter of these cylinders in the poled membrane. The backbone segment length Lb tunes the average diameter Ds of cylindrical clusters and the average number of sulfonates Ns in each cluster. A simple empirical formula is noted for the dependence of the number density of induced rod-like aggregates on the sidechain length Ls within the parameter range considered in this study.

  5. Spatial organization of plastic deformation in single crystals with different structure of slip dislocation

    SciTech Connect

    Kunitsyna, T. S.; Teplyakova, L. A. Koneva, N. A.; Poltaranin, M. A.

    2015-10-27

    It is established that different structure of slip dislocation at the end of the linear hardening stage results in different distribution of dislocation charges in the volume of a single crystal. In the alloy with a near atomic order the slip of single dislocations leads to formation of planar structures—layers with the excess density of dislocations. In the alloy with long-range atomic order the slip of superdislocations brings the formation of the system of parallel rod-like charged dislocation linking.

  6. Effect of azo and ester linkages on rod shaped Schiff base liquid crystals and their photophysical investigations

    NASA Astrophysics Data System (ADS)

    Selvarasu, Chinnaiyan; Kannan, Palaninathan

    2016-12-01

    Two new series of rod shaped Schiff base containing liquid crystal compounds with azo and ester linkages have been synthesized and characterized respectively. The rod like molecules containing cinnamate linkages with four different alkyl spacers (n = 6, 8, 10 and 12) and influence of linking group have been elucidated. Considerable changes in mesomorphic properties were noticed starting from Nematic to Smectic-C on changing of azo and ester linkages along with different terminal alkyl chain lengths. The mesomorphic properties of both series are compared. Photosensitive azobenzene group undergoes photoisomerization under UV light and monitored by UV-Visible spectroscopy.

  7. Expanded Processing Techniques for EMI Systems

    DTIC Science & Technology

    2012-07-01

    the scatter plots in the top row of Figure 3.3, both parameters are indicators of rod- like symmetry and in a noise- free case all the points would be...the+MM+Array++ During the AOL, AOL2, and MetalMapper projects we have made numerous free -air static measurements to characterize various UXO or UXO...smaller minor transients that are identical or nearly identical. This is the ideal case and the one that we always see in free -air or pit measurements

  8. Numerical study of soap-film flow by nonuniform alternating electric fields.

    PubMed

    Nasiri, M; Shirsavar, R; Mollaei, S; Ramos, A

    2017-02-01

    Fluid flow of suspended liquid films induced by non-uniform alternating electric fields has been reported. The electric fields were generated by two rod-like electrodes perpendicular to the fluid surface. The observed fluid flow was explained qualitatively by considering a charge induction mechanism, where the electric field actuates on the charge induced on the film surface. In this paper we perform a numerical study of this fluid flow taking into account the charge induction mechanism. The numerical results are compared with experiments and good agreement is found. Finally, we propose the application of the device as a new kind of two dimensional fluid pump.

  9. Morphology-Dependent Hardness of Cr7C3-Ni-Rich Alloy Composite vs Orientation Independent Hardness of Cr7C3 Primary Phase in a Laser Clad Microstructure

    NASA Astrophysics Data System (ADS)

    Venkatesh, Lakshmi Narayanan; Suresh Babu, Pitchuka; Gundakaram, Ravi Chandra; Doherty, Roger D.; Joshi, Shrikant V.; Samajdar, Indradev

    2017-02-01

    Microstructural evolution with superheating was studied in chromium carbide-nickel coatings deposited by laser cladding. At lower superheating, selective growth of <0001> direction from the high density of Cr7C3 grains nucleated resulted in a columnar structure with (0001) texture. Increased superheating lead to the loss of columnar structure as well as the (0001) texture. The hexagonal Cr7C3 showed an unusual isotropic nanoindentation hardness evidently correlated with its low c/a ratio. However, the rod-like morphology of the carbide dendrites resulted in significant anisotropy in the hardness of the composite.

  10. Update on the Notochord Including its Embryology, Molecular Development, and Pathology: A Primer for the Clinician

    PubMed Central

    Ramesh, Tushar; Nagula, Sai V; Saker, Erfanul; Shoja, Mohammadali; Loukas, Marios; Oskouian, Rod J; Tubbs, R. Shane

    2017-01-01

    The notochord is a rod-like embryological structure, which plays a vital role in the development of the vertebrate. Though embryological, remnants of this structure have been observed in the nucleus pulposus of the intervertebral discs of normal adults. Pathologically, these remnants can give rise to slow-growing and recurrent notochord-derived tumors called chordomas. Using standard search engines, the literature was reviewed regarding the anatomy, embryology, molecular development, and pathology of the human notochord. Clinicians who interpret imaging or treat patients with pathologies linked to the notochord should have a good working knowledge of its development and pathology. PMID:28480155

  11. Spin correlations in the bilayer manganite La 1.2Sr 1.8Mn 2O 7

    NASA Astrophysics Data System (ADS)

    Chatterji, T.; McIntyre, G. J.; Suryanarayanan, R.; Dhalenne, G.; Revcolevschi, A.

    1999-09-01

    We have investigated the spin correlations of the bilayer manganite La 1.2Sr 1.8Mn 2O 7, which shows colossal magnetoresistance (CMR) behaviour. Rod-like diffuse scattering parallel to c→∗ in the ( hol) plane has been observed. We have determined the temperature variation of the in-plane correlation length from the ( h,0,1.833) scan, which is perpendicular to the rod. The modulation of the diffuse-scattering intensity parallel to the rod in the scan (0.95,0, l) above Tc shows that the two ferromagnetic Mn planes in the bilayer are ferromagnetically correlated.

  12. Synthesis and Characterization of ZnO Nanorods and Nanodisks from Zinc Chloride Aqueous Solution.

    PubMed

    Long, Tengfa; Yin, Shu; Takabatake, Kouta; Zhnag, Peilin; Sato, Tsugio

    2008-12-16

    ZnO nanorods and nanodisks were synthesized by solution process using zinc chloride as starting material. The morphology of ZnO crystal changed greatly depending on the concentrations of Zn(2+) ion and ethylene glycohol (EG) additive in the solution. The effect of thermal treatment on the morphology was investigated. Photocatalytic activities of plate-like Zn(5)(OH)(8)Cl(2) . H(2)O and rod-like ZnO were characterized. About 18% of 1 ppm NO could be continuously removed by ZnO particles under UV light irradiation.

  13. Morphology evolution of ZrB{sub 2} nanoparticles synthesized by sol-gel method

    SciTech Connect

    Zhang Yun; Li Ruixing; Jiang Yanshan; Zhao Bin; Duan Huiping; Li Junping; Feng Zhihai

    2011-08-15

    Zirconium diboride (ZrB{sub 2}) nanoparticles were synthesized by sol-gel method using zirconium n-propoxide (Zr(OPr){sub 4}), boric acid (H{sub 3}BO{sub 3}), sucrose (C{sub 12}H{sub 22}O{sub 11}), and acetic acid (AcOH). Clearly, it was a non-aqueous solution system at the very beginning of the reactions. Here, AcOH was used as both chemical modifier and solvent to control Zr(OPr){sub 4} hydrolysis. Actually, AcOH could dominate the hydrolysis by self-produced water of the chemical propulsion, rather than the help of outer water. C{sub 12}H{sub 22}O{sub 11} was selected, since it can be completely decomposed to carbon. Thus, carbon might be accounted precisely for the carbothermal reduction reaction. Furthermore, we investigated the influence of the gelation temperature on the morphology of ZrB{sub 2} particles. Increasing the gelation temperature, the particle shapes changed from sphere-like particles at 65 deg. C to a particle chain at 75 deg. C, and then form rod-like particles at 85 deg. C. An in-depth HRTEM observation revealed that the nanoparticles of ZrB{sub 2} were gradually fused together to evolve into a particle chain, finally into a rod-like shape. These crystalline nature of ZrB{sub 2} related to the gelation temperature obeyed the 'oriented attachment mechanism' of crystallography. - Graphical Abstract: Increasing the gelation temperature, the particle shapes changed from sphere-like particles at 65 deg. C to a particle chain at 75 deg. C, and then form rod-like particles at 85 deg. C. Highlights: > ZrB{sub 2} nanoparticles were synthesized by sol-gel method in an non-aqueous solution system. > AcOH was used as both chemical modifier and solvent to control Zr(OPr){sub 4} hydrolysis. > C{sub 12}H{sub 22}O{sub 11} was selected since it can be completely decomposed to carbon. > Increasing the gelation temperature, the particles changed from sphere-like to rod-like ones. > Crystalline nature of ZrB{sub 2} obeyed the 'oriented attachment mechanism' of

  14. Ultrastructure of Kolmer's crystalloid in the pinealocytes of the common spiny mouse (Acomys cahirinus dimidiatus).

    PubMed

    Kappe, C

    1993-11-01

    Light- and electron-microscopical observations revealed a rod-like inclusion body in the pinealocytes of the common spiny mouse (Acomys cahirinus dimidiatus). Ultrastructurally, the body is composed of a varying number of tubes whose wall consists of thin filaments aligned in helical arrangement. The inner and outer surface of the wall is covered with ribosome-like granules. Based on a morphological analysis it is concluded that the body described in the present investigation is identical with Kolmer's crystalloid of horizontal cells in the human and primate retina.

  15. Intramolecular Charge Transfer of Conjugated Liquid Crystal Ferrocene Macromolecules - Synthesis and Characterization

    DTIC Science & Technology

    2016-04-12

    characterization of a new series of conjugated macromolecules bearing ferrocene as a highly efficient electron donor material coupled to 2,5-di(alcoxy) benzene...with efficient charge transfer, D-pi-A, are reported. The rigid, rod-like phenyleneethynylene chain bears flexible dodecanoxy group chains to impart...macromolecules illustrated in Figure 1, which bear ferrocene [(5-C5H5)Fe(5- C5H5)] as a highly efficient electron donor material. The ferrocene group is

  16. Draft genome sequence of Rhodococcus rhodochrous strain ATCC 17895

    PubMed Central

    Chen, Bi-Shuang; Otten, Linda G.; Resch, Verena; Muyzer, Gerard; Hanefeld, Ulf

    2013-01-01

    Rhodococcus rhodochrous ATCC 17895 possesses an array of mono- and dioxygenases, as well as hydratases, which makes it an interesting organism for biocatalysis. R. rhodochrous is a Gram-positive aerobic bacterium with a rod-like morphology. Here we describe the features of this organism, together with the complete genome sequence and annotation. The 6,869,887 bp long genome contains 6,609 protein-coding genes and 53 RNA genes. Based on small subunit rRNA analysis, the strain is more likely to be a strain of Rhodococcus erythropolis rather than Rhodococcus rhodochrous. PMID:24501654

  17. Transmission Electron Microscopy Study of Alumina Fiber-Reinforced Magnesium Composite.

    DTIC Science & Technology

    1987-01-01

    reported by Clark8 in Mg 5% Zn alloy aged from 149’C to 2600 C. Spherical precipitates were also observed along twin boundaries (Figure 14). These...fine dispersion of rod-like MgZn’ precipitates, dislocations, and MgZn precipitates along twin boundaries . 2. The composite interfacial reaction zone...electron micrograph of precipitates along twin boundaries . leols I=t p.. - -?? i ;- - Fiur5..Trnsisin lctonm rgrp of.’ ’’~ peitasaontw n ndris 0 mg ZMg

  18. Breaking of rod-shaped model material during compression

    NASA Astrophysics Data System (ADS)

    Lukas, Kulaviak; Vera, Penkavova; Marek, Ruzicka; Miroslav, Puncochar; Petr, Zamostny; Zdenek, Grof; Frantisek, Stepanek; Marek, Schongut; Jaromir, Havlica

    2017-06-01

    The breakage of a model anisometric dry granular material caused by uniaxial compression was studied. The bed of uniform rod-like pasta particles (8 mm long, aspect ratio 1:8) was compressed (Gamlen Tablet Press) and their size distribution was measured after each run (Dynamic Image Analysing). The compression dynamics was recorded and the effect of several parameters was tested (rate of compression, volume of granular bed, pressure magnitude and mode of application). Besides the experiments, numerical modelling of the compressed breakable material was performed as well, employing the DEM approach (Discrete Element Method). The comparison between the data and the model looks promising.

  19. Effects of Stiffness on Short, Semiflexible Homopolymer Chains

    NASA Astrophysics Data System (ADS)

    Seaton, Daniel T.; Schnabel, Stefan; Bachmann, Michael; Landau, David P.

    2012-08-01

    Conformational and transition behavior of finite, semiflexible homopolymers is studied using an extension of the Wang-Landau algorithm. Generation of a flat distribution in the sampling parameters energy and stiffness allows for efficient investigation of transitions between various conformational phases. Of particular importance is the ability to predict behavior for a given stiffness value, where three classes of minimum energy conformations are expected: Solid-globular, rod-like and toroidal. We present first results highlighting the behavior of a single N = 20 length chain.

  20. Small angle X-ray scattering of wheat seed-storage proteins: alpha-, gamma- and omega-gliadins and the high molecular weight (HMW) subunits of glutenin.

    PubMed

    Thomson, N H; Miles, M J; Popineau, Y; Harries, J; Shewry, P; Tatham, A S

    1999-03-19

    Small angle X-ray scattering in solution was performed on seed-storage proteins from wheat. Three different groups of gliadins (alpha-, gamma- and omega-) and a high molecular weight (HMW) subunit of glutenin (1Bx20) were studied to determine molecular size parameters. All the gliadins could be modelled as prolate ellipsoids with extended conformations. The HMW subunit existed as a highly extended rod-like particle in solution with a length of about 69 nm and a diameter of about 6.4 nm. Specific aggregation effects were observed which may reflect mechanisms of self-assembly that contribute to the unique viscoelastic properties of wheat dough.

  1. Synthesis and Characterization of ZnO Nanorods and Nanodisks from Zinc Chloride Aqueous Solution

    PubMed Central

    2009-01-01

    ZnO nanorods and nanodisks were synthesized by solution process using zinc chloride as starting material. The morphology of ZnO crystal changed greatly depending on the concentrations of Zn2+ion and ethylene glycohol (EG) additive in the solution. The effect of thermal treatment on the morphology was investigated. Photocatalytic activities of plate-like Zn5(OH)8Cl2 · H2O and rod-like ZnO were characterized. About 18% of 1 ppm NO could be continuously removed by ZnO particles under UV light irradiation. PMID:20596478

  2. Study of gelatin-agar intermolecular aggregates in the supernatant of its coacervate.

    PubMed

    Singh, S Santinath; Bohidar, H B; Bandyopadhyay, S

    2007-05-15

    Intermolecular interaction leading to formation of aggregates between gelatin, a polyampholyte, and agar, a polysaccharide was studied in the supernatant of the complex coacervate formed by these biopolymers. Electrophoresis, laser light scattering and viscometry data were used to determine the interaction and the physical structure of these intermolecular soluble complexes by modeling these to be prolate ellipsoids of revolution (rod-like structures with well defined axial ratio and Perrin's factor). Solution ionic strength was found to reduce the axial ratio of these complexes implying the presence of screened polarization-induced electrostatic interaction between the two biopolymers.

  3. Preparation of fluoride-substituted hydroxyapatite by a molten salt synthesis route.

    PubMed

    Zhang, Hui Gang; Zhu, Qingshan

    2006-08-01

    Fluoride-substituted hydroxyapatite (FHAp) with high thermal and morphologic stability was successfully prepared by a molten salt synthesis route. XRD patterns and FTIR spectra identified the synthesized powders as FHAp solid solution. The FHAp obtained with potassium sulfate as the flux showed the rod-like morphology without detectable decomposition up to 1300 degrees Celsius and the flux, sodium sulfate, led to the spheriodal FHAp. After investigating the effects of salt species on the FHAp morphologies, it was found that solubility was not the exclusive factor, which affected the morphological development of apatite powders, and the cations of molten salt species also played an important role.

  4. Sedimentation and gravitational instability of Escherichia coli Suspension

    NASA Astrophysics Data System (ADS)

    Douarche, Carine; Salin, Dominique; Collaboration between Laboratory FAST; LPS Collaboration

    2016-11-01

    The successive run and tumble of Escherichia coli bacteria provides an active matter suspension of rod-like particles with a large swimming diffusion. As opposed to inactive elongated particles, this diffusion prevents clustering and instability in the gravity field. We measure the time dependent E . coli concentration profile during their sedimentation. After some hours, due to the dioxygen consumption, a motile / non-motile front forms leading to a Rayleigh-Taylor type gravitational instability. Analyzing both sedimentation and instability in the framework of active particle suspensions, we can measure the relevant bacteria hydrodynamic characteristics such as its single particle sedimentation velocity and its hindrance volume.

  5. Binding of cationic dyes to DNA: distinguishing intercalation and groove binding mechanisms using simple experimental and numerical models.

    PubMed

    Del Castillo, P; Horobin, R W; Blázquez-Castro, A; Stockert, J C

    2010-08-01

    Simple methods for predicting intercalation or groove binding of dyes and analogous compounds with double stranded DNA are described. The methods are based on a quantitative assessment of the aspect (width to length) ratio of the dyes. The procedures were validated using a set of 38 cationic dyes of varied chemical structures binding to well oriented DNA fibers and assessing binding orientation by linear dichroism and polarized fluorescence. We demonstrated that low aspect ratio dyes bound by intercalation, whereas more rod-like dyes were groove binders. Some problems that result and possible applications are discussed briefly.

  6. Shape effects on dynamics of inertia-free spheroids in wall turbulence

    SciTech Connect

    Challabotla, Niranjan Reddy; Zhao, Lihao; Andersson, Helge I.

    2015-06-15

    The rotational motion of inertia-free spheroids has been studied in a numerically simulated turbulent channel flow. Although inertia-free spheroids were translated as tracers with the flow, neither the disk-like nor the rod-like particles adapted to the fluid rotation. The flattest disks preferentially aligned their symmetry axes normal to the wall, whereas the longest rods were parallel with the wall. The shape-dependence of the particle orientations carried over to the particle rotation such that the mean spin was reduced with increasing departure from sphericity. The streamwise spin fluctuations were enhanced due to asphericity, but substantially more for prolate than for oblate spheroids.

  7. Durable Heat Diaphragm from Ordered Polymer Films

    DTIC Science & Technology

    1990-05-01

    750 X =:1.079 D =3.998+ 001 * Figure 3 Needle Bearing Selection - Torringto. model B-128 needle bearings were selected as the bearings to support the...the bearings (LF) is given by the manufacturer as a function of the basic dynamic load capacity (BDC) rating, the load (in this case equal to P m/2...polyphosphoric acid, for it cannot be thermoformed . The stiff rod-like molecules give rise to a self-reinforced material which has the strength of advanced

  8. Negligible effect of grain boundaries on the thermal conductivity of rocks

    SciTech Connect

    Vandersande, J.W.; Pohl, R.O.

    1982-08-01

    The thermal conductivity of marble, gabbro, quartz-monzonite, basalt and of labradorite was measured between 0.3 and 80 K. In all cases, the phonon mean free paths l-bar were found to increase with decreasing temperature, but even at the lowest temperatures, l-bar was far smaller than the average grain sizes. This demonstrates that phonon scattering by grain boundaries has very little influence on the heat transport in these rocks. Evidence is presented that lamellae due to twinning or exsolution, rod-like large inclusions, and density fluctuations inside the grains mask the effect of grain boundaries.

  9. Distinct Regulation of Adaxial-Abaxial Polarity in Anther Patterning in Rice[C][W][OA

    PubMed Central

    Toriba, Taiyo; Suzaki, Takuya; Yamaguchi, Takahiro; Ohmori, Yoshihiro; Tsukaya, Hirokazu

    2010-01-01

    Establishment of adaxial-abaxial polarity is essential for lateral organ development. The mechanisms underlying the polarity establishment in the stamen remain unclear, whereas those in the leaf are well understood. Here, we investigated a rod-like lemma (rol) mutant of rice (Oryza sativa), in which the development of the stamen and lemma is severely compromised. We found that the rod-like structure of the lemma and disturbed anther patterning resulted from defects in the regulation of adaxial-abaxial polarity. Gene isolation indicated that the rol phenotype was caused by a weak mutation in SHOOTLESS2 (SHL2), which encodes an RNA-dependent RNA polymerase and functions in trans-acting small interfering RNA (ta-siRNA) production. Thus, ta-siRNA likely plays an important role in regulating the adaxial-abaxial polarity of floral organs in rice. Furthermore, we found that the spatial expression patterns of marker genes for adaxial-abaxial polarity are rearranged during anther development in the wild type. After this rearrangement, a newly formed polarity is likely to be established in a new developmental unit, the theca primordium. This idea is supported by observations of abnormal stamen development in the shl2-rol mutant. By contrast, the stamen filament is likely formed by abaxialization. Thus, a unique regulatory mechanism may be involved in regulating adaxial-abaxial polarity in stamen development. PMID:20511295

  10. On the "gluing" effect of lithium: the lithium-driven assembly of circum-arranged, edge-fused cyclopentadienyl lithium compounds and aza analogues.

    PubMed

    Saá, José M; Yañez, Manuel

    2009-01-01

    Predictions (DFT/B3LYP calculations) are that cyclopentadienyl lithium edge-fused to [n]circulenes in a circum-like manner should self-assemble as rod-like, nanometer long, supersandwich compounds (see figure). On the contrary, triazolyl lithium analogues prefer to dimerize thereby giving rise to shell-like dimers of variable curvatures.This study is aimed at exploring M. Etter's (T. W. Panunto, Z. Urbanczyk-Lipkowska, R. Jonhson, M. Etter, J. Am. Chem. Soc. 1987, 109, 7786-7797) bottom-up approach towards the design of organic-solid sate materials. Guided by the electrostatic paste ("gluing") effect of lithium, we examined the self-assembly modes of a series of cyclopentadienyl lithium edge-fused to benzene, as well as to [n]circulenes, arranged in a circum-like manner by means of DFT/B3 LYP calculations. We have also examined the self-assembly modes of the analogous triazolyl derivatives. Generally, well defined trends have been found. Thus, whereas cylcopentadienyl derivatives 1, 3 and 5 tend to aggregate as rod-like, nanometer-long, supersandwich compounds, the corresponding triazolyl analogues 2, 4 and 6 tend to dimerize thus giving rise to shell-like dimers of variable curvatures. In our view, M. Etter's bottom-up approach combined with high level calculations appears to have great potential for designing complex molecular architectures and nanostructures. Hopefully, these studies will spur the activity of synthetic and materials chemists.

  11. Seed-Mediated Growth of Gold Nanocrystals: Changes to the Crystallinity or Morphology as Induced by the Treatment of Seeds with a Sulfur Species

    SciTech Connect

    Zheng, Yiqun; Luo, Ming; Tao, Jing; Peng, Hsin-Chieh; Wan, Dehui; Zhu, Yimei; Xia, Younan

    2014-12-11

    We report our observation of changes to the crystallinity or morphology during seed-mediated growth of Au nanocrystals. When single-crystal Au seeds with a spherical or rod-like shape were treated with a chemical species such as S₂O₃²⁻ ions, twin defects were developed during the growth process to generate multiply twinned nanostructures. X-ray photoelectron spectroscopy analysis indicated that the S₂O₃²⁻ ions were chemisorbed on the surfaces of the seeds during the treatment. The chemisorbed S₂O₃²⁻ ions somehow influenced the crystallization of Au atoms added onto the surface during a growth process, leading to the formation of twin defects. In contrast to the spherical and rod-like Au seeds, the single-crystal structure was retained to generate a concave morphology when single-crystal Au seeds with a cubic or octahedral shape were used for a similar treatment and then seed-mediated growth. The different outcomes are likely related to the difference in spatial distribution of S₂O₃²⁻ ions chemisorbed on the surface of a seed. This approach based on surface modification is potentially extendable to other noble metals for engineering the crystallinity and morphology of nanocrystals formed via seed-mediated growth.

  12. Strengthening Effect of Extruded Mg-8Sn-2Zn-2Al Alloy: Influence of Micro and Nano-Size Mg2Sn Precipitates

    PubMed Central

    Cheng, Weili; Bai, Yang; Wang, Lifei; Wang, Hongxia; Bian, Liping; Yu, Hui

    2017-01-01

    In this study, Mg-8Sn-2Zn-2Al (TZA822) alloys with varying Mg2Sn contents prior to extrusion were obtained by different pre-treatments (without and with T4), and the strengthening response related to micro and nano-size Mg2Sn precipitates in the extruded TZA822 alloys was reported. The results showed that the morphology of nano-size Mg2Sn precipitates exhibits a significant change in basal plane from rod-like to spherical, owing to the decrement in the fraction of micro-size particles before extrusion. Meanwhile, the spherical Mg2Sn precipitates provided a much stronger strengthening effect than did the rod-like ones, which was ascribed to uniform dispersion and refinement of spherical precipitates to effectively hinder basal dislocation slip. As a consequence, the extruded TZA822 alloy with T4 showed a higher tensile yield strength (TYS) of 245 MPa, ultimate tensile strength (UTS) of 320 MPa and elongation (EL) of 26.5%, as well as a lower degree of yield asymmetry than their counterpart without T4. Detailed reasons for the strengthening effect were given and analyzed. PMID:28773180

  13. 2-D Hierarchical Structure of a Block Copolymer and Bio-nanoparticle Composites

    NASA Astrophysics Data System (ADS)

    Shin, Dongseok; Lin, Yao; Wang, Qian; Russell, Thomas

    2007-03-01

    2-dimensional hierarchical structures were generated by combining two different self assembling systems; block copolymer and bio-nanoparticle. For this study, a block copolymer having a positively charged component, i.e. poly (styrene-b-N-methyl-4-vinylpyridinium iodide), was used. Thin film composites of this block copolymer and bio-nanoparticles were fabricated by adsorbing bio-particles on the polymer film and subsequently annealing the sample under the presence of solvent vapor. 2-dimensional hierarchical structures, where block copolymer chains microphase separated inside of discrete grains surrounded by bio-nanoparticles, were obtained with rod- like bio-particles (tobacco mosaic virus and M13 phage) as well as with spherical one (ferritin). The pH effect on the assembly of rod-like bio-particles and the morphology of composites was investigated. When the pH of the solution used for the adsorption of bio-particles was low, the bio-molecules aggregated and formed large bundles, while they were dispersed well at high pH. This difference was reflected in the morphology of the resultant complexes.

  14. Hierarchical self-assembly of spider silk-like block copolymers

    NASA Astrophysics Data System (ADS)

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

    2011-03-01

    Block copolymers provide an attractive venue to study well-defined nano-structures that self-assemble to generate functionalized nano- and mesoporous materials. In the present study, a novel family of spider silk-like block copolymers was designed, bioengineered and characterized to study the impact of sequence chemistry, secondary structure and block length on assembled morphology. Genetic variants of native spider dragline silk (major ampullate spidroin I, Nephila clavipes) were used as polymer building blocks. Characterization by FTIR revealed increased ?-sheet content with increasing hydrophobic A blocks; SEM revealed spheres, rod-like structures, bowl-shaped and giant compound micelles. Langmuir Blodgett monolayers were prepared at the air-water interface at different surface pressures and monolayer films analyzed by AFM revealed oblate to prolate structures. Circular micelles, rod-like, densely packed circular structures were observed for HBA6 at increasing surface pressure. Exploiting hierarchical assembly provide a promising approach to rationale designs of protein block copolymer systems, allowing comparison to traditional synthetic systems.

  15. A bizarre Jurassic maniraptoran theropod with preserved evidence of membranous wings.

    PubMed

    Xu, Xing; Zheng, Xiaoting; Sullivan, Corwin; Wang, Xiaoli; Xing, Lida; Wang, Yan; Zhang, Xiaomei; O'Connor, Jingmai K; Zhang, Fucheng; Pan, Yanhong

    2015-05-07

    The wings of birds and their closest theropod relatives share a uniform fundamental architecture, with pinnate flight feathers as the key component. Here we report a new scansoriopterygid theropod, Yi qi gen. et sp. nov., based on a new specimen from the Middle-Upper Jurassic period Tiaojishan Formation of Hebei Province, China. Yi is nested phylogenetically among winged theropods but has large stiff filamentous feathers of an unusual type on both the forelimb and hindlimb. However, the filamentous feathers of Yi resemble pinnate feathers in bearing morphologically diverse melanosomes. Most surprisingly, Yi has a long rod-like bone extending from each wrist, and patches of membranous tissue preserved between the rod-like bones and the manual digits. Analogous features are unknown in any dinosaur but occur in various flying and gliding tetrapods, suggesting the intriguing possibility that Yi had membranous aerodynamic surfaces totally different from the archetypal feathered wings of birds and their closest relatives. Documentation of the unique forelimbs of Yi greatly increases the morphological disparity known to exist among dinosaurs, and highlights the extraordinary breadth and richness of the evolutionary experimentation that took place close to the origin of birds.

  16. Effects of hydrothermal treatment on the properties of nanoapatite crystals.

    PubMed

    Liang, Wei; Niu, Yunfei; Ge, Shuhua; Song, Shaojun; Su, Jiacan; Luo, Zhuojing

    2012-01-01

    We report the synthesis of nanoapatite crystals via a hydrothermal reaction of hydroxyapatite precipitates. The impact of the reaction conditions on the properties of the crystals obtained were evaluated. The hydrothermal reaction that takes place markedly affected the crystallinity, morphology, and size of the nanoapatite crystals formed. High crystallinity and large crystal size were obtained at higher hydrothermal temperatures and longer hydrothermal reaction times. The nanoapatite crystals were needle-like when prepared under ambient pressure conditions and rod-like when prepared under increased pressure. The crystals prepared at ambient pressure had a larger aspect ratio compared with those prepared under increased pressure. The aging time of the initial hydroxyapatite precipitate significantly affected growth of the nanoapatite crystals. With other hydrothermal reaction conditions being equal, the fresh hydroxyapatite precipitate produced notably larger crystals than the aged hydroxyapatite precipitate. The influence of apatite morphology on osteoblast viability was studied by MTT assay. The results indicate that the rod-like apatite showed a better biological response than needle-like apatite in promoting cell growth. Transmission electron microscopy showed that large quantities of needle apatite entered into cells and damaged their morphology.

  17. Kinetics-controlled growth of bimetallic RhAg on Au nanorods and their catalytic properties.

    PubMed

    Ye, Wei; Guo, Xia; Xie, Fang; Zhu, Rui; Zhao, Qing; Yang, Jian

    2014-04-21

    Controlled growth of hybrid metallic nanocomposites for a desirable structure in a combination of selected components is highly important for their applications. Herein, the controllable growth of RhAg on the gold nanorods is achieved from the dumbbell-like RhAg-tipped nanorods to the brushy RhAg-coated nanorods, or the rod-like Au@Ag-Rh nanorattles. These different growth modes of RhAg on the gold nanorods are correlated with the reducing kinetics of RhCl₃ and AgNO₃. In view of the promising catalytic properties of Rh, the gold nanorods modified by RhAg in different structures are examined as catalysts for the oxidation of o-phenylenediamine. It is found that brushy RhAg-coated nanorods present a higher catalytic efficiency than dumbbell-like RhAg-tipped nanorods and rod-like Au@Ag-Rh nanorattles. These results would benefit the overgrowth control on the one-dimensional metallic nanorods and the rational design of new generation heterogeneous catalysts and optical devices.

  18. Polyanhydride micelles with diverse morphologies for shape-regulated cellular internalization and blood circulation

    PubMed Central

    Yang, Guang; Wang, Jie; Li, Dan

    2017-01-01

    Abstract Biodegradable amphiphilic poly (ethylene glycol) (PEG) based ether-anhydride terpolymer, consisting of PEG, 1, 3-bis (p-carboxyphenoxy) propane (CPP) and sebacic acid (SA), namely PEG-CPP-SA terpolymer, was employed to self-assemble into micelles by adding water into a solution of the terpolymer in tetrahydrofuran (THF). The shape of polyanhydride micelles can be regulated by simply adjusting the water addition rate, where spherical, rod-like and comb-like micelles can obtained under water addition rate of 20, 3 and 1 ml/h, respectively. The effect of micellar morphologies on the cellular internalization and intracellular distribution were characterized qualitatively with cervical cancer cells (HeLa cells) and hepatoma cells (HepG2 cells) by fluorescence microscopy, confocal laser scanning microscopy (CLSM), flow cytometry (FCM) and transmission electron microscopy (TEM). The results reveal that the cellular uptake of micelles are micelle-shape-dependent (rod-like micelles may possess the highest cellular internalization rate) and cell-type-specific. Each endocytic pathway can make a contribution to this process in different degree. Moreover, blood circulation experiments of these micelles were carried out, demonstrating that comb-like micelles have a relatively longer blood circulating feature, which may due to its irregular shape help to increase the sensitivity to fluid forces and allows them to tumble and align with the blood flow. PMID:28596913

  19. Cu7 S4 Nanosuperlattices with Greatly Enhanced Photothermal Efficiency.

    PubMed

    Cui, Jiabin; Jiang, Rui; Xu, Suying; Hu, Gaofei; Wang, Leyu

    2015-09-02

    According to the simulation, the self-assembly of Cu7 S4 nanocrystals would enhance the photothermal conversion efficiency (PCE) because of the localized surface plasmon resonance effects, which is highly desirable for photothermal therapy (PTT). A new strategy to synthesize Cu7 S4 nanosuperlattices with greatly enhanced PCE up to 65.7% under irradiation of 808 nm near infrared light is reported here. By tuning the surface properties of Cu7 S4 nanocrystals during the synthesis via thermolysis of a new single precursor, dispersed nanoparticles (NPs), rod-like alignments, and nanosuperlattices are obtained, respectively. To explore their PTT applications, these hydrophobic nanostructures are transferred into water by coating with home-made amphiphilic polymer while maintaining their original structures. Under identical conditions, the PCE are 48.62% and 56.32% for dispersed NPs and rod-like alignments, respectively. As expected, when the nanoparticles are self-assembled into nanosuperlattices, the PCE is greatly enhanced up to 65.7%. This strong PCE, along with their excellent photothermal stability and good biocompatibility, renders these nanosuperlattices good candidates as PTT agents. In vitro photothermal ablation performances have undoubtedly proved the excellent PCE of our Cu7 S4 nanosuperlattices. This research offers a versatile and effective solution to get PTT agents with high photothermal efficiency.

  20. Self-assembly of DNA origami particles in suspension of non-absorbing depleting polymers

    NASA Astrophysics Data System (ADS)

    Siavashpouri, Mahsa; Zakhary, Mark; Wachauf, Christian; Dietz, Hendrik; Dogic, Zvonimir

    2015-03-01

    The connection between the macroscopic properties of a liquid crystalline material and the microscopic features of the constituent molecules is the essential theme that permeates the field of liquid crystals. Previous studies have shown that monodisperse rod-like colloids such as filamentous bacteriophage self-assemble into 1D twisted ribbons in presence of attractive interactions mediated by non-absorbing polymers. The microscopic properties of the colloidal particles play an important role in determining the physical properties of these mesoscopic assemblages. Using structural DNA nanotechnology, we present the design and structure of DNA origami six-helix bundles with tunable microscopic properties, which can be used as a new building block for the self-assembly of rod-like colloidal particles. We demonstrate that formation of higher order structures from the assembly of colloidal rods is universal. By tuning the chirality, aspect ratio and flexibility of the DNA origami particles we can control the physical properties of the entire self-assembled structures.

  1. Kinetics of the formation of 2D-hexagonal silica nanostructured materials by nonionic block copolymer templating in solution.

    PubMed

    Manet, Sabine; Schmitt, Julien; Impéror-Clerc, Marianne; Zholobenko, Vladimir; Durand, Dominique; Oliveira, Cristiano L P; Pedersen, Jan Skov; Gervais, Christel; Baccile, Niki; Babonneau, Florence; Grillo, Isabelle; Meneau, Florian; Rochas, Cyrille

    2011-10-06

    The different steps of the self-assembly in solution of several 2D-hexagonal silica nanostructured SBA-15 materials have been investigated by SAXS and SANS in situ experiments. Unique quantitative information about the shape and size evolution upon time of the micellar aggregates throughout the self-assembly process is obtained using a complete model that describes well the scattering data for the various synthesis conditions. In all cases, before the precipitation of the material, the micelles shape changes from spherical to rod-like, where the structure of the rod-like micelles is linked to the structure of the 2D-hexagonal precipitated material. In addition, the kinetics of hydrolysis of the inorganic precursor (TEOS) has been determined by in situ Raman spectroscopy. More specifically, by comparing synthesis made with different acids (HNO(3), HBr, HCl, H(2)SO(4), and H(3)PO(4)), it is found that materials prepared using the "salting-out" anions (SO(4)(2-) and H(2)PO(4)(-)) are much better ordered than with the "salting-in" anions (NO(3)(-) and Br(-)). © 2011 American Chemical Society

  2. A Deep Look Into Erionite Fibres: an Electron Microscopy Investigation of their Self-Assembly.

    PubMed

    Matassa, Roberto; Familiari, Giuseppe; Relucenti, Michela; Battaglione, Ezio; Downing, Clive; Pacella, Alessandro; Cametti, Georgia; Ballirano, Paolo

    2015-11-16

    The exposure of humans to erionite fibres of appropriate morphology and dimension has been unambiguously linked to the occurrence of Malignant Mesothelioma. For this reason, a detailed morpho-structural investigation through Electron Microscopy techniques has been performed on erionite samples collected at two different localities, Durkee (ED) and Rome (ER), Oregon, USA. The sample from Rome has been also investigated after a prolonged leaching with Gamble's solution (ER4G) in order to evaluate the possible occurrence of morpho-structural modifications induced by this Simulated-Lung-Fluid (SLF). Here we report how the micrometric erionite fibres evolve in irregular ribbon- or rod-like bundles as a function of different nano-structural features. The reasons for the observed morphological variability have been explained by considering the structural defects located at ED surface fibrils (bi-dimensional ribbons) and the presence of nontronite, an iron-bearing clay mineral embedding the ER fibrils (mono-dimensional rods). ER4G shows a decrease in width of the rod-like fibres due to their partial digestion by SLF leaching, which synchronously dissolves nontronite. The reported results represent a valuable background toward the full comprehension of the morphological mechanisms responsible for potentially damage of lung tissue through the potential relocation of fibers to extrapulmonary sites, increasing the carcinogenic risk to humans.

  3. Helical polyurethane-attapulgite nanocomposite: Preparation, characterization and study of optical activity

    SciTech Connect

    Wang Zhiqiang; Zhou Yuming; Sun Yanqing; Fan Kai; Guo Xingxing; Jiang Xiaolei

    2009-08-15

    Helical polyurethane-attapulgite (BM-ATT) based on R-1,1'-binaphthyl-2',2-diol (R-BINOL) composite was prepared after the surface modification of attapulgite (ATT). BM-ATT was characterized by Fourier-transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HTEM) and vibrational circular dichroism (VCD) spectroscopy. FT-IR and XRD analyses indicate that the helical polyurethane has been successfully grafted onto the surfaces of the modified ATT without destroying the original crystalline structure of ATT. BM-ATT exhibits the rod-like structure by SEM, TEM, and HTEM photographs. BM-ATT displays obvious Cotton effect for some absorbance in VCD spectrum, and its optical activity results from the singlehanded conformation of helical polyurethane. - Graphical Abstract: Helical polyurethane-attapulgite (BM-ATT) based on R-1,1'-binaphthyl-2',2-diol (R-BINOL) nanocomposite was prepared after surface modification of attapulgite (ATT). This rod-like composite is coated by the optically active polyurethane shell on the surfaces.

  4. Synthesis and Cytotoxicity of Y2O3 Nanoparticles of Various Morphologies

    NASA Astrophysics Data System (ADS)

    Andelman, Tamar; Gordonov, Simon; Busto, Gabrielle; Moghe, Prabhas V.; Riman, Richard E.

    2010-02-01

    As the field of nanotechnology continues to grow, evaluating the cytotoxicity of nanoparticles is important in furthering their application within biomedicine. Here, we report the synthesis, characterization, and cytotoxicity of nanoparticles of different morphologies of yttrium oxide, a promising material for biological imaging applications. Nanoparticles of spherical, rod-like, and platelet morphologies were synthesized via solvothermal and hydrothermal methods and characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), light scattering, surface area analysis, thermogravimetric analysis (TGA), and zeta potential measurements. Nanoparticles were then tested for cytotoxicity with human foreskin fibroblast (HFF) cells, with the goal of elucidating nanoparticle characteristics that influence cytotoxicity. Cellular response was different for the different morphologies, with spherical particles exhibiting no cytotoxicity to HFF cells, rod-like particles increasing cell proliferation, and platelet particles markedly cytotoxic. However, due to differences in the nanoparticle chemistry as determined through the characterization techniques, it is difficult to attribute the cytotoxicity responses to the particle morphology. Rather, the cytotoxicity of the platelet sample appears due to the stabilizing ligand, oleylamine, which was present at higher levels in this sample. This study demonstrates the importance of nanoparticle chemistry on in vitro cytotoxicity, and highlights the general importance of thorough nanoparticle characterization as a prerequisite to understanding nanoparticle cytotoxicity.

  5. Viroids: from genotype to phenotype just relying on RNA sequence and structural motifs.

    PubMed

    Flores, Ricardo; Serra, Pedro; Minoia, Sofía; Di Serio, Francesco; Navarro, Beatriz

    2012-01-01

    As a consequence of two unique physical properties, small size and circularity, viroid RNAs do not code for proteins and thus depend on RNA sequence/structural motifs for interacting with host proteins that mediate their invasion, replication, spread, and circumvention of defensive barriers. Viroid genomes fold up on themselves adopting collapsed secondary structures wherein stretches of nucleotides stabilized by Watson-Crick pairs are flanked by apparently unstructured loops. However, compelling data show that they are instead stabilized by alternative non-canonical pairs and that specific loops in the rod-like secondary structure, characteristic of Potato spindle tuber viroid and most other members of the family Pospiviroidae, are critical for replication and systemic trafficking. In contrast, rather than folding into a rod-like secondary structure, most members of the family Avsunviroidae adopt multibranched conformations occasionally stabilized by kissing-loop interactions critical for viroid viability in vivo. Besides these most stable secondary structures, viroid RNAs alternatively adopt during replication transient metastable conformations containing elements of local higher-order structure, prominent among which are the hammerhead ribozymes catalyzing a key replicative step in the family Avsunviroidae, and certain conserved hairpins that also mediate replication steps in the family Pospiviroidae. Therefore, different RNA structures - either global or local - determine different functions, thus highlighting the need for in-depth structural studies on viroid RNAs.

  6. Viroids: From Genotype to Phenotype Just Relying on RNA Sequence and Structural Motifs

    PubMed Central

    Flores, Ricardo; Serra, Pedro; Minoia, Sofía; Di Serio, Francesco; Navarro, Beatriz

    2012-01-01

    As a consequence of two unique physical properties, small size and circularity, viroid RNAs do not code for proteins and thus depend on RNA sequence/structural motifs for interacting with host proteins that mediate their invasion, replication, spread, and circumvention of defensive barriers. Viroid genomes fold up on themselves adopting collapsed secondary structures wherein stretches of nucleotides stabilized by Watson–Crick pairs are flanked by apparently unstructured loops. However, compelling data show that they are instead stabilized by alternative non-canonical pairs and that specific loops in the rod-like secondary structure, characteristic of Potato spindle tuber viroid and most other members of the family Pospiviroidae, are critical for replication and systemic trafficking. In contrast, rather than folding into a rod-like secondary structure, most members of the family Avsunviroidae adopt multibranched conformations occasionally stabilized by kissing-loop interactions critical for viroid viability in vivo. Besides these most stable secondary structures, viroid RNAs alternatively adopt during replication transient metastable conformations containing elements of local higher-order structure, prominent among which are the hammerhead ribozymes catalyzing a key replicative step in the family Avsunviroidae, and certain conserved hairpins that also mediate replication steps in the family Pospiviroidae. Therefore, different RNA structures – either global or local – determine different functions, thus highlighting the need for in-depth structural studies on viroid RNAs. PMID:22719735

  7. Mapping the molecular determinant of pathogenicity in a hammerhead viroid: A tetraloop within the in vivo branched RNA conformation

    PubMed Central

    De la Peña, Marcos; Navarro, Beatriz; Flores, Ricardo

    1999-01-01

    Chrysanthemum chlorotic mottle viroid (CChMVd) is an RNA of 398–399 nt that can adopt hammerhead structures in both polarity strands. We have identified by Northern-blot hybridization a nonsymptomatic strain (CChMVd-NS) that protects against challenge inoculation with the symptomatic strain (CChMVd-S). Analysis of CChMVd-NS cDNA clones has revealed a size and sequence very similar to those of the CChMVd-S strain. Some of the mutations observed in CChMVd-NS molecular variants were previously identified in CChMVd-S RNA, but others were never found in this RNA. When bioassayed in chrysanthemum, cDNA clones containing the CChMVd-NS specific mutations were infectious but nonsymptomatic. Site-directed mutagenesis showed that one of the CChMVd-NS-specific mutations, a UUUC → GAAA substitution, was sufficient to change the symptomatic phenotype into the nonsymptomatic one without altering the final accumulation level of the viroid RNA. The pathogenicity determinant–to our knowledge, a determinant of this class has not been described previously in hammerhead viroids–is located in a tetraloop of the computer-predicted branched conformation for CChMVd RNA. Analysis of the sequence heterogeneity found in CChMVd-S and -NS variants strongly supports the existence of such a conformation in vivo, showing that the rod-like or quasi-rod-like secondary structure is not a universal paradigm for viroids. PMID:10449802

  8. Behavior of osteoblast-like cells on calcium-deficient hydroxyapatite ceramics composed of particles with different shapes and sizes.

    PubMed

    Kamitakahara, Masanobu; Uno, Yuika; Ioku, Koji

    2014-01-01

    In designing the biomaterials, it is important to control their surface morphologies, because they affect the interactions between the materials and cells. We previously reported that porous calcium-deficient hydroxyapatite (HA) ceramics composed of rod-like particles had advantages over sintered porous HA ceramics; however, the effects of the surface morphology of calcium-deficient HA ceramics on cell behavior have remained unclear. Using a hydrothermal process, we successfully prepared porous calcium-deficient HA ceramics with different surface morphologies, composed of plate-like particles of 200-300, 500-800 nm, or 2-3 μm in width and rod-like particles of 1 or 3-5 μm in width, respectively. The effects of these surface morphologies on the behavior of osteoblast-like cells were examined. Although the numbers of cells adhered to the ceramic specimens did not differ significantly among the specimens, the proliferation rates of cells on the ceramics decreased with decreasing particle size. Our results reveal that controlling the surface morphology that is governed by particle shape and size is important for designing porous calcium-deficient HA ceramics.

  9. Synthesis of reticulated hollow spheres structure NiCo2S4 and its application in organophosphate pesticides biosensor.

    PubMed

    Peng, Lei; Dong, Sheying; Wei, Wenbo; Yuan, Xiaojing; Huang, Tinglin

    2017-06-15

    Electrode materials play a key role in the development of electrochemical sensors, particularly enzyme-based biosensors. Here, a novel NiCo2S4 with reticulated hollow spheres assembled from rod-like structures was prepared by a one-pot solvothermal method and its formation mechanism was discussed. Moreover, comparison of NiCo2S4 materials from different experiment conditions as biosensors was investigated by electrochemical impedance spectroscopy (EIS) and differential pulse voltammetry (DPV), and the best one that was reticulated hollow spheres assembled from rod-like structures NiCo2S4 has been successfully employed as a matrix of AChE immobilization for the special structure, superior conductivity and rich reaction active sites. When using common two kinds of organophosphate pesticides (OPs) as model analyte, the biosensors demonstrated a wide linear range of 1.0×10(-12)-1.0×10(-8)gmL(-1) with the detection limit of 4.2×10(-13)gmL(-1) for methyl parathion, and 1.0×10(-13)-1.0×10(-10)gmL(-1) with the detection limit of 3.5×10(-14)gmL(-1) for paraoxon, respectively. The proposed biosensors exhibited many advantages such as acceptable stability and low cost, providing a promising tool for analysis of OPs. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Controllable Synthesis of Formaldehyde Modified Manganese Oxide Based on Gas-Liquid Interfacial Reaction and Its Application of Electrochemical Sensing.

    PubMed

    Bai, Wushuang; Sheng, Qinglin; Nie, Fei; Zheng, Jianbin

    2015-12-30

    Controllable synthesis of manganese oxides was performed via a simple one-step synthetic method. Then obtained manganese oxides which exhibit flower-like, cloud-like, hexagon-like, and rod-like morphologies were modified by formaldehyde based on a simple self-made gas-liquid reaction device respectively and the modified manganese oxides with coral-like, scallop-like and rod-like morphology were synthesized accordingly. The obtained materials were characterized and the formation mechanism was also researched. Then the modified manganese oxides were used to fabricate electrochemical sensors to detect H2O2. Comparison of electrochemical properties between three kinds of modified manganese oxides was investigated and the best one has been successfully employed as H2O2 sensor which shows a low detection limit of 0.01 μM, high sensitivity of 162.69 μA mM(-1) cm(-2), and wide linear range of 0.05 μM-12.78 mM. The study provides a new method for controllable synthesis of metal oxides, and electrochemical application of formaldehyde modified manganese oxides will provides a new strategy for electrochemical sensing with high performance, low cost, and simple fabrication.

  11. In situ self-assembly of polarizing chromogen nanofibers catalyzed with hybrid films of gold nanoparticles and cellulose.

    PubMed

    Liu, Zhiming; Wu, Wenjian

    2017-09-20

    Hybrid materials of metal nanoparticles and biopolymers with catalytic properties are very promising to be used as detectors in biochemical reactions. In this work, the catalytic properties and relevant in situ self-assembly abilities of hybrid films of gold nanoparticles (GNPs) and cellulose for the oxidation of benign chromogen 3,3',5,5'-tetramethylbenzidine (TMB) with hydrogen peroxide (H2O2) are revealed for the first time. The peroxidase-like properties of hybrid films are inherited from those of colloidal GNPs and increase with their contents of GNPs. It is discovered that the oxidized products of TMB grow in situ and assemble into rod-like and tumbleweed-like nanofiber assemblies on hybrid films. The rod-like nanofibers show a magnificent polarizing phenomenon under polarized light because of polycrystalline globular nanoparticles inside. The in situ self-assembly of polarizing nanofibers of chromogen catalyzed with hybrid films creates an opportunity for the synthesis of novel organic nanomaterials and the enhanced detection of biochemical products under polarized light.

  12. Unfolding DNA condensates produced by DNA-like charged depletants: A force spectroscopy study

    NASA Astrophysics Data System (ADS)

    Lima, C. H. M.; Rocha, M. S.; Ramos, E. B.

    2017-02-01

    In this work, we have measured, by means of optical tweezers, forces acting on depletion-induced DNA condensates due to the presence of the DNA-like charged protein bovine serum albumin (BSA). The stretching and unfolding measurements performed on the semi-flexible DNA chain reveal (1) the softening of the uncondensed DNA contour length and (2) a mechanical behavior strikingly different from those previously observed: the force-extension curves of BSA-induced DNA condensates lack the "saw-tooth" pattern and applied external forces as high as ≈80 pN are unable to fully unfold the condensed DNA contour length. This last mechanical experimental finding is in agreement with force-induced "unpacking" detailed Langevin dynamics simulations recently performed by Cortini et al. on model rod-like shaped condensates. Furthermore, a simple thermodynamics analysis of the unfolding process has enabled us to estimate the free energy involved in the DNA condensation: the estimated depletion-induced interactions vary linearly with both the condensed DNA contour length and the BSA concentration, in agreement with the analytical and numerical analysis performed on model DNA condensates. We hope that future additional experiments can decide whether the rod-like morphology is the actual one we are dealing with (e.g. pulling experiments coupled with super-resolution fluorescence microscopy).

  13. Thermodynamic aspects of biopolymer functionality in biological systems, foods, and beverages.

    PubMed

    Tolstoguzov, Vladimir

    2002-01-01

    Molecular mimicry and molecular symbiosis are proposed to be the main factors controlling thermodynamic activity and phase behavior of macromolecular compounds in foods, beverages, and chyme. Molecular mimicry implies a chemical resemblance of hydrophilic surfaces of globular proteins with their chemical information hidden in the hydrophobic interior and low excluded volume of the globules. The molecular mimicry contributes to the efficiency of enzymes. Molecular symbiosis means that interactions attraction or repulsion) between biopolymer molecules greatly differing in conformation (globular and rod-like) favor the biological efficiency of one of them at least. The symbiosis is based on excluded volume effects of macromolecules in mixed solutions. Association-dissociation of rod-like macromolecules can dictate thermodynamic activity of an enzyme in the mixed solution. Thermodynamic incompatibility is typical of food macromolecules, whose denaturation, association, complexing, and chemical modification reduce their mimicry and co-solubility. Foods are normally phase-separated systems with highly volume-occupied phases. The phase-separated nature of the gel-like chyme is important to the efficiency of digestion of mixed diets. Phase separation of biopolymer mixtures, presumably, underlies mechanisms of nonspecific immune defense. The phase behavior-functionality relationships is presented through concrete examples of some foods (such as milk products, low-fat spreads, ice cream, wheat and rye doughs, thermoplastic extrudates, etc.), beverages (tea and coffee), and chyme.

  14. Synthesis, fractionation, and optical characterization of Au-Ag composite nanorods

    NASA Astrophysics Data System (ADS)

    Alekseeva, Anna V.; Bogatyrev, Vladimir A.; Trachuk, Lyubov A.; Khlebtsov, Nikolai G.

    2005-06-01

    We report on a synthesis procedure and optical properties of composite Au-Ag spherical and rod-like nanoparticles. The synthesis protocol is based on a seed-mediated growth in the presence of soft templates in micellar aqueous solution of ionic surfactant (CTAB). Variation of Au/Ag molar ratio allows one to produce nanorods (NRs) with different aspect ratio. The disadvantage of the method is formation of appreciable amount of spherical nanoparticles. To separate rod-like particles from spheres and surfactant, we used a fractionation procedure that involves centrifugatiori of samples in the density gradient of glycerol. The separated NRs were suspended in water or 25% glycerol solutions and their extinction and differential light scattering (at 900) spectra were recorded for 450-850 ni-n wavelengths. Theoretical spectra were calculated by T-matrix method as applied to randomly oriented gold cylinders with semispherical ends. The simulated spectra for water and glycerol suspensions can be brought in close agreement with experimental observations if the aspect ratio is used as a fitting parameter. We discuss also the absorption and light scattering contribution to the total extinction spectra and deviation of the exact solution from the classical electrostatic approximation by Gans.

  15. Computer simulations of nematic drops: Coupling between drop shape and nematic order

    NASA Astrophysics Data System (ADS)

    Rull, L. F.; Romero-Enrique, J. M.; Fernandez-Nieves, A.

    2012-07-01

    We perform Monte Carlo computer simulations of nematic drops in equilibrium with their vapor using a Gay-Berne interaction between the rod-like molecules. To generate the drops, we initially perform NPT simulations close to the nematic-vapor coexistence region, allow the system to equilibrate and subsequently induce a sudden volume expansion, followed with NVT simulations. The resultant drops coexist with their vapor and are generally not spherical but elongated, have the rod-like particles tangentially aligned at the surface and an overall nematic orientation along the main axis of the drop. We find that the drop eccentricity increases with increasing molecular elongation, κ. For small κ the nematic texture in the drop is bipolar with two surface defects, or boojums, maximizing their distance along this same axis. For sufficiently high κ, the shape of the drop becomes singular in the vicinity of the defects, and there is a crossover to an almost homogeneous texture; this reflects a transition from a spheroidal to a spindle-like drop.

  16. Strain induced insulator-to-conductor transition in conducting polymer composites from the auxetic behaviour of hierarchical microstructures.

    PubMed

    Polpaya, Indu Chanchal; Rao, C Lakshmana; Varughese, Susy

    2017-07-26

    Above their 'percolation threshold', intrinsically conducting polymer (ICP) based composites exhibit an increase or decrease in conductivity with strain. However, in this study we report an increase in conductivity and an associated insulator-to-conductor transition observed in certain conducting polymer composites below their percolation threshold under uniaxial tensile strain, thereby shifting the percolation to lower volume fractions. The 'auxetic behaviour' possible in certain types of 'hierarchical' microstructures is shown to be responsible for such changes in the polyaniline (PANI) composites studied. Using percolation models, the size and shape of the 'conducting units' that contribute to the percolation and its changes with strain were predicted. These conducting units are secondary and tertiary 'hierarchical structures' formed by the agglomeration of primary units of nano-rods (10 nm). An increase in the aspect ratio of these 'conducting units' is necessary for lowering the percolation threshold, which is possible in tertiary rod-like assemblies of PANI and not in secondary rod-like or platelet-like hierarchical structures. 'Auxetic behaviour' or a negative Poisson's ratio results in the expansion of the agglomerates and increase in the aspect ratio. This demonstrates the possibility of 'auxetic behaviour' contributing to changes in conductivity, which has not been reported before and could be used for novel applications.

  17. Mapping the molecular determinant of pathogenicity in a hammerhead viroid: a tetraloop within the in vivo branched RNA conformation.

    PubMed

    de la Peña, M; Navarro, B; Flores, R

    1999-08-17

    Chrysanthemum chlorotic mottle viroid (CChMVd) is an RNA of 398-399 nt that can adopt hammerhead structures in both polarity strands. We have identified by Northern-blot hybridization a nonsymptomatic strain (CChMVd-NS) that protects against challenge inoculation with the symptomatic strain (CChMVd-S). Analysis of CChMVd-NS cDNA clones has revealed a size and sequence very similar to those of the CChMVd-S strain. Some of the mutations observed in CChMVd-NS molecular variants were previously identified in CChMVd-S RNA, but others were never found in this RNA. When bioassayed in chrysanthemum, cDNA clones containing the CChMVd-NS specific mutations were infectious but nonsymptomatic. Site-directed mutagenesis showed that one of the CChMVd-NS-specific mutations, a UUUC --> GAAA substitution, was sufficient to change the symptomatic phenotype into the nonsymptomatic one without altering the final accumulation level of the viroid RNA. The pathogenicity determinant-to our knowledge, a determinant of this class has not been described previously in hammerhead viroids-is located in a tetraloop of the computer-predicted branched conformation for CChMVd RNA. Analysis of the sequence heterogeneity found in CChMVd-S and -NS variants strongly supports the existence of such a conformation in vivo, showing that the rod-like or quasi-rod-like secondary structure is not a universal paradigm for viroids.

  18. The effect of particle design on cellular internalization pathways

    PubMed Central

    Gratton, Stephanie E. A.; Ropp, Patricia A.; Pohlhaus, Patrick D.; Luft, J. Christopher; Madden, Victoria J.; Napier, Mary E.; DeSimone, Joseph M.

    2008-01-01

    The interaction of particles with cells is known to be strongly influenced by particle size, but little is known about the interdependent role that size, shape, and surface chemistry have on cellular internalization and intracellular trafficking. We report on the internalization of specially designed, monodisperse hydrogel particles into HeLa cells as a function of size, shape, and surface charge. We employ a top-down particle fabrication technique called PRINT that is able to generate uniform populations of organic micro- and nanoparticles with complete control of size, shape, and surface chemistry. Evidence of particle internalization was obtained by using conventional biological techniques and transmission electron microscopy. These findings suggest that HeLa cells readily internalize nonspherical particles with dimensions as large as 3 μm by using several different mechanisms of endocytosis. Moreover, it was found that rod-like particles enjoy an appreciable advantage when it comes to internalization rates, reminiscent of the advantage that many rod-like bacteria have for internalization in nonphagocytic cells. PMID:18697944

  19. Computational and Experimental Study of Spherocylinder Particles in Fluidized Beds

    NASA Astrophysics Data System (ADS)

    Mahajan, Vinay; Kuipers, Hans; Padding, Johan; Multiphase Reactors Group, TU Eindhoven Team

    2016-11-01

    Non-spherical particle flows are often encountered in fluidized process equipment. A coupled computational fluid dynamics (CFD) and discrete element method(DEM) approach has been extensively applied in recent years to study these flows at the particle scale. However, most of these studies focus on spherical particles while in reality, the constituent particles are seldom spherical. Particle shape can significantly affect the hydrodynamical response in fluidized beds. The drag force acting on a non-spherical particle can vary considerably with particle shape, orientation of the particle, Reynolds number and packing fraction. In this work, a CFD-DEM approach has been extended to model a lab scale quasi-2D fluidized bed of spherocylinder (rod-like) particles. These particles can be classified as Geldart D particles and have an aspect ratio of 4. Numerical results for the pressure drop, bed height and solid circulation patterns are compared with results from a complementary laboratory experiment. We also present results on particle orientations close to the confining walls, which provides interesting insight regarding the particle alignment. Thus the capability of the CFD-DEM approach to efficiently account for global bed dynamics in fluidized bed of rod-like particle is demonstrated. This research work is funded by ERC Grant.

  20. Molecular dynamics study of di-CF4 based reverse micelles in supercritical CO2.

    PubMed

    Liu, Bing; Tang, Xinpeng; Fang, Wenjing; Li, Xiaoqi; Zhang, Jun; Zhang, Zhiliang; Shen, Yue; Yan, Youguo; Sun, Xiaoli; He, Jianying

    2016-10-26

    Reverse micelles (RMs) in supercritical CO2 (scCO2) are promising alternatives for organic solvents, especially when both polar and non-polar components are involved. Fluorinated surfactants, particularly double-chain fluorocarbon surfactants, are able to form well-structured RMs in scCO2. The inherent self-assembly mechanisms of surfactants in scCO2 are still subject to discussion. In this study, molecular dynamics simulations are performed to investigate the self-aggregation behavior of di-CF4 based RMs in scCO2, and stable and spherical RMs are formed. The dynamics process and the self-assembly structure in the RMs reveal a three-step mechanism to form the RMs, that is, small RMs, rod-like RMs and fusion of the rod-like RMs. Hydrogen-bonds between headgroups and water molecules, and salt bridges linking Na(+) ions, headgroups and water molecules enhance the interfacial packing efficiency of the surfactant. The results show that di-CF4 molecules have a high surfactant coverage at the RM interface, implying a high CO2-philicity. This mainly results from bending of the short chain (C-COO-CH2-(CF2)3-CF3) due to the flexible carboxyl group. The microscopic insight provided in this study is helpful in understanding surfactant self-assembly phenomena and designing new CO2-philic surfactants.

  1. Nanometer to Millimeter Scale Peptide-Porphyrin Materials

    SciTech Connect

    D Zaytsev; F Xie; M Mukherjee; A Bludin; B Demeler; R Breece; D Tierney; M Ogawa

    2011-12-31

    AQ-Pal14 is a 30-residue polypeptide that was designed to form an {alpha}-helical coiled coil that contains a metal-binding 4-pyridylalanine residue on its solvent-exposed surface. However, characterization of this peptide shows that it exists as a three-stranded coiled coil, not a two-stranded one as predicted from its design. Reaction with cobalt(III) protoporphyrin IX (Co-PPIX) produces a six-coordinate Co-PPIX(AQ-Pal14){sub 2} species that creates two coiled-coil oligomerization domains coordinated to opposite faces of the porphyrin ring. It is found that this species undergoes a buffer-dependent self-assembly process: nanometer-scale globular materials were formed when these components were reacted in unbuffered H{sub 2}O, while millimeter-scale, rod-like materials were prepared when the reaction was performed in phosphate buffer (20 mM, pH 7). It is suggested that assembly of the globular material is dictated by the conformational properties of the coiled-coil forming AQ-Pal14 peptide, whereas that of the rod-like material involves interactions between Co-PPIX and phosphate ion.

  2. Why fibers are better turbulent drag reducing agents than polymers

    NASA Astrophysics Data System (ADS)

    Boelens, Arnout; Muthukumar, Murugappan

    2016-11-01

    It is typically found in literature that fibers are not as effective as drag reducing agents as polymers. However, for low concentrations, when adding charged polymers to either distilled or salt water, it is found that polymers showing rod-like behavior are better drag reducing agents than polymers showing coil-like behavior. In this study, using hybrid Direct Numerical Simulation with Langevin dynamics, a comparison is performed between polymer and fiber stress tensors in turbulent flow. The stress tensors are found to be similar, suggesting a common drag reducing mechanism in the onset regime. Since fibers do not have an elastic backbone, this must be a viscous effect. Analysis of the viscosity tensor reveals that all terms are negligible, except the off-diagonal shear viscosity associated with rotation. Based on this analysis, we are able to explain why charged polymers showing rod-like behavior are better drag reducing agents than polymers showing coil-like behavior. Additionally, we identify the rotational orientation time as the unifying time scale setting a new time criterion for drag reduction by both flexible polymers and rigid fibers. This research was supported by NSF Grant No. DMR-1404940 and AFOSR Grant No. FA9550-14-1-0164.

  3. Design and Synthesis of Efficient Fluorescent Dyes for Incorporation into DNA Backbone and Biomolecule Detection

    PubMed Central

    Wang, Wei; Li, Alexander D. Q.

    2008-01-01

    We report here the design and synthesis of a series of π-conjugated fluorescent dyes with D-A-D (D: donor; A: Acceptor), D-π-D, A-π-A, and D-π-A for applications as the signaling motif in biological-synthetic hybrid foldamers for DNA detection. Horner-Wadsworth-Emmons (HWE) reaction and Knoevenagel condensation were demonstrated as the optimum ways for construction of long π-conjugated systems. Such rod-like chromophores have distinct advantages, as their fluorescence properties are not quenched by the presence of DNA. To be incorporated into the backbone of DNA, the chromophores need to be reasonably soluble in organic solvent for solid-phase synthesis, and therefore a strategy of using flexible tetra(ethylene glycol) (TEG) linkers at either end of these rod-like dyes were developed. The presence of TEG facilitates the protection of the chain-growing hydroxyl group with DMTrCl (dimethoxy trityl chloride) as well as the activation of the coupling step with phosphoramidite chemistry on an automated DNA synthesizer. To form fluorescence resonance energy transfer (FRET) pairs, six synthetic chromophores with blue to red fluorescence have been developed and those with orthogonal fluorescent emission were chosen for incorporation into DNA-chromophore hybrid foldamers. PMID:17508711

  4. Role of reaction time in tuning the morphology and third order nonlinear optical properties of barium borate

    NASA Astrophysics Data System (ADS)

    Sabari Girisun, T. C.; Saravanan, M.; Vinitha, G.

    2017-03-01

    Single crystalline nanoclusters and nanorods like structure of barium borate (β- BaB2O4) were synthesized by organic free hydrothermal method at various reaction times of 8, 24 and 48 h. XRD shows the formation of pure and single phase of β- BaB2O4 with improved crystallinity at elevated reaction time. β- BaB2O4 crystallizes in hexagonal system with lattice parameter a=b=12.53 Å and c=12.72 Å. The surface morphology picturizes the formation of nanoclusters and rod structures with several micrometer length and nanometer diameter. By increasing the reaction time and due to prolonged pressure, aggregation followed by elongation resulted in the transformation of nanoclusters into rod like structure. The nanostructured barium borates possess strong UV absorbance and wide optical window. The nonlinear optical studies by Z- scan technique shows the material to possess saturable absorption and self-defocusing nature. A strong variation in third order nonlinear optical parameters with change in the morphology of β- BaB2O4 was observed. Also β- BaB2O4 rod like structure is identified to be more efficient optical limiters in the green regime of continuous wave lasers.

  5. In situ self-assembly of polarizing chromogen nanofibers catalyzed with hybrid films of gold nanoparticles and cellulose

    NASA Astrophysics Data System (ADS)

    Liu, Zhiming; Wu, Wenjian

    2017-09-01

    Hybrid materials of metal nanoparticles and biopolymers with catalytic properties are very promising to be used as detectors in biochemical reactions. In this work, the catalytic properties and relevant in situ self-assembly abilities of hybrid films of gold nanoparticles (GNPs) and cellulose for the oxidation of benign chromogen 3,3‧,5,5‧-tetramethylbenzidine (TMB) with hydrogen peroxide (H2O2) are revealed for the first time. The peroxidase-like properties of hybrid films are inherited from those of colloidal GNPs and increase with their contents of GNPs. It is discovered that the oxidized products of TMB grow in situ and assemble into rod-like and tumbleweed-like nanofiber assemblies on hybrid films. The rod-like nanofibers show a magnificent polarizing phenomenon under polarized light because of polycrystalline globular nanoparticles inside. The in situ self-assembly of polarizing nanofibers of chromogen catalyzed with hybrid films creates an opportunity for the synthesis of novel organic nanomaterials and the enhanced detection of biochemical products under polarized light.

  6. Hydration characteristics and environmental friendly performance of a cementitious material composed of calcium silicate slag.

    PubMed

    Zhang, Na; Li, Hongxu; Zhao, Yazhao; Liu, Xiaoming

    2016-04-05

    Calcium silicate slag is an alkali leaching waste generated during the process of extracting Al2O3 from high-alumina fly ash. In this research, a cementitious material composed of calcium silicate slag was developed, and its mechanical and physical properties, hydration characteristics and environmental friendly performance were investigated. The results show that an optimal design for the cementitious material composed of calcium silicate slag was determined by the specimen CFSC7 containing 30% calcium silicate slag, 5% high-alumina fly ash, 24% blast furnace slag, 35% clinker and 6% FGD gypsum. This blended system yields excellent physical and mechanical properties, confirming the usefulness of CFSC7. The hydration products of CFSC7 are mostly amorphous C-A-S-H gel, rod-like ettringite and hexagonal-sheet Ca(OH)2 with small amount of zeolite-like minerals such as CaAl2Si2O8·4H2O and Na2Al2Si2O8·H2O. As the predominant hydration products, rod-like ettringite and amorphous C-A-S-H gel play a positive role in promoting densification of the paste structure, resulting in strength development of CFSC7 in the early hydration process. The leaching toxicity and radioactivity tests results indicate that the developed cementitious material composed of calcium silicate slag is environmentally acceptable. This study points out a promising direction for the proper utilization of calcium silicate slag in large quantities.

  7. Strong, Tough Ceramics Containing Microscopic Reinforcements: Tailoring In-Situ Reinforced Silicon Nitride Ceramics

    SciTech Connect

    Becher, P.F.

    1999-06-27

    Ceramics with their hardness, chemical stability, and refractoriness could be used to design more efficient energy generation and conversion systems as well as numerous other applications. However, we have needed to develop a fundamental understanding of how to tailor ceramics to improve their performance, especially to overcome their brittle nature. One of the advances in this respect was the incorporation of very strong microscopic rod-like reinforcements in the form of whiskers that serve to hold the ceramic together making it tougher and resistant to fracture. This microscopic reinforcement approach has a number of features that are similar to continuous fiber-reinforced ceramics; however, some of the details are modified. For instance, the strengths of the microscopic reinforcements must be higher as they typically have much stronger interfaces. For instance, single crystal silicon carbide whiskers can have tensile strengths in excess of {ge}7 GPa or >2 times that of continuous fibers. Furthermore, reinforcement pullout is limited to lengths of a few microns in the case of microscopic reinforcement due as much to the higher interfacial shear resistance as to the limit of the reinforcement lengths. On the other hand, the microscopic reinforcement approach can be generated in-situ during the processing of ceramics. A remarkable example of this is found in silicon nitride ceramics where elongated rod-like shape grains can be formed when the ceramic is fired at elevated temperatures to form a dense component.

  8. Photoluminescence study of self-interstitial clusters and extended defects in ion-implanted silicon

    NASA Astrophysics Data System (ADS)

    Giri, P. K.

    2003-12-01

    We report on the photoluminescence (PL) studies of self-interstitial (I) clustering in ion-implanted Si at various stages of post-implantation annealing. Low-temperature PL measurements on as-implanted and low-temperature annealed (up to 450°C) samples show sharp X and W bands at 1200 and 1218 nm which are attributed to I4 and I3 clusters, respectively. Annealing at 600°C shows a drastic change in the PL spectra. In case of high-energy self-ion-implanted samples, 600°C annealing produces several peaks in the range 1250-1400 nm. For longer duration annealing, two broad bands form at 1322 and 1392 nm irrespective of the ion fluence. These PL signatures are attributed to I8 clusters and/or (1 0 0) I-chains, and they are believed to be the precursor of {3 1 1} rod-like defects. For annealing above 600°C and for fluence ⩾1×1013 cm-2, a sharp PL band is observed at 1376 nm and it is attributed to {3 1 1} rod-like defects. At higher fluences, an additional broad band appears in the PL spectrum at ∼1576 nm which is related to residual ion-damage or extended defect formation. These results illustrate the potential of silicon I-clusters as a possible source of light emission from Si.

  9. Networking and rheology of concentrated clay suspensions "matured" in mineral medicinal water.

    PubMed

    Aguzzi, Carola; Sánchez-Espejo, Rita; Cerezo, Pilar; Machado, José; Bonferoni, Cristina; Rossi, Silvia; Salcedo, Inmaculada; Viseras, César

    2013-09-10

    This work studied the influence of "maturation" conditions (time and agitation) on aggregation states, gel structure and rheological behaviour of a special kind of pharmaceutical semisolid products made of concentrated clay suspensions in mineral medicinal water. Maturation of the samples was carried out in distilled and sulphated mineral medicinal water, both in static conditions (without agitation) and with manual stirring once a week, during a maximum period of three months. At the measured pH interval (7.5-8.0), three-dimensional band-type networks resulting from face/face contacts were predominant in the laminar (disc-like) clay suspensions, whereas the fibrous (rod-like) particles formed micro-aggregates by van der Waals attractions. The high concentration of solids in the studied systems greatly determined their behaviour. Rod-like sepiolite particles tend to align the major axis in aggregates promoted by low shearing maturation, whereas aggregates of disc-like smectite particles did not have a preferential orientation and their complete swelling required long maturation time, being independent of stirring. Maturation of both kinds of suspensions resulted in improved rheological properties. Laminar clay suspensions became more structured with time, independently from static or dynamic maturation conditions, whereas for fibrous clay periodic agitation was also required. Rheological properties of the studied systems have been related to aggregation states and networking mechanisms, depending on the type of clay minerals constituents. Physical stability of the suspensions was not impaired by the specific composition of the Graena medicinal water.

  10. Evaluation of microstructural development in electron beam melted Ti-6Al-4V

    SciTech Connect

    Safdar, A.; Wei, L.-Y.; Snis, A.; Lai, Z.

    2012-03-15

    In the current work an investigation of the microstructures of EBM built Ti-6Al-4V test bars has been performed using OM, SEM, TEM and XRD. It has been found that the prior {beta} phase, that formed during the initial solidification, possesses a column shaped morphology with growing direction parallel to built direction. Typical ({alpha} + {beta}) structures namely Widmanstaetten {alpha} platelets with rod-like {beta} phase formed on the interfaces of the fine {alpha} grains, have been observed in the columnar prior {beta} grains. Grain boundary {alpha} phase was found to be formed around the boundaries of the columnar prior {beta} grains. Different phases present in the parts, especially the BCC {beta} phases have been characterized. The TEM/EDX results indicate very high V composition in the {beta} phase. Results of TEM/SAED and XRD also revealed that a superlattice structure could be present in the {beta} phase. Phase transformation sequence is discussed according to the processing history and the microstructures observed. - Highlights: Black-Right-Pointing-Pointer {alpha} + {beta} and individual {beta} phase is observed and characterized by SEM, TEM and XRD. Black-Right-Pointing-Pointer {beta}-phase is identified as rod-like structure embedded in {alpha} matrix and platelets. Black-Right-Pointing-Pointer Phase transformation sequence is discussed as per thermal history and microstructures.

  11. Small Angle X-Ray Scattering and Quasi-Elastic Light Scattering Studies of Polymer Liquid Crystals

    NASA Astrophysics Data System (ADS)

    Ao, Xiaolei

    In order to understand the structural properties of semiflexible polymer liquid crystals, small angle X -ray scattering data from the synthetic polypeptide poly -gamma-benzyl glutamate (PBG) in the nematic phase are presented. The important features of the data are discussed in terms of the current understanding of the nature of nematic ordering in main chain polymer systems. This includes analysis of the angular distribution function for the polymer segments, long wavelength fluctuations dictated by elastic phenomena, the effects of finite chain lengths, and the effects due to the short range interactions and packing of the chains. The rigid rod-like biological macromolecule, tobacco mosaic virus (TMV), in the nematic and the smectic A phases is studied by quasi-elastic light scattering in order to understand the hydrodynamic properties of rigid rod-like lyotropic liquid crystals. A nonlocal behavior of the elasticity in the nematic phase is observed and discussed in terms of a recent developed nonlocal theory. The relative diffusion and undulation modes in the smectic A phase are observed. The results are compared with theory.

  12. RodZ links MreB to cell wall synthesis to mediate MreB rotation and robust morphogenesis

    PubMed Central

    Morgenstein, Randy M.; Bratton, Benjamin P.; Nguyen, Jeffrey P.; Ouzounov, Nikolay; Shaevitz, Joshua W.; Gitai, Zemer

    2015-01-01

    The rod shape of most bacteria requires the actin homolog, MreB. Whereas MreB was initially thought to statically define rod shape, recent studies found that MreB dynamically rotates around the cell circumference dependent on cell wall synthesis. However, the mechanism by which cytoplasmic MreB is linked to extracytoplasmic cell wall synthesis and the function of this linkage for morphogenesis has remained unclear. Here we demonstrate that the transmembrane protein RodZ mediates MreB rotation by directly or indirectly coupling MreB to cell wall synthesis enzymes. Furthermore, we map the RodZ domains that link MreB to cell wall synthesis and identify mreB mutants that suppress the shape defect of ΔrodZ without restoring rotation, uncoupling rotation from rod-like growth. Surprisingly, MreB rotation is dispensable for rod-like shape determination under standard laboratory conditions but is required for the robustness of rod shape and growth under conditions of cell wall stress. PMID:26396257

  13. Preparation of molybdenum carbides with multiple morphologies using surfactants as carbon sources

    SciTech Connect

    Wang, Hongfen; Wang, Zhiqi; Chen, Shougang

    2012-10-15

    Molybdenum carbides with surfactants as carbon sources were prepared using the carbothermal reduction of the appropriate precursors (molybdenum oxides deposited on surfactant micelles) at 1023 K under hydrogen gas. The carburized products were characterized using scanning electron microscopy (SEM), X-ray diffraction and BET surface area measurements. From the SEM images, hollow microspherical and rod-like molybdenum carbides were observed. X-ray diffraction patterns showed that the annealing time of carburization had a large effect on the conversion of molybdenum oxides to molybdenum carbides. And BET surface area measurements indicated that the difference of carbon sources brought a big difference in specific surface areas of molybdenum carbides. - Graphical abstract: Molybdenum carbides having hollow microspherical and hollow rod-like morphologies that are different from the conventional monodipersed platelet-like morphologies. Highlights: Black-Right-Pointing-Pointer Molybdenum carbides were prepared using surfactants as carbon sources. Black-Right-Pointing-Pointer The kinds of surfactants affected the morphologies of molybdenum carbides. Black-Right-Pointing-Pointer The time of heat preservation at 1023 K affected the carburization process. Black-Right-Pointing-Pointer Molybdenum carbides with hollow structures had larger specific surface areas.

  14. Will fluoride toughen or weaken our teeth? Understandings based on nucleation, morphology, and structural assembly.

    PubMed

    Wang, Zhiqiang; Ma, Guobin; Liu, Xiang Yang

    2009-12-24

    Fluoride exerts a substantial impact on the biominearlization of hydroxyapatite (HAP). In this study, the effect of fluoride on the nucleation kinetics of HAP was examined quantitatively in a simulated body fluid. It was found for the first time that fluoride promotes the nucleation of HAP. Furthermore, both the concentration of fluoride and the supersaturation of HAP play a key role in the formation of an ordered assembly of rod-like HAP crystallites. At relatively low concentrations of fluoride, an ordered assembly of rod-like crystallites similar to the structure of enamel could be obtained in the simulated body fluid, which could be explained by the self-epitaxial nucleation-mediated assembly. At high concentrations, fluoride may lead to the deterioration of the ordered assembled structure of HAP crystallites. That result is caused by the fast nucleation and growth of HAP crystallites when the supply of nucleation seeds is limited, resulting in the formation of spherulites. Our results illustrate how and why fluoride influences the self-assembled structures of HAP crystallites at low and high concentrations of F(-). Thus, they will substantially advance our understanding on the impact of fluoride ions on the mineralization of HAP and consequently on the dental and bone fluorosis.

  15. Nanoscale X-Ray Microscopic Imaging of Mammalian Mineralized Tissue

    PubMed Central

    Andrews, Joy C.; Almeida, Eduardo; van der Meulen, Marjolein C.H.; Alwood, Joshua S.; Lee, Chialing; Liu, Yijin; Chen, Jie; Meirer, Florian; Feser, Michael; Gelb, Jeff; Rudati, Juana; Tkachuk, Andrei; Yun, Wenbing; Pianetta, Piero

    2010-01-01

    A novel hard transmission X-ray microscope (TXM) at the Stanford Synchrotron Radiation Light-source operating from 5 to 15 keV X-ray energy with 14 to 30 µm2 field of view has been used for high-resolution (30–40 nm) imaging and density quantification of mineralized tissue. TXM is uniquely suited for imaging of internal cellular structures and networks in mammalian mineralized tissues using relatively thick (50 µm), untreated samples that preserve tissue micro- and nanostructure. To test this method we performed Zernike phase contrast and absorption contrast imaging of mouse cancellous bone prepared under different conditions of in vivo loading, fixation, and contrast agents. In addition, the three-dimensional structure was examined using tomography. Individual osteocytic lacunae were observed embedded within trabeculae in cancellous bone. Extensive canalicular networks were evident and included processes with diameters near the 30–40 nm instrument resolution that have not been reported previously. Trabecular density was quantified relative to rod-like crystalline apatite, and rod-like trabecular struts were found to have 51–54% of pure crystal density and plate-like areas had 44–53% of crystal density. The nanometer resolution of TXM enables future studies for visualization and quantification of ultrastructural changes in bone tissue resulting from osteoporosis, dental disease, and other pathologies. PMID:20374681

  16. Systematic study on the influence of the morphology of α-MoO3 in the selective oxidation of propylene

    NASA Astrophysics Data System (ADS)

    Schuh, Kirsten; Kleist, Wolfgang; Høj, Martin; Jensen, Anker Degn; Beato, Pablo; Patzke, Greta R.; Grunwaldt, Jan-Dierk

    2015-08-01

    A variety of morphologically different α-MoO3 samples were prepared by hydrothermal synthesis and applied in the selective oxidation of propylene. Their catalytic performance was compared to α-MoO3 prepared by flame spray pyrolysis (FSP) and a classical synthesis route. Hydrothermal synthesis from ammonium heptamolybdate (AHM) and nitric acid at pH 1-2 led to ammonium containing molybdenum oxide phases that were completely transformed into α-MoO3 after calcination at 550 °C. A one-step synthesis of α-MoO3 rods was possible starting from MoO3·2H2O with acetic acid or nitric acid and from AHM with nitric acid at 180 °C. Particularly, if nitric acid was used during synthesis, the rod-like morphology of the samples could be stabilized during calcination at 550 °C and the following catalytic activity tests, which was beneficial for the catalytic performance in propylene oxidation. Characterization studies using X-ray diffraction (XRD), scanning electron microscopy (SEM) and Raman spectroscopy showed that those samples, which retained their rod-like morphology during the activity tests, yielded the highest propylene conversion.

  17. Emergent states in dense systems of active rods: from swarming to turbulence

    NASA Astrophysics Data System (ADS)

    Wensink, H. H.; Löwen, H.

    2012-11-01

    Dense suspensions of self-propelled rod-like particles exhibit a fascinating variety of non-equilibrium phenomena. By means of computer simulations of a minimal model for rigid self-propelled colloidal rods with variable shape we explore the generic diagram of emerging states over a large range of rod densities and aspect ratios. The dynamics is studied using a simple numerical scheme for the overdamped noiseless frictional dynamics of a many-body system in which steric forces are dominant over hydrodynamic ones. The different emergent states are identified by various characteristic correlation functions and suitable order parameter fields. At low density and aspect ratio, a disordered phase with no coherent motion precedes a highly cooperative swarming state with giant number fluctuations at large aspect ratio. Conversely, at high densities weakly anisometric particles show a distinct jamming transition whereas slender particles form dynamic laning patterns. In between there is a large window corresponding to strongly vortical, turbulent flow. The different dynamical states should be verifiable in systems of swimming bacteria and artificial rod-like micro-swimmers.

  18. Improving the stability of coal slurries: Final report. [Polygalacturonic acid and gum tragacanth

    SciTech Connect

    Fogler, H.S.

    1988-12-01

    Polysaccharides were found to stabilize colloidal dispersions (such as coal particles and polystyrene latex particles) even at high ionic strengths. The stability studies with various kinds of polysaccharides showed that rod-like molecules (such as poly (galacturonic acid) and gum tragacanth) are much more effective stabilizers than highly-branched molecules such as arabinogalactan. This effective stabilization with the rod-like molecules was found to result from the adsorption of polysaccharides on the particles, i.e., the steric stabilization mechanism. The stability depends significantly on the solution pH, the molecular weight and the surface charge of particles. Adsorption isotherms, the zeta potential and the conformation of adsorbed molecules (the steric layer thicknesses) were measured as a function of the solution pH, the molecular weight and the surface charge. Photon correlation spectroscopy studies showed that the conformation of adsorbed molecules is strongly dependent on the solution pH, the molecular weight and the surface charge, suggesting that the dependence of stability on these parameters is due to the change of the conformation of the molecules adsorbed on the surface. In addition, the solution pH has a significant effect on the flocculation behavior of particles and can be modulated to bring about peptization of particles. This type of stabilization is referred to as electrosteric stabilization whereby steric stabilization is induced by changing the electrical properties of the system (the solution pH in this case). 41 refs., 43 figs., 10 tabs.

  19. Investigation of the operating conditions to morphology evolution of β-L-glutamic acid during seeded cooling crystallization

    NASA Astrophysics Data System (ADS)

    Zhang, Fangkun; Liu, Tao; Huo, Yan; Guan, Runduo; Wang, Xue Z.

    2017-07-01

    In this paper the effects of operating conditions including cooling rate, initial supersaturation, and seeding temperature were investigated on the morphology evolution of β-L-glutamic acid (β-LGA) during seeded cooling crystallization. Based on the results of in-situ image acquisition of the crystal morphology evolution during the crystallization process, it was found that the crystal products tend to be plate-like or short rod-like under a slow cooling rate, low initial supersaturation, and low seeding temperature. In the opposite, the operating conditions of a faster cooling rate, higher initial supersaturation, and higher seeding temperature tend to produce long rod-like or needle-like crystals, and meanwhile, the length and width of crystal products will be increased together with a wider crystal size distribution (CSD). The aspect ratio of crystals, defined by the crystal length over width measured from in-situ or sample images, was taken as a shape index to analyze the crystal morphologies. Based on comparative analysis of the experimental results, guidelines on these operating conditions were given for obtaining the desired crystal shapes, along with the strategies for obtaining a narrower CSD for better product quality. Experimental verifications were performed to illustrate the proposed guidelines on the operating conditions for seeded cooling crystallization of LGA solution.

  20. A Deep Look Into Erionite Fibres: an Electron Microscopy Investigation of their Self-Assembly

    PubMed Central

    Matassa, Roberto; Familiari, Giuseppe; Relucenti, Michela; Battaglione, Ezio; Downing, Clive; Pacella, Alessandro; Cametti, Georgia; Ballirano, Paolo

    2015-01-01

    The exposure of humans to erionite fibres of appropriate morphology and dimension has been unambiguously linked to the occurrence of Malignant Mesothelioma. For this reason, a detailed morpho-structural investigation through Electron Microscopy techniques has been performed on erionite samples collected at two different localities, Durkee (ED) and Rome (ER), Oregon, USA. The sample from Rome has been also investigated after a prolonged leaching with Gamble’s solution (ER4G) in order to evaluate the possible occurrence of morpho-structural modifications induced by this Simulated-Lung-Fluid (SLF). Here we report how the micrometric erionite fibres evolve in irregular ribbon- or rod-like bundles as a function of different nano-structural features. The reasons for the observed morphological variability have been explained by considering the structural defects located at ED surface fibrils (bi-dimensional ribbons) and the presence of nontronite, an iron-bearing clay mineral embedding the ER fibrils (mono-dimensional rods). ER4G shows a decrease in width of the rod-like fibres due to their partial digestion by SLF leaching, which synchronously dissolves nontronite. The reported results represent a valuable background toward the full comprehension of the morphological mechanisms responsible for potentially damage of lung tissue through the potential relocation of fibers to extrapulmonary sites, increasing the carcinogenic risk to humans. PMID:26567530

  1. Synthesis, characterization and photocatalytic activity of 1D TiO2 nanostructures.

    PubMed

    Cabrera, Julieta; Alarcón, Hugo; López, Alcides; Candal, Roberto; Acosta, Dwight; Rodriguez, Juan

    2014-01-01

    Nanowire/nanorod TiO(2) structures of approximately 8 nm in diameter and around 1,000 nm long were synthesized by alkaline hydrothermal treatment of two different TiO(2) nanopowders. The first precursor was TiO(2) obtained by the sol-gel process (SG-TiO(2)); the second was the well-known commercial TiO(2) P-25 (P25-TiO(2)). Anatase-like 1D TiO(2) nanostructures were obtained in both cases. The one-dimensional (1D) nanostructures synthesized from SG-TiO(2) powders turned into rod-like nanostructures after annealing at 400 °C for 2 h. Conversely, the nanostructures synthesized from P25-TiO(2) preserved the tubular structure after annealing, displaying a higher Brunauer-Emmett-Teller surface area than the first system (279 and 97 m²/g, respectively). Despite the higher surface area shown by the 1D nanostructures, in both cases the photocatalytic activity was lower than for the P25-TiO(2) powder. However, the rod-like nanostructures obtained from SG-TiO(2) displayed slightly higher efficiency than the sol-gel prepared powders. The lower photocatalytic activity of the nanostructures with respect to P-25 can be associated with the lower crystallinity of 1D TiO(2) in both materials.

  2. Electron microscopy and computational studies of Ebh, a giant cell-wall-associated protein from Staphylococcus aureus.

    PubMed

    Sakamoto, Sou; Tanaka, Yoshikazu; Tanaka, Isao; Takei, Toshiaki; Yu, Jian; Kuroda, Makoto; Yao, Min; Ohta, Toshiko; Tsumoto, Kouhei

    2008-11-14

    Ebh, a giant protein found in staphylococci, contains several domains, including a large central region with 52 imperfect repeats of a domain composed of 126 amino acids. We used electron microscopy to observe the rod-like structure of a partial Ebh protein containing 10 repeating units. This is the first report of the direct observation of an Ebh structure containing a large number of repeating units, although structures containing one, two, or four repeating units have been reported. The observed structure of the partial Ebh protein was distorted and had a length of ca. 520A and a width of ca. 21A. The observed structures were consistent with those deduced from crystal structure analysis, suggesting that the Ebh domains are connected to form a rod-like structure. The crystal structure data revealed distorted, string-like features in the simulated structure of the whole-length Ebh protein. Superposition of fragments of the simulated whole-length structure of the Ebh protein onto each electron micrograph showed a high level of correlation between the observed and calculated structures. These results suggest that Ebh is composed of highly flexible filate molecules. The highly repetitive structure and the associated unique structural flexibility of Ebh support the proposed function of this protein, i.e. binding to sugars in the cell wall. This binding might result in intra-cell-wall cross-linking that contributes to the rigidity of bacterial cells.

  3. Structural and Rheological Properties of Temperature-Responsive Amphiphilic Triblock Copolymers in Aqueous Media.

    PubMed

    Nielsen, Josefine Eilsø; Zhu, Kaizheng; Sande, Sverre Arne; Kováčik, Lubomír; Cmarko, Dušan; Knudsen, Kenneth D; Nyström, Bo

    2017-05-11

    Thermoresponsive amphiphilic biodegradable block copolymers of the type poly(ε-caprolactone-co-lactide)-poly(ethylene glycol)-poly(ε-caprolactone-co-lactide) (PCLA-PEGm-PCLA) have great potential for various biomedical applications. In the present study, we have surveyed the effects of PEG spacer length (m = 1000 and 1500), temperature, and polymer concentration on the self-assembling process to form supramolecular structures in aqueous solutions of the PCLA-PEGm-PCLA copolymer. This copolymer has a lower critical solution temperature, and the cloud point depends on both concentration and PEG length. Thermoreversible hydrogels are formed in the semidilute regime; the gel windows in the phase diagrams can be tuned by the concentration and length of the PEG spacer. The rheological properties of both dilute and semidilute samples were characterized; especially the sol-to-gel transition was examined. Small-angle neutron scattering (SANS) experiments reveal fundamental structural differences between the two copolymers for both dilute and semidilute samples. The intensity profiles for the copolymer with the long PEG spacer could be described by a spherical core-shell model over a broad temperature domain, whereas the copolymer with the short hydrophilic spacer forms rod-like species over an extended temperature range. This finding is supported by cryo-TEM images. At temperatures approaching macroscopic phase separation, both copolymers seem to assume extended rod-like structures.

  4. Seed-Mediated Growth of Gold Nanocrystals: Changes to the Crystallinity or Morphology as Induced by the Treatment of Seeds with a Sulfur Species

    DOE PAGES

    Zheng, Yiqun; Luo, Ming; Tao, Jing; ...

    2014-12-11

    We report our observation of changes to the crystallinity or morphology during seed-mediated growth of Au nanocrystals. When single-crystal Au seeds with a spherical or rod-like shape were treated with a chemical species such as S₂O₃²⁻ ions, twin defects were developed during the growth process to generate multiply twinned nanostructures. X-ray photoelectron spectroscopy analysis indicated that the S₂O₃²⁻ ions were chemisorbed on the surfaces of the seeds during the treatment. The chemisorbed S₂O₃²⁻ ions somehow influenced the crystallization of Au atoms added onto the surface during a growth process, leading to the formation of twin defects. In contrast to themore » spherical and rod-like Au seeds, the single-crystal structure was retained to generate a concave morphology when single-crystal Au seeds with a cubic or octahedral shape were used for a similar treatment and then seed-mediated growth. The different outcomes are likely related to the difference in spatial distribution of S₂O₃²⁻ ions chemisorbed on the surface of a seed. This approach based on surface modification is potentially extendable to other noble metals for engineering the crystallinity and morphology of nanocrystals formed via seed-mediated growth.« less

  5. Electron microscopy and computational studies of Ebh, a giant cell-wall-associated protein from Staphylococcus aureus

    SciTech Connect

    Sakamoto, Sou; Tanaka, Yoshikazu; Tanaka, Isao; Takei, Toshiaki; Yu, Jian; Kuroda, Makoto; Yao Min; Ohta, Toshiko; Tsumoto, Kouhei

    2008-11-14

    Ebh, a giant protein found in staphylococci, contains several domains, including a large central region with 52 imperfect repeats of a domain composed of 126 amino acids. We used electron microscopy to observe the rod-like structure of a partial Ebh protein containing 10 repeating units. This is the first report of the direct observation of an Ebh structure containing a large number of repeating units, although structures containing one, two, or four repeating units have been reported. The observed structure of the partial Ebh protein was distorted and had a length of ca. 520 A and a width of ca. 21 A. The observed structures were consistent with those deduced from crystal structure analysis, suggesting that the Ebh domains are connected to form a rod-like structure. The crystal structure data revealed distorted, string-like features in the simulated structure of the whole-length Ebh protein. Superposition of fragments of the simulated whole-length structure of the Ebh protein onto each electron micrograph showed a high level of correlation between the observed and calculated structures. These results suggest that Ebh is composed of highly flexible filate molecules. The highly repetitive structure and the associated unique structural flexibility of Ebh support the proposed function of this protein, i.e. binding to sugars in the cell wall. This binding might result in intra-cell-wall cross-linking that contributes to the rigidity of bacterial cells.

  6. Synthesis and Magnetic Properties of Cobalt Ferrite with Different Morphologies

    NASA Astrophysics Data System (ADS)

    Nayak, Bibhuti B.; Nayak, Nadiya Bihary; Mallik, Rahul Kumar; Mondal, Aparna

    Different morphologies (spherical, flake and rod) of cobalt ferrite were synthesized using cobalt salt, iron salts, hydrazine hydrate (as a precipitating agent) and CTAB (surfactant) in water as well as ethylene glycol solvents. Four different synthesis ways (HIS, SIH, HISCO and HISG) were adopted to synthesize cobalt ferrite nanopowders using precipitation method. The as-prepared powders obtained after different synthesis ways were calcined at 800°C and structure, microstructure as well as magnetic properties are studied. X-ray diffraction (XRD), scanning electron microscope (SEM) and magnetization studies using pulsed field loop tracer were employed to characterize these cobalt ferrite powders, prepared using different precipitation ways. All the samples are identified with single phase cobalt ferrite and the crystallite size was found to be around 40 nm. Nearly spherical (multifaceted), rod with flake-like, nearly spherical and rod-like morphologies are obtained while synthesizing using HIS, SIH, HISCO and HISG ways, respectively. Rod with flake-like (SIH sample) and rod-like morphologies (HISG sample) show higher coercivity, than the spherical-like (SIH and HISCO smaples) morphology. The highest coericivty was found to be around 925 Oe for HISG sample and highest magnetization is 67 emu/g for HISCO sample.

  7. Reduced excimer formation in polyfluorenes by introducing coil-like poly[penta(ethylene glycol) methyl ether methacrylate] block segments

    NASA Astrophysics Data System (ADS)

    Noh, Seung Ju; Heo, Seong Ik; Jang, Se Hyun; Ahn, Haeng Hee; Han, Jin Young; Suk, Min Gyun; Jin, Sun Jin; Kwon, Yong Ku

    2012-09-01

    The formation of the aggregate and excimer in light-emitting polyfluorenes during annealing at high temperatures was reduced by adding coil-like block segments through atom transfer radical polymerization (ATRP), initialized by 2- bromoisobutyrate end-capped PF macroinitiator using CuBr/N,N,N',N',N''-pentamethyldiethylenetriamine (PMDETA) catalyst system. The rod-like macroinitiator was synthesized by the Yamamoto-type coupling using a Ni(COD)2 catalyst. The structure and physical properties were characterized by 1H NMR, thermal analysis, GPC, photoluminescence, small angle X-ray scattering and transmission electron microscopy. The addition of the coil-like block segments to the rod-like block segment resulted in the microphase separation between the component blocks which decreased the effective conjugation length of the conjugated moieties. The photoluminescence spectra measured from the thin films of the block copolymers revealed that the coil-like endblocks, attached to the conjugated block segments, suppressed the excimer formation of the PF molecules during annealing at high temperature.

  8. Imide modified epoxy matrix resins

    NASA Technical Reports Server (NTRS)

    Scola, D. A.

    1982-01-01

    Results of a program designed to develop tough imide modified epoxy (IME) resins cured by bisimide amine (BIA) hardeners are presented. State of the art epoxy resin, MY720, was used. Three aromatic bisimide amines and one aromatic aliphatic BIA were evaluated. BIA's derived from 6F anhydride (3,3 prime 4,4 prime-(hexafluoro isopropyl idene) bis (phthalic anhydride) and diamines, 3,3 prime-diam nodiphenyl sulfone (3,3 prime-DDS), 4,4 prime-diamino diphenyl sulfone (4,4 prime-DDS), 1.12-dodecane diamine (1,12-DDA) were used. BIA's were abbreviated 6F-3,3 prime-DDS, 6F-4,4 prime-DDS, 6F-3,3 prime-DDS-4,4 prime DDS, and 6F-3,3 prime-DDS-1,12-DDA corresponding to 6F anhydride and diamines mentioned. Epoxy resin and BIA's (MY720/6F-3,3 prime-DDS, MY720/6F-3,3 prime-DDS-4,4 prime-DDS, MY720/6F-3,3 prime-DDS-1,12-DDA and a 50:50 mixture of a BIA and parent diamine, MY720/6F-3,3 prime-DDS/3,3 prime-DDS, MY720/6F-3,3 prime-DDS-4,4 prime-DDS/3,3 prime-DDS, MY720/6F-3,3 prime-DDS-1,12-DDA/3,3 prime-DDS were studied to determine effect of structure and composition. Effect of the addition of two commercial epoxies, glyamine 200 and glyamine 100 on the properties of several formulations was evaluated. Bisimide amine cured epoxies were designated IME's (imide modified epoxy). Physical, thermal and mechanical properties of these resins were determined. Moisture absorption in boiling water exhibited by several of the IME's was considerably lower than the state of the art epoxies (from 3.2% for the control and state of the art to 2.0 wt% moisture absorption). Char yields are increased from 20% for control and state of the art epoxies to 40% for IME resins. Relative toughness characteristics of IME resins were measured by 10 deg off axis tensile tests of Celion 6000/IME composites. Results show that IME's containing 6F-3,3 prime-DDS or 6F-3,3 prime-DDS-1,12-DDA improved the "toughness" characteristics of composites by about 35% (tensile strength), about 35% (intralaminar shear

  9. Increased calcium content and inhomogeneity of mineralization render bone toughness in osteoporosis: mineralization, morphology and biomechanics of human single trabeculae.

    PubMed

    Busse, Björn; Hahn, Michael; Soltau, Markus; Zustin, Jozef; Püschel, Klaus; Duda, Georg N; Amling, Michael

    2009-12-01

    The differentiation and degree of the effects of mineral content and/or morphology on bone quality remain, to a large extent, unanswered due to several microarchitectural particularities in spatial measuring fields (e.g., force transfer, trajectories, microcalli). Therefore, as the smallest basic component of cancellous bone, we focused on single trabeculae to investigate the effects of mineralization and structure, both independently and in superposition. Transiliac Bordier bone cores and T12 vertebrae were obtained from 20 females at autopsy for specimen preparation, enabling radiographical analyses, histomorphometry, Bone Mineral Density Distribution (BMDD) analyses, and trabecular singularization to be performed. Evaluated contact X-rays and histomorphometric limits from cases with osteoporotic vertebral fractures generated two subdivisions, osteoporotic (n=12, Ø 78 years) and non-osteoporotic (n=8, Ø 49 years) cases, based on fracture appearance and bone volume (BV/TV). Measurements of trabecular number (Tb.N.), trabecular separation (Tb.Sp.), trabecular thickness (Tb.Th.), trabecular bone pattern factor (TBPf) and eroded surface (ES/BS) were carried out to provide detailed structural properties of the investigated groups. The mechanical properties of 400 rod-like single vertebral trabeculae, assessed by three-point bending, were matched with mineral properties as quantified by BMDD analyses of cross-sectioned rod-like and plate-like trabeculae, both in superposition and independently. Non-osteoporotic iliac crests and vertebrae displayed linear dependency on structure parameters, whereas osteoporotic compartments proved to be non-correlated with bone structure. Independent of trabecular thickness, osteoporotic rod-like trabeculae showed decreases in Young's modulus, fracture load, yield strength, ultimate stress, work to failure and bending stiffness, along with significantly increased mean calcium content and calcium width. Non-osteoporotic trabeculae

  10. Facile synthesis, spectral properties and formation mechanism of sulfur nanorods in PEG-200

    SciTech Connect

    Xie, Xin-yuan; Li, Li-yun; Zheng, Pu-sheng; Zheng, Wen-jie; Bai, Yan; Cheng, Tian-feng; Liu, Jie

    2012-11-15

    Graphical abstract: Homogeneous rod-like structure of sulfur with a typical diameter of about 80 nm and an average aspect ratio of about 6–8 was obtained. The sulfur nanoparticles could self-assemble from spherical particles to nanorods in PEG-200. During the self-assembling process, the absorption band showed a red shift which was due to the production of nanorods. Highlights: ► A novel, facile and greener method to synthesize sulfur nanorods by the solubilizing and templating effect of PEG-200 was reported. ► S{sup 0} nanoparticles could self assemble in PEG-200 and finally form monodisperse and homogeneous rod-like structure with an average diameter of about 80 nm, the length ca. 600 nm. ► The absorption band showed a red shift and the RRS intensity enhanced continuously during the self-assembling process. ► PEG-200 induced the oriented attachment of sulfur nanoparticles by the terminal hydroxyl groups. -- Abstract: The synthesis of nano-sulfur sol by dissolving sublimed sulfur in a green solvent-PEG-200 was studied. Homogeneous rod-like structure of sulfur with a typical diameter of about 80 nm and an average aspect ratio of 6–8 was obtained. The structure, morphology, size, and stability of the products were investigated by transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and dynamic light scattering (DLS) measurements. The spectral properties of the products were investigated by ultraviolet-visible (UV–vis) absorption and resonance Rayleigh scattering spectroscopy (RRS). The results showed that the spherical sulfur nanoparticles could self-assemble into nanorods in PEG-200. During the self-assembling process, the absorption band showed a red shift and the RRS intensity enhanced continuously. There was physical cross-linking between PEG and sulfur nanoparticles. PEG-200 induced the oriented attachment of sulfur nanoparticles by

  11. Role of nanomaterial physicochemical properties on fate and toxicity in bacteria and plants

    NASA Astrophysics Data System (ADS)

    Slomberg, Danielle

    Nanomaterials, defined as those having at least one dimension <100 nm, are ubiquitous in nature. However, engineered nanomaterials have gained increasing attention for use in drug-delivery applications and consumer goods. Examination of nanomaterial toxicity, both beneficial (e.g., drug delivery to bacterial pathogens) and detrimental (e.g., death of terrestrial plants), thus warranted. Herein, I present the evaluation of nitric oxide-releasing nanomaterial toxicity to bacteria and silica particle toxicity to plants as a function of nanomaterial physicochemical properties. Nanomaterial toxicity toward planktonic (i.e., free-floating) Pseudomonas aeruginosa and Staphylococcus aureus bacteria was evaluated as a function of scaffold size, shape, and exterior functionality using nitric oxide-releasing (NO) silica particles, dendrimers, and chitosan oligosaccharides. Improved bactericidal efficacy was observed for silica particles with decreased size and increased aspect ratio (i.e., rod-like) due to improved particle-cell interactions. Likewise, better nanomaterial-bacteria association and biocidal action was noted for more hydrophobic NO-releasing dendrimers and chitosan oligosaccharides. Planktonic bacterial killing was not dependent on chitosan molecular weight due to rapid association between the cationic scaffolds and negatively-charged bacterial cell membranes. Given the importance of nanomaterial physicochemical properties in planktonic bacterial killing, the NO-releasing scaffolds were also evaluated against clinically-relevant bacterial biofilms. Similar to planktonic studies, smaller particle sizes proved more efficient in delivering NO throughout the biofilm. Particles with rod-like shape also eradicated biofilms more effectively. The role of NO-releasing dendrimer and chitosan oligosaccharide hydrophobicity was prominent in scaffold diffusion through the biofilm and subsequent NO delivery, with hydrophobic functionalities generally exhibiting better

  12. Phosphorus-containing imide resins - Modification by elastomers

    NASA Technical Reports Server (NTRS)

    Varma, I. K.; Fohlen, G. M.; Parker, J. A.; Varma, D. S.

    1984-01-01

    The syntheses and general features of addition-type maleimide resins based on bis(m-aminophenyl)phosphine oxide and tris(m-aminophenyl)phosphine oxide have been reported previously. These resins have been used to fabricate graphite cloth laminates having excellent flame resistance. These composites did not burn even in pure oxygen. However, these resins were somewhat brittle. This paper reports the modification of these phosphorus-containing resins by an amine-terminated butadiene-acrylonitrile copolymer (ATBN) and a perfluoroalkylene diaromatic amine elastomer (3F). An approximately two-fold increase in short beam shear strength and flexural strength was observed at 7 percent ATBN concentration. The tensile, flexural, and shear strengths were reduced when 18 percent ATBN was used. Anaerobic char yields of the resins at 800 C and the limiting oxygen indexes of the laminates decreased with increasing ATBN concentration. The perfluorodiamine (3F) was used with both imide resins at 6.4 percent concentration. The shear strength was doubled in the case of the bisimide with no loss of flammability characteristics. The modified trisimide laminate also had improved properties over the unmodified one. The dynamic mechanical analysis of a four-ply laminate indicated a glass transition temperature above 300 C. Scanning electron micrographs of the ATBN modified imide resins were also recorded.

  13. Electrochemical Capture and Release of CO2 in Aqueous Electrolytes Using an Organic Semiconductor Electrode.

    PubMed

    Apaydin, Dogukan H; Gora, Monika; Portenkirchner, Engelbert; Oppelt, Kerstin T; Neugebauer, Helmut; Jakesova, Marie; Głowacki, Eric D; Kunze-Liebhäuser, Julia; Zagorska, Malgorzata; Mieczkowski, Jozef; Sariciftci, Niyazi Serdar

    2017-04-19

    Developing efficient methods for capture and controlled release of carbon dioxide is crucial to any carbon capture and utilization technology. Herein we present an approach using an organic semiconductor electrode to electrochemically capture dissolved CO2 in aqueous electrolytes. The process relies on electrochemical reduction of a thin film of a naphthalene bisimide derivative, 2,7-bis(4-(2-(2-ethylhexyl)thiazol-4-yl)phenyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (NBIT). This molecule is specifically tailored to afford one-electron reversible and one-electron quasi-reversible reduction in aqueous conditions while not dissolving or degrading. The reduced NBIT reacts with CO2 to form a stable semicarbonate salt, which can be subsequently oxidized electrochemically to release CO2. The semicarbonate structure is confirmed by in situ IR spectroelectrochemistry. This process of capturing and releasing carbon dioxide can be realized in an oxygen-free environment under ambient pressure and temperature, with uptake efficiency for CO2 capture of ∼2.3 mmol g(-1). This is on par with the best solution-phase amine chemical capture technologies available today.

  14. Photorefractive polymer device with improved sensitizing property

    NASA Astrophysics Data System (ADS)

    Nguyen, Tam V.; Giang, Ha N.; Kinashi, K.; Sakai, W.; Tsutsumi, N.

    2015-09-01

    photorefractive (PR) application because of a fast hole mobility. In most of the previous studies, phenyl-C61-butyric acid methyl ester (PCBM) was used as a sensitizer. In this study, a high-performance charge generator perylene bisimide (PBI) is synthesized and added into the composite. PBI derivatives owning a large core of π-conjugated rings provide a high electron affinity and high charge carrier mobility. These features are promising to improve PR properties. To the best of our knowledge, it is the first time for using a combine of PCBM and PBI to improve the PR performance of PDAA-based composites. 2-(4-(azepan-1-yl)benzylidene)malononitrile (7-DCST) is used as a nonlinear optical chromophore. (4-diphenylamino)phenyl)methanol (TPAOH) is used as a plasticizer. Consequently, a diffraction efficiency of 76 % and a response time of 8 ms were obtained with 532 nm green laser under the electric field of 55 V μm-1. As a conclusion, the introduction of PBI is a promising approach for the photorefractive composite owning the video rate response.

  15. Large-Scale Quantum Many-Body Perturbation on Spin and Charge Separation in the Excited States of the Synthesized Donor-Acceptor Hybrid PBI-Macrocycle Complex.

    PubMed

    Ziaei, Vafa; Bredow, Thomas

    2017-03-17

    The reliable calculation of the excited states of charge-transfer (CT) compounds poses a major challenge to the ab initio community because the frequently employed method, time-dependent density functional theory (TD-DFT), massively relies on the underlying density functional, resulting in heavily Hartree-Fock (HF) exchange-dependent excited-state energies. By applying the highly sophisticated many-body perturbation approach, we address the encountered unreliabilities and inconsistencies of not optimally tuned (standard) TD-DFT regarding photo-excited CT phenomena, and present results concerning accurate vertical transition energies and the correct energetic ordering of the CT and the first visible singlet state of a recently synthesized thermodynamically stable large hybrid perylene bisimide-macrocycle complex. This is a large-scale application of the quantum many-body perturbation approach to a chemically relevant CT system, demonstrating the system-size independence of the quality of the many-body-based excitation energies. Furthermore, an optimal tuning of the ωB97X hybrid functional can well reproduce the many-body results, making TD-DFT a suitable choice but at the expense of introducing a range-separation parameter, which needs to be optimally tuned. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. The preparation of nylon-tube-supported hexokinase and glucose 6-phosphate dehydrogenase and the use of the co-immobilized enzymes in the automated determination of glucose.

    PubMed Central

    Morris, D L; Campbell, J; Hornby, W E

    1975-01-01

    Triethyloxonium tetrafluoroborate was used to O-alkylate nylon-tube thus producing the imidate salt of the nylon which was further made to react with 1,6-diaminohexane. 2. Hexokinase (EC 2.7.1.1) and glucose 6-phosphate dehydrogenase (EC 1.1.1.49) were immobilized on the amino-substituted nylon tube through glutaraldeyde and bisimidates. 3. The effect of varying the conditions of O-alkylation and the amount of enzyme immobilized on the activity of nylon tube-hexokinase derivatives was determined. 4. The effect of varying the amount of enzyme immobilized on the activity of nylon-tube-glucose 6-phosphate dehydrogenase derivatives was determined. 5. The thermal stability of nylon-tube-hexokinase and nylon-tube-glucose 6-phosphate dehydrogenase derivatives was studied. 6. Different ratios of hexokinase and glucose 6-phosphate dehydrogenase were co-immobilized on nylon tube, and the rate of conversion of glucose into 6-phosphogluconolactone was compared with the individual activities of the immobilized enzymes. 7. Hexokinase and glucose 6-phosphate dehydrogenase co-immobilized on nylon tube were used in the automated analysis of glucose. PMID:1167161

  17. Cyclization and Catenation Directed by Molecular Self-Assembly

    SciTech Connect

    Wang, Wei; Wang, Li Q; Palmer, Bruce J; Exarhos, Gregory J; Li, Alexander D

    2006-08-30

    We report here that molecular self-assembly can effectively direct and enhance specific reaction pathways. Using perylene π-π stacking weak attractive forces, we succeeded in synthesizing perylene bisimide macrocyclic dimer and a concatenated dimer-dimer ring from dynamic self-assembly of monomeric bis-N, N’-(2-(2-(2-(2-thioacetyl ethoxy) ethoxy) ethoxy) ethyl) perylene tetracarboxylic diimide. The monocyclic ring closure and the dimer-dimer ring concatenation were accomplished through formation of disulfide bonds, which was readily triggered by air oxidization under basic deacetylation conditions. The perylene cyclic dimer and its concatenated tetramer were characterized using both structural methods (NMR, mass spectroscopy) and photophysical measurements (UV-vis spectroscopy). Kinetic analyses offer informative insights about reaction pathways and possible mechanisms, which lead to the formation of fascinating concatenated rings. Molecular dynamic behaviors of both the monocyclic dimer and the concatenated dimer-dimer ring were modeled with the NWChem molecular dynamics software module, which shows distinct stacking activities for the monocyclic dimer and the concatenated tetramer.

  18. Reevaluation of Tetrahydrophthalic Anhydride as an End Cap for Improved Oxidation Resistance in Addition Polyimides

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B.; Frimer, Aryeh A.; Johnston, J. Christopher

    2003-01-01

    Several substituted 1,2,3,6-tetrahydrophthalic anhydride end caps - including the 3-phenyl, 3-methoxy, 3-trimethylsilyloxy, and 3,6-diphenyl analogs - were synthesized via the Diels-Alder condensation of the corresponding butadienes and maleic anhydride. These anhydrides, as well as the commercially available 3-hydro and 4-methyl analogs, were each ground together with methylenedianiline in a 2:1 ratio and heated gradually from 204 C to 371 C, with the thermolysis followed by NMR. Generally speaking, a transformation via monoimide to bisimide was observed in the lower temperature range, followed by competition between crosslinking and aromatization. We believe that this competition produces a substantial percentage of aromatic product, with the concomitant lowering of the relative amount of crosslinking and is responsible for improving both thermal oxidative stability of tetrahydrophthalic end capped polyimides and their substantial frangibility. The thermolysis of the tetrahydrophthalimides under inert atmosphere dramatically lowers the amount of aromatization hence, the mechanism for aromatization is an oxidative one.

  19. Sensitivity and specificity of PS/AA-modified nanoparticles used in malaria detection.

    PubMed

    Thiramanas, Raweewan; Jangpatarapongsa, Kulachart; Asawapirom, Udom; Tangboriboonrat, Pramuan; Polpanich, Duangporn

    2013-07-01

    Polystyrene (PS) nanoparticle (NP) copolymerized with acrylic acid (AA) and coloured monomer, i.e. 2,3,6,7-tetra(2,2'-bithiophene)-1,4,5,8-naphthalenetetracarboxylic-N,N'-di(2-methylallyl)-bisimide (ALN8T), was synthesized via the miniemulsion polymerization. Before applying for malaria antigen detection, the blue NP was conjugated with human polyclonal malaria IgG antibody (Ab) specific to Plasmodium falciparum. For the conjugation, three methods, i.e. physical adsorption, covalent coupling and affinity binding via streptavidin (SA) and biotin interaction, were employed. The optimum ratio of Ab to NPs used in each immobilization procedure and the latex agglutination test based on the reaction between Ab conjugated NPs and malaria patient plasma were investigated. All Ab-latex conjugates provided the high sensitivity for the detection of P. falciparum malaria plasma. The highest specificity to P. falciparum was obtained from using Ab-NPs conjugated via the SA-biotin interaction. © 2013 The Authors. Microbial Biotechnology published by John Wiley & Sons Ltd and Society for Applied Microbiology.

  20. Sensitivity and specificity of PS/AA-modified nanoparticles used in malaria detection

    PubMed Central

    Thiramanas, Raweewan; Jangpatarapongsa, Kulachart; Asawapirom, Udom; Tangboriboonrat, Pramuan; Polpanich, Duangporn

    2013-01-01

    Summary Polystyrene (PS) nanoparticle (NP) copolymerized with acrylic acid (AA) and coloured monomer, i.e. 2,3,6,7-tetra(2,2′-bithiophene)-1,4,5,8-naphthalenetetracarboxylic-N,N′-di(2-methylallyl)-bisimide (ALN8T), was synthesized via the miniemulsion polymerization. Before applying for malaria antigen detection, the blue NP was conjugated with human polyclonal malaria IgG antibody (Ab) specific to Plasmodium falciparum. For the conjugation, three methods, i.e. physical adsorption, covalent coupling and affinity binding via streptavidin (SA) and biotin interaction, were employed. The optimum ratio of Ab to NPs used in each immobilization procedure and the latex agglutination test based on the reaction between Ab conjugated NPs and malaria patient plasma were investigated. All Ab–latex conjugates provided the high sensitivity for the detection of P. falciparum malaria plasma. The highest specificity to P. falciparum was obtained from using Ab–NPs conjugated via the SA–biotin interaction. PMID:23298152

  1. P3HT:DiPBI bulk heterojunction solar cells: morphology and electronic structure probed by multiscale simulation and UV/vis spectroscopy.

    PubMed

    Winands, Thorsten; Böckmann, Marcus; Schemme, Thomas; Ly, Phong-Minh Timmy; de Jong, Djurre H; Wang, Zhaohui; Denz, Cornelia; Heuer, Andreas; Doltsinis, Nikos L

    2016-02-17

    Coarse grained molecular dynamics simulations are performed for a mixture of poly(3-hexylthiophene) (P3HT) and diperylene bisimide (DiPBI). The effect of different annealing and cooling protocols on the morphology is investigated and the resulting domain structures are analyzed. In particular, π-stacked clusters of DiPBI molecules are observed whose size decreases with increasing temperature. Domain structure and diffusivity data suggest that the DiPBI subsystem undergoes an order → disorder phase transition between 700 and 900 K. Electronic structure calculations based on density functional theory are carried out after backmapping the coarse grained model onto an atomistic force field representation built upon first principles. UV/vis absorption spectra of the P3HT:DiPBI mixture are computed using time-dependent density functional linear response theory and recorded experimentally for a spin-coated thin film. It is demonstrated that the absorption spectrum depends sensitively on the details of the amorphous structure, thus providing valuable insight into the morphology. In particular, the results show that the tempering procedure has a significant influence on the material's electronic properties. This knowledge may help to develop effective processing routines to enhance the performance of bulk heterojunction solar cells.

  2. Fire and heat resistant laminating resin based on maleimido and citraconimido substituted 1-(diorganooxyphosphonyl-methyl)-2,4- and -2,6-diaminobenzenes

    NASA Technical Reports Server (NTRS)

    Beggs, James M. (Inventor); Mikroyannidis, John A. (Inventor); Kourtides, Demetrius A. (Inventor)

    1988-01-01

    The subject invention pertains to a novel class of fire-and heat-resistant bisimide resins prepared by thermal polymerization of maleimido or citraconimido substituded 1-(dialkoxyphosphonyl)-methyl-2-4 and -2,6-diaminobenzenes. Typical polymer presursors have the chemical structure wherein R is alkyl, substituted alkyl or aryl, and R sup 1 is hydrogen or lower alkyl. The polymer precursors are prepared by reacting 1-(diorganooxyphosphonyl)methyl-2-4 and -2,6-diaminobenzenes with maleic anhydride or citraconic anhydride in a mole ratio 1:2. Chains extension of the monomers is achieved by reacting the mono-N-maleimido derivatives of 1-(diorganooxyphosphonyl)methyl-2,4 and -2,6-diaminobenzenes with aryl tetracarboxylic dianhydrides, such as benzophenone tetracarboxylic diandydride, or aryl diisocyanates, such as methylenebis (4-phenylisocyanate), in a mole ratio 2:1. The polymerization of the monomers is studied by differential scanning calorimetry (DSC) and the thermal stability of the polymers is ascertained by thermogravimetric analysis (TGA).

  3. Dipole-moment-driven cooperative supramolecular polymerization.

    PubMed

    Kulkarni, Chidambar; Bejagam, Karteek K; Senanayak, Satyaprasad P; Narayan, K S; Balasubramanian, S; George, Subi J

    2015-03-25

    While the mechanism of self-assembly of π-conjugated molecules has been well studied to gain control over the structure and functionality of supramolecular polymers, the intermolecular interactions underpinning it are poorly understood. Here, we study the mechanism of self-assembly of perylene bisimide derivatives possessing dipolar carbonate groups as linkers. It was observed that the combination of carbonate linkers and cholesterol/dihydrocholesterol self-assembling moieties led to a cooperative mechanism of self-assembly. Atomistic molecular dynamics simulations of an assembly in explicit solvent strongly suggest that the dipole-dipole interaction between the carbonate groups imparts a macro-dipolar character to the assembly. This is confirmed experimentally through the observation of a significant polarization in the bulk phase for molecules following a cooperative mechanism. The cooperativity is attributed to the presence of dipole-dipole interaction in the assembly. Thus, anisotropic long-range intermolecular interactions such as dipole-dipole interaction can serve as a way to obtain cooperative self-assembly and aid in rationalizing and predicting the mechanisms in various synthetic supramolecular polymers.

  4. Phosphorus-containing imide resins - Modification by elastomers

    NASA Technical Reports Server (NTRS)

    Varma, I. K.; Fohlen, G. M.; Parker, J. A.; Varma, D. S.

    1984-01-01

    The syntheses and general features of addition-type maleimide resins based on bis(m-aminophenyl)phosphine oxide and tris(m-aminophenyl)phosphine oxide have been reported previously. These resins have been used to fabricate graphite cloth laminates having excellent flame resistance. These composites did not burn even in pure oxygen. However, these resins were somewhat brittle. This paper reports the modification of these phosphorus-containing resins by an amine-terminated butadiene-acrylonitrile copolymer (ATBN) and a perfluoroalkylene diaromatic amine elastomer (3F). An approximately two-fold increase in short beam shear strength and flexural strength was observed at 7 percent ATBN concentration. The tensile, flexural, and shear strengths were reduced when 18 percent ATBN was used. Anaerobic char yields of the resins at 800 C and the limiting oxygen indexes of the laminates decreased with increasing ATBN concentration. The perfluorodiamine (3F) was used with both imide resins at 6.4 percent concentration. The shear strength was doubled in the case of the bisimide with no loss of flammability characteristics. The modified trisimide laminate also had improved properties over the unmodified one. The dynamic mechanical analysis of a four-ply laminate indicated a glass transition temperature above 300 C. Scanning electron micrographs of the ATBN modified imide resins were also recorded.

  5. Charge carrier mobilities in organic semiconductor crystals based on the spectral overlap.

    PubMed

    Stehr, Vera; Fink, Reinhold F; Deibel, Carsten; Engels, Bernd

    2016-09-05

    The prediction of substance-related charge-transport properties is important for the tayloring of new materials for organic devices, such as organic solar cells. Assuming a hopping process, the Marcus theory is frequently used to model charge transport. Here another approach, which is already widely used for exciton transport, is adapted to charge transport. It is based on the spectral overlap of the vibrational donor and acceptor spectra. As the Marcus theory it is derived from Fermi's Golden rule, however, it contains less approximations, as the molecular vibrations are treated quantum mechanically. In contrast, the Marcus theory reduces all vibrational degrees of freedom to one and treats its influence classically. The approach is tested on different acenes and predicts most of the experimentally available hole mobilities in these materials within a factor of 2. This represents a significant improvement to values obtained from Marcus theory which is qualitatively correct but frequently overestimates the mobilities by factors up to 10. Furthermore, the charge-transport properties of two derivatives of perylene bisimide are investigated. © 2016 Wiley Periodicals, Inc.

  6. Solvent Clathrate Driven Dynamic Stereomutation of a Supramolecular Polymer with Molecular Pockets.

    PubMed

    Kulkarni, Chidambar; Korevaar, Peter A; Bejagam, Karteek K; Palmans, Anja R A; Meijer, E W; George, Subi J

    2017-09-26

    Control over the helical organization of synthetic supramolecular systems is intensively pursued to manifest chirality in a wide range of applications ranging from electron spin filters to artificial enzymes. Typically, switching the helicity of supramolecular assemblies involves external stimuli or kinetic traps. However, efforts to achieve helix reversal under thermodynamic control and to understand the phenomena at a molecular level are scarce. Here we present a unique example of helix reversal (stereomutation) under thermodynamic control in the self-assembly of a coronene bisimide that has a 3,5-dialkoxy substitution on the imide phenyl groups (CBI-35CH), leading to "molecular pockets" in the assembly. The stereomutation was observed only if the CBI monomer possesses molecular pockets. Detailed chiroptical studies performed in alkane solvents with different molecular structures reveal that solvent molecules intercalate or form clathrates within the molecular pockets of CBI-35CH at low temperature (263 K), thereby triggering the stereomutation. The interplay among the helical assembly, molecular pockets, and solvent molecules is further unraveled by explicit solvent molecular dynamics simulations. Our results demonstrate how the molecular design of self-assembling building blocks can orchestrate the organization of surrounding solvent molecules, which in turn dictates the helical organization of the resulting supramolecular assembly.

  7. Tuning Supramolecular Structure and Functions of Peptide bola-Amphiphile by Solvent Evaporation-Dissolution.

    PubMed

    Wang, Anhe; Cui, Lingyun; Debnath, Sisir; Dong, Qianqian; Yan, Xuehai; Zhang, Xi; Ulijn, Rein V; Bai, Shuo

    2017-06-28

    Solvent molecules significantly affect the supramolecular self-assembly, for example, in forming solvent-bridged hydrogen bonding networks. Even small changes in solvent composition can have dramatic impact on supramolecular assembly. Herein, we demonstrate the use of trace solvents (as low as 0.04%) to tune the morphology and consequent functions of supramolecular nanostructures based on an aromatic peptide bola-amphiphile. Specifically, perylene bisimide-(di)glycine-tyrosine (PBI-[GY]2) bola-amphiphile was shown to give rise to red-emitting nanofibers when assembled in water, while exposure to trace organic solvents such as tetrahydrofuran (THF) and others via solvent-evaporation followed by aqueous assembly gave rise to white-light-emitting nanospheres. Differential hydrogen bonding between water (donor and acceptor) and THF (acceptor only) impacts supramolecular organization, which was verified using a density functional theory (DFT) simulation. The tunable consequent surface hydrophobicity was utilized in staining the cytoplasm and membrane of cells, respectively. The trace-solvent effect achieved through evaporation-dissolution provides a methodology to mediate the morphologies and consequent functions for supramolecular biomaterials controlled by the self-assembly pathway.

  8. Electrochemical Capture and Release of CO2 in Aqueous Electrolytes Using an Organic Semiconductor Electrode

    PubMed Central

    2017-01-01

    Developing efficient methods for capture and controlled release of carbon dioxide is crucial to any carbon capture and utilization technology. Herein we present an approach using an organic semiconductor electrode to electrochemically capture dissolved CO2 in aqueous electrolytes. The process relies on electrochemical reduction of a thin film of a naphthalene bisimide derivative, 2,7-bis(4-(2-(2-ethylhexyl)thiazol-4-yl)phenyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (NBIT). This molecule is specifically tailored to afford one-electron reversible and one-electron quasi-reversible reduction in aqueous conditions while not dissolving or degrading. The reduced NBIT reacts with CO2 to form a stable semicarbonate salt, which can be subsequently oxidized electrochemically to release CO2. The semicarbonate structure is confirmed by in situ IR spectroelectrochemistry. This process of capturing and releasing carbon dioxide can be realized in an oxygen-free environment under ambient pressure and temperature, with uptake efficiency for CO2 capture of ∼2.3 mmol g–1. This is on par with the best solution-phase amine chemical capture technologies available today. PMID:28378994

  9. Blue, green, and orange-red emission from polystyrene microbeads for solid-state white-light and multicolor emission.

    PubMed

    Sonawane, Swapnil L; Asha, S K

    2014-08-07

    Solid-state white-light emission was achieved from polystyrene (PS) microbeads incorporated with fluorophores based on perylene bisimide (PBITEG) and oligo(p-phenylenevinylene) (OPV) as acrylic cross-linkers. The PS beads incorporated with only PBITEG gave intense orange-red emission; PS incorporated with OPV exhibited blue-emission, whereas a series of polymers incorporating both cross-linkers exhibited varying shades of white-light emission. One of the PS samples, PS-PBITEG-6.25-OPV-4.28 (PBITEG incorporation: 6.25 × 10(-7) mole; OPV incorporation: 4.28 × 10(-7) mol), exhibited pure white-light emission in the powder form with CIE coordinates (0.33, 0.32). The rigid aromatic cross-linkers were incorporated into the PS backbone in a two-stage dispersion polymerization to afford PS beads in the size range 2 to 3 μm. The incorporation of fluorophores as cross-linkers enabled covalent attachment of the dye to the polymer backbone, avoiding dye leakage besides avoiding aggregation-induced fluorescence quenching.

  10. Cleavage of hydrazine and 1,1-dimethylhydrazine by dinuclear tantalum hydrides: formation of imides, nitrides, and N,N-dimethylamine.

    PubMed

    Shaver, Michael P; Fryzuk, Michael D

    2005-01-19

    The complexes (RPh[NPN]Ta)2(mu-H)4 (RPh[NPN] = RP(CH2SiMe2NPh)2) activate molecular nitrogen to give (RPh[NPN]Ta)2(mu-eta1-eta2-N2)(mu-H)2; however, addition of hydrazine to (CyPh[NPN]Ta)2(mu-H)4 promotes cleavage of the N-N bond and N-H activation to give the bridging bisimide complex (CyPh[NPN]Ta)2(mu-H)2(mu-NH)2. Substitution of the phosphine substituent from cyclohexyl to phenyl allows for characterization of (PhPh[NPN]Ta)2(mu-H)2(mu-NH)2 crystallographically. Addition of the substituted hydrazine Me2NNH2 results in formation of a mono(nitride) complex, (RPh[NPN]Ta)2(mu-H)3(mu-N). The N-N bond has again been cleaved, but the second nitrogen atom has been functionalized and ejected as Me2NH.

  11. Hierarchical Assembly of Model Cell Surfaces: Synthesis of Mucin Mimetic Polymers and their Display on Supported Bilayers

    PubMed Central

    Rabuka, David; Parthasarathy, Raghuveer; Lee, Goo Soo; Chen, Xing; Groves, Jay T.; Bertozzi, Carolyn R.

    2008-01-01

    Molecular level analysis of cell surface phenomena could benefit from model systems comprising structurally-defined components. Here we present the first step toward bottom-up assembly of model cell surfaces – the synthesis of mucin mimetics and their incorporation into artificial membranes. Natural mucins are densely glycosylated O-linked glycoproteins that serve numerous functions on cell surfaces. Their large size and extensive glycosylation makes the synthesis of these biopolymers impractical. We designed synthetically tractable glycosylated polymers that possess rod-like extended conformations similar to natural mucins. The glycosylated polymers were end-functionalized with lipid groups and embedded into supported lipid bilayers where they interact with protein receptors in a structure-dependent manner. Furthermore, their dynamic behavior in synthetic membranes mirrored that of natural biomolecules. This system provides a unique framework with which to study the behavior of mucin-like macromolecules in a controlled, cell surface-mimetic environment. PMID:17425309

  12. Dissecting biological "dark matter" with single-cell genetic analysis of rare and uncultivated TM7 microbes from the human mouth.

    PubMed

    Marcy, Yann; Ouverney, Cleber; Bik, Elisabeth M; Lösekann, Tina; Ivanova, Natalia; Martin, Hector Garcia; Szeto, Ernest; Platt, Darren; Hugenholtz, Philip; Relman, David A; Quake, Stephen R

    2007-07-17

    We have developed a microfluidic device that allows the isolation and genome amplification of individual microbial cells, thereby enabling organism-level genomic analysis of complex microbial ecosystems without the need for culture. This device was used to perform a directed survey of the human subgingival crevice and to isolate bacteria having rod-like morphology. Several isolated microbes had a 16S rRNA sequence that placed them in candidate phylum TM7, which has no cultivated or sequenced members. Genome amplification from individual TM7 cells allowed us to sequence and assemble >1,000 genes, providing insight into the physiology of members of this phylum. This approach enables single-cell genetic analysis of any uncultivated minority member of a microbial community.

  13. Fabrication of shape controlled Fe{sub 3}O{sub 4} nanostructure

    SciTech Connect

    Zheng, Y.Y.; Wang, X.B.; Shang, L.; Li, C.R.; Cui, C.; Dong, W.J.; Tang, W.H.; Chen, B.Y.

    2010-04-15

    Shape-controlled Fe{sub 3}O{sub 4} nanostructure has been successfully prepared using polyethylene glycol as template in a water system at room temperature. Different morphologies of Fe{sub 3}O{sub 4} nanostructures, including spherical, cubic, rod-like, and dendritic nanostructure, were obtained by carefully controlling the concentration of the Fe{sup 3+}, Fe{sup 2+}, and the molecular weight of the polyethylene glycol. Transmission Electron Microscope images, X-ray powder diffraction patterns and magnetic properties were used to characterize the final product. This easy procedure for Fe{sub 3}O{sub 4} nanostructure fabrication offers the possibility of a generalized approach to the production of single and complex nanocrystalline oxide with tunable morphology.

  14. Recessive RYR1 mutations in a patient with severe congenital nemaline myopathy with ophthalomoplegia identified through massively parallel sequencing.

    PubMed

    Kondo, Eri; Nishimura, Takafumi; Kosho, Tomoki; Inaba, Yuji; Mitsuhashi, Satomi; Ishida, Takefumi; Baba, Atsushi; Koike, Kenichi; Nishino, Ichizo; Nonaka, Ikuya; Furukawa, Toru; Saito, Kayoko

    2012-04-01

    Nemaline myopathy (NM) is a group of congenital myopathies, characterized by the presence of distinct rod-like inclusions "nemaline bodies" in the sarcoplasm of skeletal muscle fibers. To date, ACTA1, NEB, TPM3, TPM2, TNNT1, and CFL2 have been found to cause NM. We have identified recessive RYR1 mutations in a patient with severe congenital NM, through high-throughput screening of congenital myopathy/muscular dystrophy-related genes using massively parallel sequencing with target gene capture. The patient manifested fetal akinesia, neonatal severe hypotonia with muscle weakness, respiratory insufficiency, swallowing disturbance, and ophthalomoplegia. Skeletal muscle histology demonstrated nemaline bodies and small type 1 fibers, but without central cores or minicores. Congenital myopathies, a molecularly, histopathologically, and clinically heterogeneous group of disorders are considered to be a good candidate for massively parallel sequencing. Copyright © 2012 Wiley Periodicals, Inc.

  15. Virus hybrids as nanomaterials for biotechnology.

    PubMed

    Soto, Carissa M; Ratna, Banahalli R

    2010-08-01

    The current review describes advances in the field of bionanotechnology in which viruses are used to fabricate nanomaterials. Viruses are introduced as protein cages, scaffolds, and templates for the production of biohybrid nanostructured materials where organic and inorganic molecules are incorporated in a precise and a controlled fashion. Genetic engineering enables the insertion or replacement of selected amino acids on virus capsids for uses from bioconjugation to crystal growth. The variety of nanomaterials generated in rod-like and spherical viruses is highlighted for tobacco mosaic virus (TMV), M13 bacteriophage, cowpea chlorotic mottle virus (CCMV), and cowpea mosaic virus (CPMV). Functional biohybrid nanomaterials find applications in biosensing, memory devices, nanocircuits, light-harvesting systems, and nanobatteries. Published by Elsevier Ltd.

  16. Filamentous Phages As a Model System in Soft Matter Physics

    PubMed Central

    Dogic, Zvonimir

    2016-01-01

    Filamentous phages have unique physical properties, such as uniform particle lengths, that are not found in other model systems of rod-like colloidal particles. Consequently, suspensions of such phages provided powerful model systems that have advanced our understanding of soft matter physics in general and liquid crystals in particular. We described some of these advances. In particular we briefly summarize how suspensions of filamentous phages have provided valuable insight into the field of colloidal liquid crystals. We also describe recent experiments on filamentous phages that have elucidated a robust pathway for assembly of 2D membrane-like materials. Finally, we outline unique structural properties of filamentous phages that have so far remained largely unexplored yet have the potential to further advance soft matter physics and material science. PMID:27446051

  17. Biomimetic synthesis of calcium carbonate with different morphologies and polymorphs in the presence of bovine serum albumin and soluble starch.

    PubMed

    Liu, Yuxi; Chen, Yuping; Huang, Xuechen; Wu, Gang

    2017-10-01

    Calcium carbonate has been synthesized by the reaction of Na2CO3 and CaCl2 in the presence of bovine serum albumin (BSA) and soluble starch. Effects of various bovine serum albumin (BSA) and soluble starch on the polymorph and morphology of CaCO3 crystals were investigated. Crystallization of vaterite is favored in the presence of BSA and soluble starch, respectively, while calcite is favored in the presence of a mixture of BSA and soluble starch. The morphologies of CaCO3 particles in the presence of mixture of BSA and soluble starch are mainly rod-like, suggesting that the BSA, soluble and their assemblies play key roles in stabilizing and directing the CaCO3 crystal growth. Copyright © 2017. Published by Elsevier B.V.

  18. Efficient Thermolysis Route to Monodisperse Cu2ZnSnS4 Nanocrystals with Controlled Shape and Structure

    PubMed Central

    Zhang, Xiaoyan; Guo, Guobiao; Ji, Cheng; Huang, Kai; Zha, Chenyang; Wang, Yifeng; Shen, Liming; Gupta, Arunava; Bao, Ningzhong

    2014-01-01

    Monodisperse Cu2ZnSnS4 (CZTS) nanocrystals with tunable shape, crystalline phase, and composition are synthesized by efficient thermolysis of a single source precursor of mixed metal-oleate complexes in hot organic solvents with dissolved sulfur sources. Suitable tuning of the synthetic conditions and the Cu/(Zn + Sn) ratio of the precursor has enabled precise control of the crystalline phase in the form of kesterite, or a newly observed wurtzite structure. Nanocrystals with morphology in the form of spherical, rice-like, or rod-like shapes are obtained over a wide range of compositions (0.5 ≤ Cu/(Zn + Sn) ≤ 1.2). Both the final products and intermediates for each shape exhibit consistent composition and structure, indicating homogenous nucleation and growth of single-phase nanocrystals. Thin films prepared from colloidal nanocrystal suspensions display interesting shape-dependent photoresponse behavior under white light illumination from a solar simulator. PMID:24866987

  19. 40% Efficiency enhancement in solar cells using ZnO nanorods as shell prepared via novel hydrothermal synthesis

    NASA Astrophysics Data System (ADS)

    Ebadi, Mohammad; Zarghami, Zabihullah; Motevalli, Kourosh

    2017-03-01

    Herein, rod-like ZnO nanostructures were synthesized via a novel hydrothermal route using Zn(OAc)2, ethylenediamine and hydrazine as a new set of starting reagents. The as-synthesized products were characterized by techniques including XRD, EDS, SEM, XPS, Pl and FTIR. The prepared ZnO nanostructures were utilized as shell on TiO2 film in DSSCs. Effect of precursor type, morphology and thickness of ZnO shell (number of electrophoresis cycle) on solar cells efficiency were well studied. Our results showed that ethylenediamine has crucial effect on morphology of synthesized ZnO nanostructures and using ZnO nanostructures leads to an increase in DSSCs efficiency compared to bare TiO2 from 4.66 to 7.13% ( 40% improvement). Moreover, highest amount of solar cell efficiency (7.13%) was obtained by using ZnO nanorods with two cycle of electrophoresis for deposition.

  20. A new species of Strongylacron (Copepoda, Harpacticoida, Cletodidae) from intertidal mudflats in the Korean peninsula

    PubMed Central

    Kim, Jong Guk; Jung, Tae Won; Yoon, Seong Myeong

    2016-01-01

    Abstract A new species, Strongylacron glabrum sp. n. is described from intertidal mudflats in the Korean peninsula. The new species is assigned to the monospecific genus Strongylacron Gee & Huys, 1996 in accordance with the generic morphological features of the rostrum, antennary exopod, and thoracic legs. However, Strongylacron glabrum sp. n. is clearly distinguished from the type species, Strongylacron buchholtzi (Boeck, 1873), by the naked anterior margin of rostrum, the elongate exopod and endopodal lobe of female P5 approximately 3.5 and 2.7 times as long as width, respectively, and the presence of 8–10 rod-like projections on prosomites. The genus Strongylacron is first recorded from Korean waters by the present study. PMID:27667951

  1. Light absorption and plasmon – exciton interaction in three-layer nanorods with a gold core and outer shell composed of molecular J- and H-aggregates of dyes

    SciTech Connect

    Shapiro, B I; Tyshkunova, E S; Kondorskiy, A D; Lebedev, V S

    2015-12-31

    Optical properties of hybrid rod-like nanoparticles, consisting of a gold core, an intermediate passive organic layer (spacer) and outer layer of ordered molecular cyanine dye aggregates, are experimentally and theoretically investigated. It is shown that these dyes can form not only ordered J-aggregates but also H-aggregates (differing by the packing angle of dye molecules in an aggregate and having other spectral characteristics) in the outer shell of the hybrid nanostructure. Absorption spectra of synthesised three-layer nanorods are recorded, and their sizes are determined. The optical properties of the composite nanostructures under study are found to differ significantly, depending on the type of the molecular aggregate formed in the outer shell. The experimental data are quantitatively explained based on computer simulation using the finite-difference time-domain (FDTD) method, and characteristic features of the plasmon – exciton interaction in the systems under study are revealed. (nanophotonics)

  2. Length-dependence of intramolecular electron transfer in σ-bonded rigid molecular rods: an ab initio molecular orbital study

    NASA Astrophysics Data System (ADS)

    Pati, Ranjit; Karna, Shashi P.

    2002-01-01

    The dependence of electron transfer (ET) coupling element, VAB, on the length of rigid-rod-like systems consisting of bicyclo[1.1.1]pentane (BCP), cubane (CUB), and bicyclo[2.2.2]octane (BCO) monomers, has been investigated with the use of ab initio Hartree-Fock (HF) method employing Marcus-Hush two-state (TS) model. The value of VAB decreases exponentially with increase in the number of the cage units of the σ-bonded molecules. The calculated decay constant, β, shows good agreement with previously reported data. For molecular length⩾15 Å, the value of VAB becomes negligibly small, suggesting complete suppression of the through bond direct tunneling contribution to ET process.

  3. The human RNA polymerase II interacts with the terminal stem-loop regions of the hepatitis delta virus RNA genome

    SciTech Connect

    Greco-Stewart, Valerie S.; Miron, Paul; Abrahem, Abrahem; Pelchat, Martin . E-mail: mpelchat@uottawa.ca

    2007-01-05

    The hepatitis delta virus (HDV) is an RNA virus that depends on DNA-dependent RNA polymerase (RNAP) for its transcription and replication. While it is generally accepted that RNAP II is involved in HDV replication, its interaction with HDV RNA requires confirmation. A monoclonal antibody specific to the carboxy terminal domain of the largest subunit of RNAP II was used to establish the association of RNAP II with both polarities of HDV RNA in HeLa cells. Co-immunoprecipitations using HeLa nuclear extract revealed that RNAP II interacts with HDV-derived RNAs at sites located within the terminal stem-loop domains of both polarities of HDV RNA. Analysis of these regions revealed a strong selection to maintain a rod-like conformation and demonstrated several conserved features. These results provide the first direct evidence of an association between human RNAP II and HDV RNA and suggest two transcription start sites on both polarities of HDV RNA.

  4. Positional-dependent luminescence property of β-SiAlON:Eu2+ phosphor particle

    NASA Astrophysics Data System (ADS)

    Zhang, Chenning; Uchikoshi, Tetsuo; Liu, Lihong; Dierre, Benjamin; Sakka, Yoshio; Hirosaki, Naoto

    2014-01-01

    The relationship between the luminescence property and particle faces of the β-SiAlON:Eu2+ phosphors was investigated by performing the cathodoluminescence (CL) measurements on the tip and side faces of the rod-like phosphor particles. It was found a positional dependence of the CL intensity on the particle faces, that is, the side face possessed higher CL intensity than the tip face, probably due to uneven distribution of the Eu2+ sites in the β-SiAlON host particles: the Eu2+ ions more intensively concentrated at the side face of the particle, particularly at the central area of the side face, than at the tip face.

  5. Photoinduced electron transfer in ordered polymers

    SciTech Connect

    Jones, G. II.

    1993-01-01

    The present report gives a brief account of the following elements of work related to photochemical electron transfer themes: (1) the synthesis and Photochemical characterization of chromophore-bound peptides and amino acid model compounds based on the amino acids, tryptophan and the spacer residue, alanine (Ala); (2) the study of binding of cationic organic dyes to a peptide electrolyte, for which cooperative dye loading and helix formation is important; (3) the completion of work on a new series of acridinium chromophores that have rod-like'' arrangements of linked aryl rings for assembly of electron donor-acceptor systems that exhibit long lived charge separation; and (4) use of the modified form of the peptide, poly-L-histidine, as a template for sulfide oxidation.

  6. Annealing behaviors of residual defects in high-dose BF +2-implanted (001)Si under different implantation conditions

    NASA Astrophysics Data System (ADS)

    Chu, C. H.; Tsai, E. L.; Chao, W. Y.; Chen, L. J.

    1991-04-01

    The annealing behavior of residual defects in high-dose BF +2-implanted (001)Si under different implantation conditions has been studied by cross-sectional transmission electron microscopy and four-point probe sheet resistance measurements. Three kinds of samples were prepared with different implanters. M, MC and H samples were implanted with 80 keV, 4×10 15/cm 2 BF +2 in a medium-current implanter without deliberate end-station cooling, a medium-current implanter with a freon-cooled end station, and a high-current implanter with a water-cooled end station, respectively. The BF +2 ion dissociation effects were revealed by the comparison of M or MC and H samples. Rod-like and equi-axial dislocation loops beneath the original a/c interface were observed in the M and MC samples. The dopant activation of the annealed samples was found to correlate well with microstructural changes.

  7. Conformational change from rigid rod to star: a triple-helical peptide with a linker domain at the C-terminal end.

    PubMed

    Terao, Ken; Mizuno, Kazunori; Bächinger, Hans Peter

    2015-03-05

    Small-angle X-ray scattering and circular dichroism measurements were made for a triple-helical peptide of which one end was linked by the thermally stable trimerization domain of type XIX collagen. The radius of gyration decreased steeply around the transition temperature while the scattering intensity at zero angle did not significantly change, indicating no molar mass change through the conformational transition. Thus, the data were analyzed in terms of the rigid cylinder model for the data at low temperatures and the wormlike star model at high temperatures. It was confirmed that the peptide molecules behave as a rod-like cylinder at low temperature and a semi flexible three-arm star-like chain at high temperature of which the single-coil peptide chain is appreciably extended by the high segment density nearby the linking domain.

  8. Bound water in Kevlar 49 fibers

    SciTech Connect

    Garza, R.G.; Pruneda, C.O.; Morgan, R.J.

    1981-04-01

    From elemental analyses, thermogravimetric-mass spectroscopy studies and re-evaluation of previous water diffusion studies in Kevlar 49 fibers it is concluded that these fibers can contain two types of sorbed moisture. The fibers can absorb up to approx. 6 wt % loosely bound water with an activation energy for outgassing by desorption of 6 kcal/mole. This loosely bound water is a direct result of the presence of Na/sub 2/SO/sub 4/ impurities and the perturbations they induce on the packing of the rod-like poly (p-phenylene terephthalamide) macromolecules. Kevlar 49 fibers also inherently contain up to 30 wt % additional water which is tightly bound within the crystal lattice. This water exhibits an activation energy for outgassing by diffusion of approx. 40 kcal/mole and is only evolved from the fiber in significant quantities at t > 350/sup 0/C over a period of hours.

  9. A new human gene (DXS1357E) with ubiquitous expression, located in Xq28 adjacent to the adrenoleukodystrophy gene

    SciTech Connect

    Mosser, J.; Sarde, C.O.; Vicaire, S.

    1994-07-15

    The authors have isolated a new human gene (DXS1357E; laboratory name: CDM) localized in Xq28. This gene is transcribed from the same CpG island as the adrenoleukodystrophy gene (ALD) and is oriented in the opposite direction. It encodes a 1.5-kb transcript that exhibits ubiquitous expression and contains a single open reading frame. The 246 deduced amino acid sequence suggests the presence of membrane-associated segments and a weak similarity with the rod-like tail portion of heavy chain myosins from different species. The DXS1357E gene may be a candidate for one of the many diseases mapping to this region. A preliminary analysis did not show rearrangements of the gene in 19 independent patients with Emery-Dreifuss muscular dystrophy. 21 refs., 2 figs.

  10. DNA-Grafted Supramolecular Polymers: Helical Ribbon Structures Formed by Self-Assembly of Pyrene-DNA Chimeric Oligomers.

    PubMed

    Vyborna, Yuliia; Vybornyi, Mykhailo; Rudnev, Alexander V; Häner, Robert

    2015-06-26

    The controlled arraying of DNA strands on adaptive polymeric platforms remains a challenge. Here, the noncovalent synthesis of DNA-grafted supramolecular polymers from short chimeric oligomers is presented. The oligomers are composed of an oligopyrenotide strand attached to the 5'-end of an oligodeoxynucleotide. The supramolecular polymerization of these oligomers in an aqueous medium leads to the formation of one-dimensional (1D) helical ribbon structures. Atomic force and transmission electron microscopy show rod-like polymers of several hundred nanometers in length. DNA-grafted polymers of the type described herein will serve as models for the development of structurally and functionally diverse supramolecular platforms with applications in materials science and diagnostics.

  11. Particle-Directed Assembly of Semiflexible Polymer Chains

    NASA Astrophysics Data System (ADS)

    McGovern, Michael; Dorfman, Kevin; Morse, David

    We use molecular dynamics simulations to investigate several models of semiflexible polymers that exhibit an attractive interaction with spherical particles. The organization of semiflexible polymer chains through attractive interactions with spherical particles occurs in several important processes in nature, such as the winding of DNA around histones and counter-ion condensation of charged polymers. The process is also of technological interest in the packaging of DNA for delivery to cells. In this presentation, we will present data on both the phase behavior and the kinetics of self-assembly as a function of the stiffness of the polymers, the attractive potential between the monomers and the particles, and the relative size of the monomers and particles. Our simulations suggest a transition between globular and rod-like aggregates that changes from a gradual to a sudden transition depending on particle size, and that rod formation is a slow, nucleation dependent process.

  12. Clustering and pasta phases in nuclear density functional theory

    DOE PAGES

    Schuetrumpf, Bastian; Zhang, Chunli; Nazarewicz, Witold

    2017-05-23

    Nuclear density functional theory is the tool of choice in describing properties of complex nuclei and intricate phases of bulk nucleonic matter. It is a microscopic approach based on an energy density functional representing the nuclear interaction. An attractive feature of nuclear DFT is that it can be applied to both finite nuclei and pasta phases appearing in the inner crust of neutron stars. While nuclear pasta clusters in a neutron star can be easily characterized through their density distributions, the level of clustering of nucleons in a nucleus can often be difficult to assess. To this end, we usemore » the concept of nucleon localization. We demonstrate that the localization measure provides us with fingerprints of clusters in light and heavy nuclei, including fissioning systems. Furthermore we investigate the rod-like pasta phase using twist-averaged boundary conditions, which enable calculations in finite volumes accessible by state of the art DFT solvers.« less

  13. Fast switching from isotropic liquids to nematic liquid crystals: rotaxanes as smart fluids.

    PubMed

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

    2015-11-28

    We examine a solution of rod-like piston-rotaxanes, which can switch their length by external excitation (for example optically) from a short state of length L to a long state of length qL. We show that this solution can exhibit a number of different behaviours. In particular it can rapidly switch from an isotropic to a nematic liquid crystalline state. There is a minimum ratio q* = 1.13 for which transitions from a pure isotropic state to a pure nematic state are possible. We present a phase-switching diagram, which gives the six possible behaviours for this system. It turns out that a large fraction of the phase switching diagram is occupied by the transition from a pure isotropic to a pure nematic state.

  14. Unique transducins expressed in long and short photoreceptors of lamprey Petromyzon marinus

    PubMed Central

    Muradov, Hakim; Kerov, Vasily; Boyd, Kimberly K.; Artemyev, Nikolai O.

    2008-01-01

    Lampreys represent the most primitive vertebrate class of jawless fish and serve as an evolutionary model of the vertebrate visual system. Transducin-α (Gαt) subunits were investigated in lamprey Petromyzon marinus in order to understand the molecular origins of rod and cone photoreceptor G proteins. Two Gαt subunits, GαtL and GαtS, were identified in the P. marinus retina. GαtL is equally distant from cone and rod G proteins and is expressed in the lamprey’s long photoreceptors. The short photoreceptor GαtS is a rod-like transducin-α that retains several unique features of cone transducins. Thus, the duplication of the ancestral transducin gene giving rise to rod transducins has already occurred in the last common ancestor of the jawed and jawless vertebrates. PMID:18687354

  15. Synthesis of biocompatible hybrid magnetic hollow spheres based on encapsulation strategy.

    PubMed

    Ha, Wei; Wu, Hao; Ma, Yuan; Fan, Min-Min; Peng, Shu-Lin; Ding, Li-Sheng; Zhang, Sheng; Li, Bang-Jing

    2013-01-30

    A kind of novel magnetic hollow spheres was prepared by encapsulating magnetofluid into polymeric hollow spheres. Polymeric hollow nanospheres were constructed by self-assembly of rod-coil complexes, in which the rod-like segments were formed by inclusion of α-cyclodextrins (α-CD) and grafting poly(ethylene glycol) (PEG) chains of chitosan-graft-PEG (CS-g-PEG). Structural characteristics of CS-g-PEG/α-CD hollow spheres were investigated in detail by NMR, XRD, TEM, etc. Furthermore, those hollow spheres showed a pH responsive property which induced a considerable change of their radius. Magnetofluid was physically entrapped into the empty domain while hollow spheres were formed, it was found that the hollow spheres can encapsulate large quantities of magnetofluid and the encapsulated magnetofluid still possess magnetic responsiveness properties. We expect that this strategy may be served as a novel and more straightforward approach to obtain magnetic hollow spheres for biomedical application.

  16. Complexation between dodecyl sulfate surfactant and zein protein in solution.

    PubMed

    Ruso, Juan M; Deo, Namita; Somasundaran, P

    2004-10-12

    Interactions between sodium dodecyl sulfate and zein protein, a model system for the understanding of the effect of surfactants on skin, were investigated using a range of techniques involving UV-vis spectroscopy, TOC (total organic carbon analysis), electrophoresis, and static and dynamic light scattering. Zein protein was solubilized by SDS. The adsorption of SDS onto insoluble protein fraction caused the zeta potential of the complex to become more negative. From these values, we calculated the Gibbs energy of absorption, which decreases when the SDS concentration is raised. Finally the structure of the complex, based on the analysis by static and dynamic light scattering, is proposed to be rod like. Copyright 2004 American Chemical Society

  17. Surfactant-assisted Nanocasting Route for Synthesis of Highly Ordered Mesoporous Graphitic Carbon and Its Application in CO2 Adsorption

    PubMed Central

    Wang, Yangang; Bai, Xia; Wang, Fei; Qin, Hengfei; Yin, Chaochuang; Kang, Shifei; Li, Xi; Zuo, Yuanhui; Cui, Lifeng

    2016-01-01

    Highly ordered mesoporous graphitic carbon was synthesized from a simple surfactant-assisted nanocasting route, in which ordered mesoporous silica SBA-15 maintaining its triblock copolymer surfactant was used as a hard template and natural soybean oil (SBO) as a carbon precursor. The hydrophobic domain of the surfactant assisted SBO in infiltration into the template’s mesoporous channels. After the silica template was carbonized and removed, a higher yield of highly-ordered graphitic mesoporous carbon with rod-like morphology was obtained. Because of the improved structural ordering, the mesoporous carbon after amine modification could adsorb more CO2 compared with the amine-functionalized carbon prepared without the assistance of surfactant. PMID:27220563

  18. Viscosity of Sheared Helical filament Suspensions

    NASA Astrophysics Data System (ADS)

    Sartucci, Matthew; Urbach, Jeff; Blair, Dan; Schwenger, Walter

    The viscosity of suspensions can be dramatically affected by high aspect ratio particles. Understanding these systems provides insight into key biological functions and can be manipulated for many technological applications. In this talk, the viscosity as a function of shear rate of suspensions of helical filaments is compared to that of suspensions of straight rod-like filaments. Our goal is to determine the impact of filament geometry on low volume fraction colloidal suspensions in order to identify strategies for altering viscosity with minimal volume fraction. In this research, the detached flagella of the bacteria Salmonella Typhimurium are used as a model system of helical filaments and compared to mutated straight flagella of the Salmonella. We compare rheological measurements of the suspension viscosity in response to shear flow and use a combination of the rheology and fluorescence microscopy to identify the microstructural changes responsible for the observed rheological response.

  19. Simulation of alnico coercivity

    DOE PAGES

    Ke, Liqin; Skomski, Ralph; Hoffmann, Todd D.; ...

    2017-07-10

    Micromagnetic simulations of alnico show substantial deviations from Stoner-Wohlfarth behavior due to the unique size and spatial distribution of the rod-like Fe-Co phase formed during spinodal decomposition in an external magnetic field. Furthemore, the maximum coercivity is limited by single-rod effects, especially deviations from ellipsoidal shape, and by interactions between the rods. In both the exchange interaction between connected rods and magnetostatic we consider the interaction between rods, and the results of our calculations show good agreement with recent experiments. Unlike systems dominated by magnetocrystalline anisotropy, coercivity in alnico is highly dependent on size, shape, and geometric distribution of themore » Fe-Co phase, all factors that can be tuned with appropriate chemistry and thermal-magnetic annealing.« less

  20. Dissecting Biological Dark Matter: Single Cell Genetic Analysis of TM7, a Rare and Uncultivated Microbe from the Human Mouth

    SciTech Connect

    Fenner, Marsha W; Marcy, Yann; Ouverney, Cleber; Bik, Elisabeth M.; Losekann, Tina; Ivanova, Natalia; Martin, H. Garcia; Szeto, E.; Platt, Darren; Hugenholtz, Philip; Relman, David A.; Quake, Stephen R.

    2007-07-01

    We have developed a microfluidic device that allows the isolation and genome amplification of individual microbial cells, thereby enabling organism-level genomic analysis of complex microbial ecosystems without the need for culture. This device was used to perform a directed survey of the human subgingival crevice and to isolate bacteria having rod-like morphology. Several isolated microbes had a 16S rRNA sequence that placed them in candidate phylum TM7, which has no cultivated or sequenced members. Genome amplification from individual TM7 cells allowed us to sequence and assemble >1,000 genes, providing insight into the physiology of members of this phylum. This approach enables single-cell genetic analysis of any uncultivated minority member of a microbial community.

  1. Funalichnus bhubani isp. nov. from Bhuban Formation, Surma Group (Lower -Middle Miocene) of Aizawl, Mizoram, India

    PubMed Central

    Tiwari, Raghavendra Prasad; Rajkonwar, Chinmoy; Patel, Satish Jaychandbhai

    2013-01-01

    A new ichnospecies of the ichnogenus Funalichnus Pokorný is described from the Middle Bhuban Unit, Bhuban Formation, Surma Group (Lower - Middle Miocene) of Aizawl, Mizoram, India. Funalichnus bhubani isp. Nov. Is a large burrow displaying cylindrical segments that are oriented nearly perpendicular to the bedding plane. The new ichnospecies can be identified on the basis of general form, size, unlined passive filling and twisted rod-like structure. The association of Funalichnus bhubani isp. Nov. With Arenicolites, Diplocraterion, Ophiomorpha Psilonichnus Skolithos and Thalassinoides points to its bathymetric restriction. The deep extension of the burrow in clastic sediments provides a favourable condition for preservation in the shoreface environment and occurrence in fine- to medium-grained clastic sediments may be a preservational preference. PMID:24204992

  2. Optimization of experimental parameters based on the Taguchi robust design for the formation of zinc oxide nanocrystals by solvothermal method

    SciTech Connect

    Yiamsawas, Doungporn; Boonpavanitchakul, Kanittha; Kangwansupamonkon, Wiyong

    2011-05-15

    Research highlights: {yields} Taguchi robust design can be applied to study ZnO nanocrystal growth. {yields} Spherical-like and rod-like shaped of ZnO nanocrystals can be obtained from solvothermal method. {yields} [NaOH]/[Zn{sup 2+}] ratio plays the most important factor on the aspect ratio of prepared ZnO. -- Abstract: Zinc oxide (ZnO) nanoparticles and nanorods were successfully synthesized by a solvothermal process. Taguchi robust design was applied to study the factors which result in stronger ZnO nanocrystal growth. The factors which have been studied are molar concentration ratio of sodium hydroxide and zinc acetate, amount of polymer templates and molecular weight of polymer templates. Transmission electron microscopy and X-ray diffraction technique were used to analyze the experiment results. The results show that the concentration ratio of sodium hydroxide and zinc acetate ratio has the greatest effect on ZnO nanocrystal growth.

  3. Green self-assembly of zein-conjugated ZnO/Cd(OH)Cl hierarchical nanocomposites with high cytotoxicity and immune organs targeting

    NASA Astrophysics Data System (ADS)

    Wang, Hua-Jie; Cao, Ying; Wang, Cai-Feng; Cui, Shi-Zhong; Mi, Li-Wei; Miyazawa, Teruo

    2016-04-01

    Inorganic nanomedicines in the fight against cancer have progressed rapidly during recent years, with the synergistic advantages of multifunctional nanosystems compared to single component. Herein, a drug-combination opinion was introduced into “nanomedicine” based on the understanding of Trojan horse-anti-tumor mechanism of inorganic nano-medicines. Moreover, we reported the green and facile synthesis route of mono-dispersed and rod-like zein-conjugated ZnO/Cd(OH)Cl hierarchical nanocomposites. We found that the nanocomposites exhibited high-efficiency killing ability to tumor cells through lipid peroxidation mediated-membrane disintegration route. The safety studies in BALB/c mice didn’t detect injection anaphylaxis, hemolysis and cytotoxicity. More interestingly, the nano-composites could specially accumulate in liver and kidney, which will be helpful for targeting cure to these regional cancers.

  4. Spectroscopic and Electrochemical Properties of Lithium-Rich LiFePO4 Cathode Synthesized by Solid-State Reaction

    NASA Astrophysics Data System (ADS)

    Rosaiah, P.; Hussain, O. M.; Zhu, Jinghui; Qiu, Yejun

    2017-08-01

    Lithium iron phosphate (Li x FePO4) is synthesized by a solid-state reaction method. The structural, electrical and electrochemical properties are studied in detail. It is found that the increment of lithium concentration (up to x = 1.05) does not affect the structure of LiFePO4 but improves its electrical conductivity as well as electrochemical performance. Surface morphological studies exhibited the formation of rod-like nanoparticles with small size. Electric and dielectric properties are also investigated over a frequency range of 1 Hz-1 MHz at different temperatures. The conductivity increased with increasing temperature, which follows the Arrhenius relation with the activation energy of about 0.31 eV. And the electrochemical tests found that the Li1.05FePO4 cathode possessed improved discharge capacity with better cycling performance.

  5. Nanoparticle-Loaded Multifunctional Block Copolymer Micelles

    NASA Astrophysics Data System (ADS)

    Bae, Jinhye; Lawrence, Jimmy; Miesch, Caroline; Ribbe, Alexander; Li, Weikun; Emrick, Todd; Zhu, Jintao; Hayward, Ryan

    2012-02-01

    We have studied the incorporation of pre-synthesized hydrophobic inorganic nanoparticles within the cores of amphiphilic polystyrene-block-poly(ethylene oxide) (PS-PEO) diblock copolymer micelles formed through solvent-evaporation-induced interfacial instabilities of emulsion droplets. Using iron oxide, gold, and cadmium selenide nanoparticles coated with native alkane ligands, highly uniform encapsulation is obtained for cylindrical micelles, while spherical micelles can be enriched to ˜ 90 % of loaded micelles through simple magnetic or centrifugal purification steps. Multiple different types of nanoparticles can easily be incorporated into each micelle, yielding multi-functional micelles. The ability to encapsulate both spherical and rod-like particles of different core chemistries and sizes ranging from ˜ 1 to 20 nm, without the necessity of coating particles with specially designed ligands, makes this a versatile route to prepare hybrid micelle structures.

  6. Spherical nanocrystalline cellulose (NCC) from oil palm empty fruit bunch pulp via ultrasound assisted hydrolysis.

    PubMed

    Zianor Azrina, Z A; Beg, M Dalour H; Rosli, M Y; Ramli, Ridzuan; Junadi, Norhafzan; Alam, A K M Moshiul

    2017-04-15

    Nanocrystalline cellulose (NCC) was isolated from oil palm empty fruit bunch pulp (EFBP) using ultrasound assisted acid hydrolysis. The obtained NCC was analysed using FESEM, XRD, FTIR, and TGA, and compared with raw empty fruit bunch fibre (REFB), empty fruit bunch pulp (EFBP), and treated empty fruit bunch pulp (TEFBP). Based on FESEM analysis, it was found that NCC has a spherical shaped after acid hydrolysis with the assistance of ultrasound. This situation was different compared to previous studies that obtained rod-like shaped of NCC. Furthermore, the crystallinity of NCC is higher compared to REFB and EFBP. According to thermal stability, the NCC obtained shows remarkable sign of high thermal stability compared to REFB and EFBP. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Tumor-Triggered Geometrical Shape Switch of Chimeric Peptide for Enhanced in Vivo Tumor Internalization and Photodynamic Therapy.

    PubMed

    Han, Kai; Zhang, Jin; Zhang, Weiyun; Wang, Shibo; Xu, Luming; Zhang, Chi; Zhang, Xianzheng; Han, Heyou

    2017-03-28

    Geometrical shape of nanoparticles plays an important role in cellular internalization. However, the applicability in tumor selective therapeutics is still scarcely reported. In this article, we designed a tumor extracellular acidity-responsive chimeric peptide with geometrical shape switch for enhanced tumor internalization and photodynamic therapy. This chimeric peptide could self-assemble into spherical nanoparticles at physiological condition. While at tumor extracellular acidic microenvironment, chimeric peptide underwent detachment of acidity-sensitive 2,3-dimethylmaleic anhydride groups. The subsequent recovery of ionic complementarity between chimeric peptides resulted in formation of rod-like nanoparticles. Both in vitro and in vivo studies demonstrated that this acidity-triggered geometrical shape switch endowed chimeric peptide with accelerated internalization in tumor cells, prolonged accumulation in tumor tissue, enhanced photodynamic therapy, and minimal side effects. Our results suggested that fusing tumor microenvironment with geometrical shape switch should be a promising strategy for targeted drug delivery.

  8. Influence of TiCl4 precursor in hydrothermal synthesis of TiO2 nanostructures

    NASA Astrophysics Data System (ADS)

    Kartikay, Purnendu; Nemala, Siva Sankar; Mallick, Sudhanshu

    2017-05-01

    Rutile TiO2 films were deposited on the FTO substrate by the hydrothermal process using TTIP and TiCl4 as the titania precursor. Our study manifestly exhibits the influence of TiCl4 precursor on the hydrothermal growth of the TiO2 structure. The morphology of prepared film varies from nano-cauliflower to nano-flower to nano-parallelepiped rod-like structure with the addition of TiCl4 as the precursor. When TiCl4 is introduced in the precursor HCl corresponding to four times of the Ti4+ concentration is generated as a by-product during the reaction, these additional HCl promotes the etching of the nanostructure enabling the nanostructure to unfurl. We conclude that the tailoring of the nanostructure can be performed by addition of TiCl4 in the precursor

  9. Thermal and mechanical properties of bio-nanocomposites reinforced by Luffa cylindrica cellulose nanocrystals.

    PubMed

    Siqueira, Gilberto; Bras, Julien; Follain, Nadège; Belbekhouche, Sabrina; Marais, Stéphane; Dufresne, Alain

    2013-01-16

    Cellulose nanocrystals have been prepared by acid hydrolysis of Luffa cylindrica fibers. The acid-resistant residue consisted of rod-like nanoparticles with an average length an diameter around 242 and 5.2nm, respectively (aspect ratio around 46). These cellulose nanocrystals have been used as a reinforcing phase for the processing of bio-nanocomposites using polycaprolactone (PCL) as matrix. To promote interfacial filler/matrix interactions the surface of cellulose nanocrystals was chemically modified with n-octadecyl isocyanate (C(18)H(37)NCO). Evidence of the grafting was supported by infrared spectroscopy and elemental analysis. X-ray diffraction analysis was used to confirm the integrity of cellulose nanocrystals after chemical modification. Both unmodified and chemically modified nanocrystals were used to prepare nanocomposites. The thermal properties of these materials were determined from differential scanning calorimetry and their mechanical behavior was evaluated in both the linear and non-linear range. Copyright © 2012 Elsevier Ltd. All rights reserved.

  10. Fuel Element for a Nuclear Reactor

    DOEpatents

    Duffy, Jr., J. G.

    1961-05-30

    A lattice-type fissionable fuel structure for a nuclear reactor is offered. The fissionable material is formed into a plurality of rod-like bodies each encased in a fluid-tight jacket. A plurality of spaced longitudinal fins are mounted on the exterior of and extend radially from each jacket, and a portion of the fins extends radially beyond the remainder of the fins. A collar of short lengih for each body is mounted on the extended fins for spacing the bodies, and adjacent bodies abut each other through these collars. Should distortion of the bodies take place, collapse of the outer fins is limited by the shorter fins thereby insuring some coolant flow therethrough at all times.

  11. Bionanowhiskers from jute: preparation and characterization.

    PubMed

    Kasyapi, Nibedita; Chaudhary, Vidhi; Bhowmick, Anil K

    2013-02-15

    Bionanowhiskers were extracted from jute by acid hydrolysis. At first cellulose microfibrils were formed by alkali treatment. Addition of an acid to the microfibrils triggered the formation of cellulose nanowhiskers. These were characterized by using different techniques viz. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetry (TGA), scanning electron microscopy (SEM) and atomic force microscopy (AFM). In the FTIR study, absence of peak at 1738 cm(-1) indicated removal of hemicellulose. The rod like morphology of the nanowhiskers (length - 550±100 nm, width - 77±30 nm) was observed after 1h of acid hydrolysis, whereas further increase in time resulted in triangular shape morphology. Acid hydrolysis increased crystallinity, but decreased the temperature corresponding to major degradation (T(max)) and onset of degradation (T(i)). These bionanowhiskers might be useful as reinforcing element in nanocomposites.

  12. Atomic force microscopy of gastric mucin

    NASA Astrophysics Data System (ADS)

    Chasan, Bernard; Hong, Zhenning; Bansil, Rama; Turner, Bradley; Ramakrishnan Bhaskar, K.; Afdhal, Nezam

    2001-03-01

    We report on the first results from an AFM study of porcine gastric mucin employing the tapping mode technique in aqueous solution. This glycoprotein is responsible for protecting the stomach epithelium from acid damage. Mucin was imaged on a mica substrate at pH7, and at pH2. At the higher pH we detected individual molecules in disordered configuration, with characteristic lengths of 20-40 nm. At the lower pH the mucin forms extended rod-like clusters that, at high concentrations, are aligned into planar arrays. Individual clusters are of order 50 nm long and 20 nm wide while the entire array is of order several hundred nm both in length and width. The clustering behavior at low pH is consistent with that previously detected in dynamic light scattering experiments by Cao et. al. (Biophysical J. 76:120-1258 1999).

  13. Dissecting biological “dark matter” with single-cell genetic analysis of rare and uncultivated TM7 microbes from the human mouth

    PubMed Central

    Marcy, Yann; Ouverney, Cleber; Bik, Elisabeth M.; Lösekann, Tina; Ivanova, Natalia; Martin, Hector Garcia; Szeto, Ernest; Platt, Darren; Hugenholtz, Philip; Relman, David A.; Quake, Stephen R.

    2007-01-01

    We have developed a microfluidic device that allows the isolation and genome amplification of individual microbial cells, thereby enabling organism-level genomic analysis of complex microbial ecosystems without the need for culture. This device was used to perform a directed survey of the human subgingival crevice and to isolate bacteria having rod-like morphology. Several isolated microbes had a 16S rRNA sequence that placed them in candidate phylum TM7, which has no cultivated or sequenced members. Genome amplification from individual TM7 cells allowed us to sequence and assemble >1,000 genes, providing insight into the physiology of members of this phylum. This approach enables single-cell genetic analysis of any uncultivated minority member of a microbial community. PMID:17620602

  14. Self-contained instrument for measuring subterranean tunnel wall deflection

    DOEpatents

    Rasmussen, Donald Edgar; Hof, Jr., Peter John

    1978-01-01

    The deflection of a subterranean tunnel is measured with a rod-like, self-contained instrument that is adapted to be inserted into a radially extending bore of the tunnel adjacent an end of the tunnel where the tunnel is being dug. One end of the instrument is anchored at the end of the bore remote from the tunnel wall, while the other end of the intrument is anchored adjacent the end of the wall in proximity to the tunnel wall. The two ends of the instrument are linearly displaceable relative to each other; the displacement is measured by a transducer means mounted on the instrument. Included in the instrument is a data storage means including a paper tape recorder periodically responsive to a parallel binary signal indicative of the measured displacement.

  15. Defect structures mediate the isotropic-nematic transition in strongly confined liquid crystals.

    PubMed

    Gârlea, Ioana C; Mulder, Bela M

    2015-01-21

    Using Monte Carlo simulations, we study rod-like lyotropic liquid crystals confined to a square slab-like geometry with lateral dimensions comparable to the length of the particles. We observe that this system develops linear defect structures upon entering the planar nematic phase. These defect structures flank a lens-shaped nematic region oriented along a diagonal of the square box. We interpret these structures as a compromise between the 2-fold order of the bulk nematic phase and the 4-fold order imposed by the lateral boundaries. A simple Onsager-type theory that effectively implements these competing tendencies is used to model the phase behavior in the center of the box and shows that the free-energy cost of forming the defect structures strongly offsets the transition-inducing effects of both the transverse and lateral confinement.

  16. Measuring the equation of state for a 2D colloidal membrane: A microfluidic approach to buffer exchange

    NASA Astrophysics Data System (ADS)

    Balchunas, Andrew; Cabanas, Rafael; Fraden, Seth; Dogic, Zvonimir

    Previous work has shown that monodisperse rod-like colloidal particles, such as a filamentous bacteriophage, self assemble into a 2D monolayer smectic in the presence of a non-adsorbing depleting polymer. These structures have the same functional form of bending rigidity and lateral compressibility as conventional lipid bi-layers, so we name the monolayer smectic a colloidal membrane. We have developed a microfluidic device such that the osmotic pressure acting on a colloidal membrane may be controlled via a full in situ buffer exchange. Rod density within individual colloidal membranes was measured as a function of osmotic pressure and a first order phase transition, from 2D fluid to 2D solid, was observed. kon and koff rates of rod to membrane binding were measured by lowering the osmotic pressure until membrane evaporation occurred.

  17. Understanding nanocellulose chirality and structure-properties relationship at the single fibril level

    NASA Astrophysics Data System (ADS)

    Usov, Ivan; Nyström, Gustav; Adamcik, Jozef; Handschin, Stephan; Schütz, Christina; Fall, Andreas; Bergström, Lennart; Mezzenga, Raffaele

    2015-06-01

    Nanocellulose fibrils are ubiquitous in nature and nanotechnologies but their mesoscopic structural assembly is not yet fully understood. Here we study the structural features of rod-like cellulose nanoparticles on a single particle level, by applying statistical polymer physics concepts on electron and atomic force microscopy images, and we assess their physical properties via quantitative nanomechanical mapping. We show evidence of right-handed chirality, observed on both bundles and on single fibrils. Statistical analysis of contours from microscopy images shows a non-Gaussian kink angle distribution. This is inconsistent with a structure consisting of alternating amorphous and crystalline domains along the contour and supports process-induced kink formation. The intrinsic mechanical properties of nanocellulose are extracted from nanoindentation and persistence length method for transversal and longitudinal directions, respectively. The structural analysis is pushed to the level of single cellulose polymer chains, and their smallest associated unit with a proposed 2 × 2 chain-packing arrangement.

  18. Initial stages of organic film growth characterized by thermal desorption spectroscopy

    PubMed Central

    Winkler, Adolf

    2015-01-01

    In the wake of the increasing importance of organic electronics, a more in-depth understanding of the early stages of organic film growth is indispensable. In this review a survey of several rod-like and plate-like organic molecules (p-quaterphenyl, p-sexiphenyl, hexaazatriphenylene-hexacarbonitrile (HATCN), rubicene, indigo) deposited on various application relevant substrates (gold, silver, mica, silicon dioxide) is given. The focus is particularly put on the application of thermal desorption spectroscopy to shed light on the kinetics and energetics of the molecule-substrate interaction. While each adsorption system reveals a manifold of features that are specific for the individual system, one can draw some general statements on the early stages of organic film formation from the available datasets. Among the important issues in this context is the formation of wetting layers and the dewetting as a function of the substrate surface conditions, organic film thickness and temperature. PMID:26778860

  19. Impact of diffusion limited aggregates of impurities on nematic ordering

    NASA Astrophysics Data System (ADS)

    Harkai, S.; Ambrožič, M.; Kralj, S.

    2017-02-01

    We study the impact of random bond-type disorder on two-dimensional (2D) orientational ordering of nematic liquid crystal (LC) configurations. The lattice Lebwohl-Lasher pseudospin model is used to model orientational ordering perturbed by frozen-in rod-like impurities of concentration p exhibiting the isotropic orientational probability distribution. The impurities are either (i) randomly spatially distributed or (ii) form diffusion limited aggregation (DLA)-type patterns characterized by the fractal dimensions df, where we consider cases df ∼ 1.7 and df ∼ 1.9. The degree of orientational ordering is quantified in terms of the orientational pair correlation function G(r) . Simulations reveal that the DLA pattern imposed disorder has a significantly weaker impact for a given concentration of impurities. Furthermore, if samples are quenched from the isotropic LC phase, then the fractal dimension is relatively strongly imprinted on quantitative characteristics of G(r) .

  20. Morphogenesis of simple leaves: regulation of leaf size and shape.

    PubMed

    Rodriguez, Ramiro E; Debernardi, Juan M; Palatnik, Javier F

    2014-01-01

    Plants produce new organs throughout their life span. Leaves first initiate as rod-like structures protruding from the shoot apical meristem, while they need to pass through different developmental stages to become the flat organ specialized in photosynthesis. Leaf morphogenesis is an active process regulated by many genes and pathways that can generate organs with a wide variety of sizes and shapes. Important differences in leaf architecture can be seen among different species, but also in single individuals. A key aspect of leaf morphogenesis is the precise control of cell proliferation. Modification or manipulation of this process may lead to leaves with different sizes and shapes, and changes in the organ margins and curvature. Many genes required for leaf development have been identified in Arabidopsis thaliana, and the mechanisms underlying leaf morphogenesis are starting to be unraveled at the molecular level. © 2013 Wiley Periodicals, Inc.

  1. A magnetic protein biocompass

    NASA Astrophysics Data System (ADS)

    Qin, Siying; Yin, Hang; Yang, Celi; Dou, Yunfeng; Liu, Zhongmin; Zhang, Peng; Yu, He; Huang, Yulong; Feng, Jing; Hao, Junfeng; Hao, Jia; Deng, Lizong; Yan, Xiyun; Dong, Xiaoli; Zhao, Zhongxian; Jiang, Taijiao; Wang, Hong-Wei; Luo, Shu-Jin; Xie, Can

    2016-02-01

    The notion that animals can detect the Earth’s magnetic field was once ridiculed, but is now well established. Yet the biological nature of such magnetosensing phenomenon remains unknown. Here, we report a putative magnetic receptor (Drosophila CG8198, here named MagR) and a multimeric magnetosensing rod-like protein complex, identified by theoretical postulation and genome-wide screening, and validated with cellular, biochemical, structural and biophysical methods. The magnetosensing complex consists of the identified putative magnetoreceptor and known magnetoreception-related photoreceptor cryptochromes (Cry), has the attributes of both Cry- and iron-based systems, and exhibits spontaneous alignment in magnetic fields, including that of the Earth. Such a protein complex may form the basis of magnetoreception in animals, and may lead to applications across multiple fields.

  2. Wave optics modelling of amplified spontaneous emission

    SciTech Connect

    Ritchie, B.; Garrison, J.

    1990-11-06

    A laser works by amplified spontaneous emission (ASE) of inverted atomic ions confined in an amplifier of rod-like geometry, such that ASE radiation is directed out of both ends of the rod. The forward and backward ASE waves are coupled through the population-rate equations and cause the saturation of the lasing transition (gain saturation). Diffraction of the waves in the transverse direction is responsible for the radiation pattern (angular distribution) observed on a distant screen and for the degree of spatial coherence of the radiation. Refraction of the light also occurs due to spatial gradients in the electron density. In order to describe this situation a code has been developed which numerically solves paraxial Maxwell's equations in the time and two spatial dimensions. The code uses the Peaceman-Rachford Alternating-Direction-Implicit algorithm and is benchmarked against laboratory DYE-LASER experiments. 4 refs., 1 fig.

  3. Size and shape of charged micelles of ionic surfactants in aqueous salt solutions.

    PubMed

    Ikeda, S; Ozeki, S; Hayashi, S

    1980-06-01

    Light-scattering has been measured on aqueous NaCl solutions of dodecyldimethylammonium chloride and sodium dodecyl sulfate. From molecular weight determination it is confirmed that spherical micelles are formed at low NaCl concentrations, but at high NaCl concentrations the small micelles formed at the critical micelle concentration further associate to form large rod-like micelles with increasing micelle concentration. The reduction of repulsion between charged groups induces the sphere-rod transition of micelle shape. The dependence of molecular weight on ionic strength can be expressed by double logarithmic relations, which are dependent on the micelle shape. While dodecyldimethylammonium chloride dissolves even in 4.00 M NaCl, sodium dodecyl sulfate solutions exhibit some XXX in angular dissymmetry at NaCl concentrations higher than 0.50 M at low temperatures.

  4. Spiky gold nanoshells.

    PubMed

    Sanchez-Gaytan, Brenda L; Park, So-Jung

    2010-12-21

    We report a high-yield synthetic method for a new type of metal nanostructure, spiky gold nanoshells, which combine the morphological characteristics of hollow metal nanoshells and nanorods. Our method utilizes block copolymer assemblies and polymer beads as templates for the growth of spiky nanoshells. Various shapes of spiky metal nanoshells were prepared in addition to spherical nanoshells by using block copolymer assemblies such as rod-like micelles, vesicles, and bilayers as templates. Furthermore, spiky gold shells encapsulating magnetic nanoparticles or quantum dots were prepared based on the ability of block copolymers to self-assemble with various types of nanoparticles and molecules. The capability to encapsulate other materials in the core, the shape tunability, and the highly structured surface of spiky nanoshells should benefit a range of imaging, sensing, and medical applications of metal nanostructures.

  5. Fundamental measure theory for smectic phases: scaling behavior and higher order terms.

    PubMed

    Wittmann, René; Marechal, Matthieu; Mecke, Klaus

    2014-08-14

    The recent extension of Rosenfeld's fundamental measure theory to anisotropic hard particles predicts nematic order of rod-like particles. Our analytic study of different aligned shapes provides new insights into the structure of this density functional, which is basically founded on experience with hard spheres. We combine scaling arguments with dimensional crossover and motivate a modified expression, which enables an appropriate description of smectic layering. We calculate the nematic-smectic-A transition of monodisperse hard spherocylinders with and without orientational degrees of freedom and present the equation of state and phase diagram including these two liquid crystalline phases in good agreement with simulations. We also find improved results related to the isotropic-nematic interface. We discuss the quality of empirical corrections and the convergence towards an exact second virial coefficient, including higher order terms.

  6. Identification and molecular properties of a 306 nucleotide viroid associated with apple dimple fruit disease.

    PubMed

    Di Serio, F; Aparicio, F; Alioto, D; Ragozzino, A; Flores, R

    1996-11-01

    A new viroid associated with an apple fruit disorder similar to, but more severe than, the dapple apple disease induced in some varieties by apple scar skin viroid (ASSVd) has been found. The new viroid, tentatively termed apple dimple fruit viroid (ADFVd), is a circular RNA of 306 nucleotides which adopts a quasi-rod-like conformation of minimum free energy. It contains the core nucleotides of the central conserved region (CCR) of the ASSVd group as well as the terminal conserved region (TCR) present in all members of the ASSVd and potato spindle tuber viroid (PSTVd) monophyletic groups. ADFVd has the highest sequence similarity with ASSVd and the 294 nucleotide citrus viroid CVd-IIIb sharing with the latter an almost identical left terminal domain. The right- and left-hand termini of ADFVd are formed by almost perfect duplications of sequences found in the CCR upper and lower strands, respectively, of PSTVd and closely related viroids.

  7. Mechanism of adhesion of Alysiella bovis to glass surfaces.

    PubMed Central

    Irvin, R T; To, M; Costerton, J W

    1984-01-01

    Alysiella bovis adheres to surfaces by means of short, ruthenium red-staining, rod-like fimbriae. The fimbriae remain associated with the cell envelope of A. bovis, even when sonicated or exposed sequentially to toluene, Triton X-100, lysozyme, ribonuclease, and deoxyribonuclease. Adhesion of outer membrane-derived cell wall ghosts of A. bovis to glass was inhibited by IO4-, sodium dodecyl sulfate, urea, pronase, and trypsin. Protease treatment digested the fimbriae from the distal end, and exposure to sodium dodecyl sulfate depolymerized the fimbriae. Exposure of ghosts to 1% sodium dodecyl sulfate preferentially solubilized a 16,500-dalton protein which was subsequently purified by gel filtration and demonstrated to be a glycoprotein (ca. 17% carbohydrate). Antibodies raised against the 16,500-dalton glycoprotein agglutinated whole cells and inhibited adhesion of ghosts to glass. Images PMID:6209260

  8. Fundamental measure theory for smectic phases: Scaling behavior and higher order terms

    NASA Astrophysics Data System (ADS)

    Wittmann, René; Marechal, Matthieu; Mecke, Klaus

    2014-08-01

    The recent extension of Rosenfeld's fundamental measure theory to anisotropic hard particles predicts nematic order of rod-like particles. Our analytic study of different aligned shapes provides new insights into the structure of this density functional, which is basically founded on experience with hard spheres. We combine scaling arguments with dimensional crossover and motivate a modified expression, which enables an appropriate description of smectic layering. We calculate the nematic-smectic-A transition of monodisperse hard spherocylinders with and without orientational degrees of freedom and present the equation of state and phase diagram including these two liquid crystalline phases in good agreement with simulations. We also find improved results related to the isotropic-nematic interface. We discuss the quality of empirical corrections and the convergence towards an exact second virial coefficient, including higher order terms.

  9. Connection between the conformation and emission properties of poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] single molecules during thermal annealing

    NASA Astrophysics Data System (ADS)

    Ou, Jiemei; Yang, Yuzhao; Lin, Wensheng; Yuan, Zhongke; Gan, Lin; Lin, Xiaofeng; Chen, Xudong; Chen, Yujie

    2015-03-01

    We investigated the transitions of conformations and their effects on emission properties of poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) single molecules in PMMA matrix during thermal annealing process. Total internal reflection fluorescence microscopy measurements reveal the transformation from collapsed conformations to extended, highly ordered rod-like structures of MEH-PPV single molecules during thermal annealing. The blue shifts in the ensemble single molecule PL spectra support our hypnosis. The transition occurs as the annealing temperature exceeds 100 °C, implying that an annealing temperature near the glass transition temperature Tg of matrix is ideal for the control and optimization of blend polymer films.

  10. Self-catalytic crystal growth, formation mechanism, and optical properties of indium tin oxide nanostructures

    NASA Astrophysics Data System (ADS)

    Liang, Yuan-Chang; Zhong, Hua

    2013-08-01

    In-Sn-O nanostructures with rectangular cross-sectional rod-like, sword-like, and bowling pin-like morphologies were successfully synthesized through self-catalytic growth. Mixed metallic In and Sn powders were used as source materials, and no catalyst layer was pre-coated on the substrates. The distance between the substrate and the source materials affected the size of the Sn-rich alloy particles during crystal growth in a quartz tube. This caused In-Sn-O nanostructures with various morphologies to form. An X-ray photoelectron spectroscope and a transmittance electron microscope with an energy-dispersive X-ray spectrometer were used to investigate the elemental binding states and compositions of the as-synthesized nanostructures. The Sn doping and oxygen vacancies in the In2O3 crystals corresponded to the blue-green and yellow-orange emission bands of the nanostructures, respectively.

  11. Torpedo marmorata acetylcholinesterase; a comparison with the Electrophorus electricus enzyme. Molecular forms, subunits, electron microscopy, immunological relationship.

    PubMed

    Rieger, F; Bon, S; Massoulié, J; Cartauld, J; Picard, B; Benda, P

    1976-09-15

    Electron microscopy, sequential degradation by hydrolytic enzymes and the physical-chemical properties of the molecular forms of Torpedo acetylcholinesterase indicate that these molecules are structurally related to each other in the same way as the molecular forms of Electrophorus acetylcholinesterase: all are derived from a complex structure in which three tetrameric groups of subunits are associated with a rod-like 'tail'. In aged preparations the catalytic subunits are split into fragments in a manner similar to those of Electrophorus acetylcholinesterase. Immunological cross-reaction between both enzymes demonstrates the occurrence of common antigenic sites. The enzymes from the two sources, however, are different in their molecular weights and susceptibility to hydrolytic enzymes. Also, Torpedo acetylcholinesterase does not precipitate with either isologous or heterologous antibodies.

  12. Preparation and photoluminescence study of mesoporous indium hydroxide nanorods

    SciTech Connect

    Li, Changyu; Lian, Suoyuan; Liu, Yang; Liu, Shouxin; Kang, Zhenhui

    2010-02-15

    Mesoporous indium hydroxide nanorods were successfully synthesized by a mild one-step one-pot method. The obtained samples were characterized by X-ray diffraction, transmission electron microscopy with selected area electron diffraction, N{sub 2} adsorption, ultraviolet-visible absorption and photoluminescence, respectively. Transmission electron microscopy showed that there were some pores in the samples, which were mainly composed of rod-like shapes with length of 300 nm and diameter of 90 nm. N{sub 2} adsorption/desorption measurements confirmed that the prepared powder was mesoporous with average pore diameter of 3.1 nm. The ultraviolet-visible absorption spectroscopy analysis indicated that the band gap energy of the samples was 5.15 eV. Photoluminescence spectrum showed that there were two strong emissions under ultraviolet light irradiation. The growth mechanism of indium hydroxide nanorods and the role of cetyltrimethyl ammonium bromide were also discussed.

  13. Efficient thermolysis route to monodisperse Cu₂ZnSnS₄ nanocrystals with controlled shape and structure.

    PubMed

    Zhang, Xiaoyan; Guo, Guobiao; Ji, Cheng; Huang, Kai; Zha, Chenyang; Wang, Yifeng; Shen, Liming; Gupta, Arunava; Bao, Ningzhong

    2014-05-28

    Monodisperse Cu2ZnSnS4 (CZTS) nanocrystals with tunable shape, crystalline phase, and composition are synthesized by efficient thermolysis of a single source precursor of mixed metal-oleate complexes in hot organic solvents with dissolved sulfur sources. Suitable tuning of the synthetic conditions and the Cu/(Zn + Sn) ratio of the precursor has enabled precise control of the crystalline phase in the form of kesterite, or a newly observed wurtzite structure. Nanocrystals with morphology in the form of spherical, rice-like, or rod-like shapes are obtained over a wide range of compositions (0.5 ≤ Cu/(Zn + Sn) ≤ 1.2). Both the final products and intermediates for each shape exhibit consistent composition and structure, indicating homogenous nucleation and growth of single-phase nanocrystals. Thin films prepared from colloidal nanocrystal suspensions display interesting shape-dependent photoresponse behavior under white light illumination from a solar simulator.

  14. Synthesis and conformation of 3,6-connected cyclohexadiene chains.

    PubMed

    Golling, Florian E; Koch, Amelie H R; Fytas, George; Müllen, Klaus

    2015-05-01

    3,6-Connected cyclohexadienes as precursors for polyphenylenes are synthesized and characterized by mass spectrometry and NMR spectroscopy. Pure fractions of trimers, hexamers, and nonamers are collected after separation of the product mixture by recycling GPC. The anticipated formation of rigid linear structures, due to the trans-configuration of the monomeric units, is supported by density functional theory and experimentally confirmed by dynamic light scattering from dilute solution at low scattering angles. The obtained translational diffusion coefficients are represented by rigid rod-like or prolate ellipsoid-like molecular shapes. The measurements of diffusion coefficients reveal a length-dependent ratio of 1:2:3 between the three oligomers, which directly correlates to the expected length extension from trimer to nonamer.

  15. Theoretical study of spectroscopic properties of dimethoxy-p-phenylene-ethynylene oligomers: planarization of the conjugated backbone.

    PubMed

    Li, Na; Jia, Ke; Wang, Sufan; Xia, Andong

    2007-09-27

    The optical spectra of the dimethoxy-p-phenylene-ethynylene oligomers (up to n = 10) are calculated by DFT and TD-DFT methods. It is found that the conformational rotations around the cylindrical triple-bonded carbon links impact significantly the optical spectrum. The effective conjugation length (ECL) of the oligomer is obtained by extrapolating the HOMO-LUMO gap to infinite chain length with an alternative exponential function. The spectral shift is mainly dependent on the high pi-conjugation segment of oligomers, resulting from the planarization of the backbone. Although the rotational barrier is very low, the calculated results further indicate that rotation about the cylindrical triple bond still interrupts the conjugation of rod-like oligomers to some extent, and leads to an angle-dependent HOMO-LUMO gap. The results are helpful to interpret the conformational-dependent spectroscopic phenomena of p-phenyleneethynylene oligomers and polymers (PPEs) observed in ensemble and single molecule spectroscopy.

  16. Scanning electron microscopy of bacteria Tetrasphaera duodecadis.

    PubMed

    Arroyo, E; Enríquez, L; Sánchez, A; Ovalle, M; Olivas, A

    2014-01-01

    This study reports the characterization of the Tetrasphaera duodecadis bacteria and the techniques used therein. In order to evaluate the morphological characteristics of the T. duodecadis bacteria scanning electron microscope (SEM) was used throughout its different growth stages. These microorganisms were grown in vitamin B12 broths with 1% tryptone, 0.2% yeast extract, and 0.1% glucose. The turbidimetric method was employed for the determination of bacterial concentration and growth curve. The SEM results show small agglomerates of 0.8 ± 0.05 µm during the lag phase, and rod-like shapes during the exponential phase with similar shapes in the stationary phase.

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

    SciTech Connect

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

    1999-09-23

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

  18. Active tensor magnetic gradiometer system final report for Project MM–1514

    USGS Publications Warehouse

    Smith, David V.; Phillips, Jeffrey D.; Hutton, S. Raymond

    2014-01-01

    An interactive computer simulation program, based on physical models of system sensors, platform geometry, Earth environment, and spheroidal magnetically-permeable targets, was developed to generate synthetic magnetic field data from a conceptual tensor magnetic gradiometer system equipped with an active primary field generator. The system sensors emulate the prototype tensor magnetic gradiometer system (TMGS) developed under a separate contract for unexploded ordnance (UXO) detection and classification. Time-series data from different simulation scenarios were analyzed to recover physical dimensions of the target source. Helbig-Euler simulations were run with rectangular and rod-like source bodies to determine whether such a system could separate the induced component of the magnetization from the remanent component for each target. This report concludes with an engineering assessment of a practical system design.

  19. Complex liquid-crystal nanostructures in semiflexible ABC linear triblock copolymers: A self-consistent field theory.

    PubMed

    Li, Shiben; Jiang, Ying; Chen, Jeff Z Y

    2016-11-14

    We show that two series of ABC linear triblock copolymers possess sequences of order-to-order phase transitions between microphase-separated states, as the degree of flexibility of the semiflexible middle B-blocks varies. The spatial and orientational symmetries of these phases, some of them containing liquid-crystal ordering, are analysed in comparison with related structures previously determined experimentally and theoretically. A theoretical framework based on the self-consistent field treatment of the wormlike-chain model, which incorporates the Flory-Huggins and Maier-Saupe interactions in the free energy, is used here as a basic foundation for numerical calculations. We suggest that tuning the flexibility parameter, which reduces to the concept of degree of polymerization in the coil-like limit and characterizes the chain-persistency in the rod-like limit, provides a promising approach that can be used to design the resulting microphase-separated structures in semiflexible copolymer melts.

  20. A photographic approach to the possible mechanism of retrogradation of sweet potato starch.

    PubMed

    Lian, Xijun; Zhao, Shuyi; Liu, Qinsheng; Zhang, Xu

    2011-01-01

    Although the subject of starch retrogradation has been studied for about 20 years, the mechanism of starch retrogradation seems not yet to be completely established. In this paper, the possible retrogradation mechanism of sweet potato starch was postulated from four optical micrographs at the stages of melting of the starch granules, autoclaving treatment and aging. The possible process of retrogradation consists of three stages. Firstly, starch granules was swelled and melted with loss of X-ray crystallinity and formation of both crystalline and amorphous lamellae; secondly, in crystalline lamellae, amylopectin began to form nucleation when they were autoclaved; finally, the nucleus grew up to great rod-like crystals as the result of congregating of amylose on plates which were composed of and prolongated by amylopectin.

  1. Mean-Field Limit and Phase Transitions for Nematic Liquid Crystals in the Continuum

    NASA Astrophysics Data System (ADS)

    Bachmann, Sven; Genoud, François

    2017-08-01

    We discuss thermotropic nematic liquid crystals in the mean-field regime. In the first part of this article, we rigorously carry out the mean-field limit of a system of N rod-like particles as N→ ∞, which yields an effective `one-body' free energy functional. In the second part, we focus on spatially homogeneous systems, for which we study the associated Euler-Lagrange equation, with a focus on phase transitions for general axisymmetric potentials. We prove that the system is isotropic at high temperature, while anisotropic distributions appear through a transcritical bifurcation as the temperature is lowered. Finally, as the temperature goes to zero we also prove, in the concrete case of the Maier-Saupe potential, that the system converges to perfect nematic order.

  2. Improved stoichiometry and photoanode efficiency of thermally evaporated CdS film with quantum dots as precursor.

    PubMed

    Fan, Libo; Wang, Peng; Guo, Qiuquan; Lei, Yan; Li, Ming; Han, Hongpei; Zhao, Haifeng; Yang, Dongluo; Zheng, Zhi; Yang, Jun

    2015-08-21

    Good stoichiometry of cadmium sulfide (CdS) film facilitates its application in photovoltaic devices; however, traditional thermal evaporation usually results in a Cd-deficient CdS film at a low-substrate temperature. In this study, Cd-rich CdS quantum dots (QDs) were synthesized by a facile co-precipitation method and used as the precursor to thermally evaporate CdS film on indium tin oxide-coated glass (ITO/glass). As a consequence, the stoichiometry of CdS film was greatly improved with atomic ratio of Cd to S restored to unity. More importantly, the newly developed CdS film, with its rod-like surface microstructure, acted as an efficient photoanode in a photoelectrochemical (PEC) cell. Its properties, including surface morphology and roughness, crystal structure, chemical composition, film thickness, energy-level structure and photosensitivity, are studied in detail.

  3. STM characterization of DNA immobilized via Zr ion glue onto gold thiol SAMs

    NASA Astrophysics Data System (ADS)

    Pourbeyram, S.; Shervedani, R. K.; Sabzyan, H.

    2013-10-01

    In this paper layer-by-layer (LBL) assembly of calf thymus DNA (ct-DNA) onto gold-mercaptopropionic acid self-assembled monolayer via Zr(IV) ion glue, Au-MPA-Zr(IV)-ct-DNA SAM, is monitored by scanning tunneling microscopy (STM) technique. The STM images of Au-MPA-Zr(IV) template show well-organized arrays of rod-like peaks. ct-DNA has been immobilized on the Au-MPA-Zr(IV) surface in hilly forms, implying globular structure for the immobilized ct-DNA. This immobilization strategy offers a simple and fast method to prepare the Au-MPA-Zr(IV)-ct-DNA template with promising applications for immobilization and study of the other compounds.

  4. Synthesis of MoS(2) nanorods and their catalytic test in the HDS of dibenzothiophene.

    PubMed

    Albiter, M A; Huirache-Acuña, R; Paraguay-Delgado, F; Rico, J L; Alonso-Nuñez, G

    2006-07-28

    Partially sulfided nanostructures were synthesized by direct sulfurization of alpha-MoO(3) nanorods using a mixture of H(2)S/H(2), 15 vol%, at several temperatures (400, 500, 600, 700, and 800 degrees C). These materials were tested as catalysts in the hydrodesulfurization (HDS) of dibenzothiophene (DBT) and characterized by specific surface areas using the expression developed by Brunauer, Emmett, and Teller (BET equation), x-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The TEM images show a gradual evolution from a smooth surface to a rough material, presenting some type of holes all over the particles, but keeping their rod-like structure throughout sulfidation. The results of evaluating the catalysts in the HDS of DBT showed that the best temperature for sulfidation is 500 degrees C. In all samples, a higher selectivity for hydrogenation over sulfur removal was observed.

  5. Highly ordered Pb(Zr0.52Ti0.48)O3 piezoelectric nanorod arrays

    NASA Astrophysics Data System (ADS)

    Yang, Su Chul; Sanghadasa, Mohan; Priya, Shashank

    2013-06-01

    One-dimensional (1D) piezoelectric nanostructures have attracted significant attention for a broad range of applications including optoelectronics, thermoelectrics, electrochemical and electromechanical converters. We demonstrate the synthesis of 1D nanostructures based upon Pb(Zr0.52Ti0.48)O3 (PZT) on conductive substrates via sol-gel template synthesis. The vertically aligned PZT nanostructures with heights around one micron were synthesized by vacuum infiltration of sol-gel precursors into highly ordered cylindrical pores of anodized aluminum oxide templates. The 1D nanostructures were developed on large scale platinized silicon wafers and exhibited dense rod-like structure with a uniform diameter of 90 nm and an aspect ratio of 10. Scanning probe microscopy conducted on individual nanorods demonstrated good electromechanical properties with a high piezoelectric magnitude of 41 pm V-1. We believe that this study opens the possibility of developing high performance nanoscale piezoelectric sensors and transducers.

  6. Highly ordered Pb(Zr₀.₅₂ Ti₀.₄₈)O₃ piezoelectric nanorod arrays.

    PubMed

    Yang, Su Chul; Sanghadasa, Mohan; Priya, Shashank

    2013-06-07

    One-dimensional (1D) piezoelectric nanostructures have attracted significant attention for a broad range of applications including optoelectronics, thermoelectrics, electrochemical and electromechanical converters. We demonstrate the synthesis of 1D nanostructures based upon Pb(Zr0.52Ti0.48)O3 (PZT) on conductive substrates via sol-gel template synthesis. The vertically aligned PZT nanostructures with heights around one micron were synthesized by vacuum infiltration of sol-gel precursors into highly ordered cylindrical pores of anodized aluminum oxide templates. The 1D nanostructures were developed on large scale platinized silicon wafers and exhibited dense rod-like structure with a uniform diameter of 90 nm and an aspect ratio of 10. Scanning probe microscopy conducted on individual nanorods demonstrated good electromechanical properties with a high piezoelectric magnitude of 41 pm V(-1). We believe that this study opens the possibility of developing high performance nanoscale piezoelectric sensors and transducers.

  7. Statistical foundations of liquid-crystal theory

    PubMed Central

    Seguin, Brian; Fried, Eliot

    2013-01-01

    We develop a mechanical theory for systems of rod-like particles. Central to our approach is the assumption that the external power expenditure for any subsystem of rods is independent of the underlying frame of reference. This assumption is used to derive the basic balance laws for forces and torques. By considering inertial forces on par with other forces, these laws hold relative to any frame of reference, inertial or noninertial. Finally, we introduce a simple set of constitutive relations to govern the interactions between rods and find restrictions necessary and sufficient for these laws to be consistent with thermodynamics. Our framework provides a foundation for a statistical mechanical derivation of the macroscopic balance laws governing liquid crystals. PMID:23772091

  8. Collective motion of microswimmers in viscoelastic fluids

    NASA Astrophysics Data System (ADS)

    Li, Gaojin; Ardekani, Arezoo

    2015-11-01

    The dynamics of suspension of self-propelled microorganisms show fascinating hydrodynamic phenomena, such as, large scale swarming motion, locally correlated motion, enhanced particle diffusion, and enhanced fluid mixing. Even though many studies have been conducted in a Newtonian fluid, the collective motion of microorganisms in non-Newtonian fluids is less understood. The non-Newtonian fluid rheological properties, such as viscoelasticity and shear-dependent viscosity in saliva, mucus and biofilm, significantly affect the swimming properties and hydrodynamic interaction of microorganisms. In this work, we use direct numerical simulation to investigate the collective motion of rod-like swimmers in viscoelastic fluids. Two swimming types, pusher and puller, are investigated. The background viscoelastic fluid is modeled using an Oldroyd-B constitutive equation. This work is supported by NSF CBET-1445955 and Indiana CTSI TR001108.

  9. Orientation of N-(1-(2-chlorophenyl)-2-(2-nitrophenyl)ethyl)-4-methylbenzenesulfonamide on silver nanoparticles: SERS studies.

    PubMed

    Anuratha, M; Jawahar, A; Umadevi, M; Sathe, V G; Vanelle, P; Terme, T; Meenakumari, V; Milton Franklin Benial, A

    2014-10-15

    In the present study, the silver nanoparticles were synthesized using a solution combustion method with urea as fuel. The prepared silver nanoparticles show an FCC crystalline structure with particle size of 59nm. FESEM image shows the prepared silver is a rod like structure. The surface-enhanced Raman scattering (SERS) spectrum indicates that the N-(1-(2-chlorophenyl)-2-(2-nitrophenyl)ethyl)-4-methylbenzenesulfonamide (CS) molecule adsorbed on the silver nanoparticles. The spectral analysis reveals that the sulfonamide is adsorbed by tilted orientation on the silver surface. The Hatree Fock calculations were also performed to predict the vibrational motions of CS. This present investigation has been a model system to deduce the interaction of drugs with DNA. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. Enhanced magnetorheological response of magnetic chromium dioxide nanoparticle added carbonyl iron suspension

    NASA Astrophysics Data System (ADS)

    Kim, Min Hwan; Choi, Kisuk; Do Nam, Jae; Choi, Hyoung Jin

    2017-09-01

    Hard-magnetic chromium dioxide nanoparticles with a rod-like shape were introduced as an additive to a soft-magnetic carbonyl iron (CI)-based magnetorheological (MR) fluid. The magnetic stimuli-response of the MR fluid in terms of the steady shear and dynamic oscillation tests was examined using a rotational rheometer. While the Bingham fluid model fitted the flow curves, the dynamic yield stress followed the universal yield stress scale function quite well. Compared to the CI-based MR fluid without chromium dioxide nanoparticles, the MR fluid with the chromium dioxide additive exhibited remarkably higher yield behavior with increasing magnetic field strength, enhancing its MR performance and dispersion stability.

  11. Controlled synthesis of crystalline calcium carbonate aggregates with unusual morphologies involving the phase transformation from amorphous calcium carbonate

    SciTech Connect

    Tang Hua; Yu Jiaguo Zhao Xiufeng

    2009-04-02

    Peanut-shaped CaCO{sub 3} aggregates, featured of two dandelion-like heads built up from rod-like subunits, have been synthesized via a facile precipitation reaction between Na{sub 2}CO{sub 3} and CaCl{sub 2} at ambient temperature in the presence of magnesium ions and ethanol solvent. The as-prepared products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and inductively coupled plasma atomic emission spectrometry (ICP-AES). The results show that a high magnesium concentration and ethanol solvent are necessary for the formation of the unusual peanut-like aggregates. In addition, a multistep phase transformation process from amorphous calcium carbonate (ACC) to a mixture of ACC and calcite and ultimately to calcite and aragonite was observed in the formation process of the unusual structures. A possible mechanism for the formation of the unusual peanut-shape aggregates has been proposed and discussed.

  12. Filamentous Phages As a Model System in Soft Matter Physics.

    PubMed

    Dogic, Zvonimir

    2016-01-01

    Filamentous phages have unique physical properties, such as uniform particle lengths, that are not found in other model systems of rod-like colloidal particles. Consequently, suspensions of such phages provided powerful model systems that have advanced our understanding of soft matter physics in general and liquid crystals in particular. We described some of these advances. In particular we briefly summarize how suspensions of filamentous phages have provided valuable insight into the field of colloidal liquid crystals. We also describe recent experiments on filamentous phages that have elucidated a robust pathway for assembly of 2D membrane-like materials. Finally, we outline unique structural properties of filamentous phages that have so far remained largely unexplored yet have the potential to further advance soft matter physics and material science.

  13. Imbibition in mesoporous silica: rheological concepts and experiments on water and a liquid crystal.

    PubMed

    Gruener, Simon; Huber, Patrick

    2011-05-11

    We present, along with some fundamental concepts regarding imbibition of liquids in porous hosts, an experimental, gravimetric study on the capillarity-driven invasion dynamics of water and of the rod-like liquid crystal octyloxycyanobiphenyl (8OCB) in networks of pores a few nanometers across in monolithic silica glass (Vycor). We observe, in agreement with theoretical predictions, square root of time invasion dynamics and a sticky velocity boundary condition for both liquids investigated. Temperature-dependent spontaneous imbibition experiments on 8OCB reveal the existence of a paranematic phase due to the molecular alignment induced by the pore walls even at temperatures well beyond the clearing point. The ever present velocity gradient in the pores is likely to further enhance this ordering phenomenon and prevent any layering in molecular stacks, eventually resulting in a suppression of the smectic phase in favor of the nematic phase.

  14. Luminescent infinite coordination polymer materials from metal-terpyridine ligation.

    PubMed

    Eryazici, Ibrahim; Farha, Omar K; Compton, Owen C; Stern, Charlotte; Hupp, Joseph T; Nguyen, SonBinh T

    2011-09-28

    A new class of infinite coordination polymers (CP) was synthesized using a tetrahedral tetrakis[4-(4'-phenyl-2,2':6',2''-terpyridine)phenyl]methane ligand as an organic node to direct the three-dimensional growth of the network and M(II) (M = Zn, Fe, Ni, and Ru) ions as inorganic linkers, an approach that is the opposite of the metal-as-a-node strategy used in the construction of metal-organic frameworks (MOFs). The unusual rod-like morphology of the resulting microporous materials can be tuned via solvents and reaction conditions. The covalent entrapment of a [Ru(tpy)(2)](2+) moiety in the skeleton of the 3D-network enables the Ru-CP to exhibit room-temperature luminescence.

  15. The avian intervertebral disc arises from rostral sclerotome and lacks a nucleus pulposus: Implications for evolution of the vertebrate disc

    PubMed Central

    Bruggeman, Bradley J.; Maier, Jennifer A.; Mohiuddin, Yasmin S.; Powers, Rae; Lo, YinTing; Guimarães-Camboa, Nuno; Evans, Sylvia M.; Harfe, Brian D.

    2012-01-01

    Deterioration of the intervertebral discs is an unfortunate consequence of aging. The intervertebral disc in mammals is composed of three parts: a jelly-like center called the nucleus pulposus, the cartilaginous annulus fibrosus and anterior and posterior endplates that attach the discs to vertebrae. In order to understand the origin of the disc, we have investigated the intervertebral region of chickens. Surprisingly, our comparison of mouse and chicken discs revealed that chicken discs lack nuclei pulposi. In addition, the notochord, which in mice forms nuclei pulposi, was found to persist as a rod-like structure and express Shh throughout chicken embryogenesis. Our fate mapping data indicates that cells originating from the rostral half of each somite are responsible for forming the avian disc while cells in the caudal region of each somite form vertebrae. A histological analysis of mammalian and non-mammalian organisms suggests that nuclei pulposi are only present in mammals. PMID:22354863

  16. Flexibility of the cytoplasmic domain of the phototaxis transducer II from Natronomonas pharaonis.

    PubMed

    Budyak, Ivan L; Mironova, Olga S; Yanamala, Naveena; Manoharan, Vijayalaxmi; Büldt, Georg; Schlesinger, Ramona; Klein-Seetharaman, Judith

    2008-01-01

    Chemo- and phototaxis systems in bacteria and archaea serve as models for more complex signal transduction mechanisms in higher eukaryotes. Previous studies of the cytoplasmic fragment of the phototaxis transducer (pHtrII-cyt) from the halophilic archaeon Natronomonas pharaonis showed that it takes the shape of a monomeric or dimeric rod under low or high salt conditions, respectively. CD spectra revealed only approximately 24% helical structure, even in 4 M KCl, leaving it an open question how the rod-like shape is achieved. Here, we conducted CD, FTIR, and NMR spectroscopic studies under different conditions to address this question. We provide evidence that pHtrII-cyt is highly dynamic with strong helical propensity, which allows it to change from monomeric to dimeric helical coiled-coil states without undergoing dramatic shape changes. A statistical analysis of predicted disorder for homologous sequences suggests that structural flexibility is evolutionarily conserved within the methyl-accepting chemotaxis protein family.

  17. Simulation of alnico coercivity

    NASA Astrophysics Data System (ADS)

    Ke, Liqin; Skomski, Ralph; Hoffmann, Todd D.; Zhou, Lin; Tang, Wei; Johnson, Duane D.; Kramer, Matthew J.; Anderson, Iver E.; Wang, C.-Z.

    2017-07-01

    Micromagnetic simulations of alnico show substantial deviations from Stoner-Wohlfarth behavior due to the unique size and spatial distribution of the rod-like Fe-Co phase formed during spinodal decomposition in an external magnetic field. The maximum coercivity is limited by single-rod effects, especially deviations from ellipsoidal shape, and by interactions between the rods. Both the exchange interaction between connected rods and magnetostatic interaction between rods are considered, and the results of our calculations show good agreement with recent experiments. Unlike systems dominated by magnetocrystalline anisotropy, coercivity in alnico is highly dependent on size, shape, and geometric distribution of the Fe-Co phase, all factors that can be tuned with appropriate chemistry and thermal-magnetic annealing.

  18. A unique case of magnet ingestion with respect to presentation and management.

    PubMed

    Yalçin, Sule; Karnak, Ibrahim; Ekinci, Saniye; Senocak, Mehmet Emin

    2012-01-01

    Magnet ingestion may lead to serious complications with delay in diagnosis and treatment. The forceful attraction between magnets, with gastric and/or intestinal wall entrapped between them, can cause injury through pressure necrosis. The radiological appearance of more than one magnet on X-ray can be easily misinterpreted as belonging to only one rod-like radiopaque foreign body, even if the magnets are located in different parts of the gastrointestinal tract, thus delaying the management up to the onset of emergent surgical complications. A 17-month-old female with ingestion of a pair of magnets is presented, together with introduction of the clinical picture and therapeutic approach, which differed from the other previously reported cases. The ovoid shape of the magnets, their localization in the gastrointestinal tract (leading to entrapped gastric and intestinal wall between them), absence of any complication, and the therapeutic approach of endoscopic retrieval are the main distinguishing features of this case from those previously reported.

  19. Controlling electrical percolation in multicomponent carbon nanotube dispersions.

    PubMed

    Kyrylyuk, Andriy V; Hermant, Marie Claire; Schilling, Tanja; Klumperman, Bert; Koning, Cor E; van der Schoot, Paul

    2011-04-10

    Carbon nanotube reinforced polymeric composites can have favourable electrical properties, which make them useful for applications such as flat-panel displays and photovoltaic devices. However, using aqueous dispersions to fabricate composites with specific physical properties requires that the processing of the nanotube dispersion be understood and controlled while in the liquid phase. Here, using a combination of experiment and theory, we study the electrical percolation of carbon nanotubes introduced into a polymer matrix, and show that the percolation threshold can be substantially lowered by adding small quantities of a conductive polymer latex. Mixing colloidal particles of different sizes and shapes (in this case, spherical latex particles and rod-like nanotubes) introduces competing length scales that can strongly influence the formation of the system-spanning networks that are needed to produce electrically conductive composites. Interplay between the different species in the dispersions leads to synergetic or antagonistic percolation, depending on the ease of charge transport between the various conductive components.

  20. Morphology and inner structure of ethanol sensitive thin films of tin oxide operating at near room temperature

    NASA Astrophysics Data System (ADS)

    Mahdi, O. S.; Malyar, I. V.; Galushka, V. V.; Smirnov, A. V.; Sinev, I. V.; Venig, S. B.

    2017-06-01

    Thin tin oxide films were fabricated by reactive RF magnetron sputtering. It was shown that the films possess gas sensitivity to ethanol vapor at 38°C. Measurements of the morphology and cleavage inner structure of the samples by atomic-force and scanning electron microscopy demonstrate that the films are composed of nanodimensional rod-like grains oriented normally to the substrate. The grains are separated by pores piercing the whole film. It was found that the grain diameter distribution is normal logarithmic one with several centers related as small integers, which indicates that the grains coalesce. The minimum grain size of 6 nm might correspond to the critical nucleus size under the used conditions of film deposition.

  1. ELECTROMAGNETISM, OPTICS, ACOUSTICS, HEAT TRANSFER, CLASSICAL MECHANICS, AND FLUID DYNAMICS: Apparently Negative Electric Polarization in Shaped Graded Dielectric Materials

    NASA Astrophysics Data System (ADS)

    Fan, Chun-Zhen; Gao, Yin-Hao; Gao, Yong; Huang, Ji-Ping

    2010-05-01

    By using a first-principles approach, we investigate the pathway of electric displacement fields in shaped graded dielectric materials existing in the form of cloaks with various shapes. We reveal a type of apparently negative electric polarization (ANEP), which is due to a symmetric oscillation of the paired electric permittivities, satisfying a sum rule. The ANEP does not occur for a spherical cloak, but appears up to maximum as a/b (the ratio between the long and short principal axis of the spheroidal cloak) is about 5/2, and eventually disappears as a/b becomes large enough corresponding to a rod-like shape. Further, the cloaking efficiency is calculated for different geometrical shapes and demonstrated to closely relate to the ANEP. The possibility of experiments is discussed. This work has relevance to dielectric shielding based on shaped graded dielectric materials.

  2. Effect of polysaccharide nanocrystals on structure, properties, and drug release kinetics of alginate-based microspheres.

    PubMed

    Lin, Ning; Huang, Jin; Chang, Peter R; Feng, Liangdong; Yu, Jiahui

    2011-07-01

    Polysaccharide nanocrystals, such as rod-like cellulose nanocrystals and chitin whiskers and platelet-like starch nanocrystals, were incorporated into alginate-based nanocomposite microspheres with the aim of enhancing mechanical strength and regulating drug release behavior. The structures and properties of the sols and the resultant nanocomposite microspheres were characterized by rheological testing, Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The presence of polysaccharide nanocrystals increased the stability of the crosslinked network structure, and the nanocomposite microspheres consequently exhibited prominent sustained release profiles, as demonstrated by inhibited diffusion of theophylline. Furthermore, based on the drug release results, the release kinetics and transport mechanisms were analyzed and discussed. Crown Copyright © 2011. Published by Elsevier B.V. All rights reserved.

  3. Glycans as biofunctional ligands for gold nanorods: stability and targeting in protein-rich media.

    PubMed

    García, Isabel; Sánchez-Iglesias, Ana; Henriksen-Lacey, Malou; Grzelczak, Marek; Penadés, Soledad; Liz-Marzán, Luis M

    2015-03-18

    Poly(ethylene glycol) (PEG) has become the gold standard for stabilization of plasmonic nanoparticles (NPs) in biofluids, because it prevents aggregation while minimizing unspecific interactions with proteins. Application of Au NPs in biological environments requires the use of ligands that can target selected receptors, even in the presence of protein-rich media. We demonstrate here the stabilizing effect of low-molecular-weight glycans on both spherical and rod-like plasmonic NPs under physiological conditions, as bench-marked against the well-established PEG ligands. Glycan-coated NPs are resistant to adsorption of proteins from serum-containing media and avoid phagocytosis by macrophage-like cells, but retain selectivity toward carbohydrate-binding proteins in protein-rich biological media. These results open the way toward the design of efficient therapeutic/diagnostic glycan-decorated plasmonic nanotools for specific biological applications.

  4. A simple method to tailor spherical nanocrystal hydroxyapatite at low temperature

    NASA Astrophysics Data System (ADS)

    Zhang, Yanjie; Lu, Jinjun

    2007-08-01

    A simple method, chemical precipitation at low temperature from Ca(NO3)2·4H2O and (NH4)2HPO4 to tailor single phase, highly crystalline nanocrystal hydroxyapatite (HAp) powders was introduced in this paper. HAp powders with controlled morphologies (spherical and rod-like) and different grain sizes have been obtained by varying the reaction temperature, reaction mode, and heat treatment accordingly. X-ray diffraction (XRD) results combined with the Fourier transform-infrared spectroscopy (FT-IR) indicates that the single phase, nanocrystal HAp powder could be obtained in one-step without further heat treatment. At 40 °C with a quick mixing mode, ultra-fine complete spherical HAp particles with diameter range size of 20-50 nm could be obtained.

  5. Phase Transformation Behavior at Low Temperature in Hydrothermal Treatment of Stable and Unstable Titania Sol

    PubMed

    So; Park; Kim; Moon

    1997-07-15

    Nanosize titania sol was prepared from titanium tetraisopropoxide (TTIP) and conditions for the formation of stable sol were identified. As the H+/TTIP mole ratio decreased and H2O/TTIP mole ratio increased, stable sol was likely to be formed. The size and crystallinity remained unchanged after hydrothermal treatment of the stable sol at between 160 and 240°C. However, hydrothermal treatment of unstable sol produced rod-like particles and crystallinity of particles was changed from anatase to rutile. This difference in phase transformation at low hydrothermal treatment temperature was likely to be caused by the fact that stable sol remained to be stable even after hydrothermal treatment, while unstable sol had a tendency to be aggregated.

  6. Growth of gold nanoclusters and nanocrystals induced by lysozyme protein in thin film conformation

    NASA Astrophysics Data System (ADS)

    Bhowal, Ashim Chandra; Kundu, Sarathi

    2016-08-01

    Structures and growth behavior of gold nanoclusters and nanocrystals have been explored on thin films of globular protein lysozyme by using UV-vis and photoluminescence spectroscopy, X-ray diffraction (XRD) and atomic force microscopy (AFM). A simple and one-step environment friendly method has been used to grow nanocrystals on protein surface from HAuCl4 solution. It has been found that if different interaction times are provided between lysozyme films and HAuCl4 solution, then initially formed tiny gold nanoclusters on protein surface transform into nanocrystals with the passage of time. XRD analysis shows the formation of faced-centered cubic lattice along (1 1 1) crystalline direction and AFM images confirm the presence of circular, rod-like, triangular and hexagonal crystal structures. Langmuir-like growth behavior has been identified for both the gold nanoclusters and nanocrystals formation induced by the lysozyme films, however, nanocrystal growth is relatively slower than nanocluster.

  7. Observation of Precipitation Evolution in Fe-Ni-Mn-Ti-Al Maraging Steel by Atom Probe Tomography

    NASA Astrophysics Data System (ADS)

    Pereloma, E. V.; Stohr, R. A.; Miller, M. K.; Ringer, S. P.

    2009-12-01

    We describe the full decomposition sequence in an Fe-Ni-Mn-Ti-Al maraging steel during isothermal annealing at 550 °C. Following significant pre-precipitation clustering reactions within the supersaturated martensitic solid solution, (Ni,Fe)3Ti and (Ni,Fe)3(Al,Mn) precipitates eventually form after isothermal aging for ~60 seconds. The morphology of the (Ni,Fe)3Ti particles changes gradually during aging from predominantly plate-like to rod-like, and, importantly, Mn and Al were observed to segregate to these precipitate/matrix interfaces. The (Ni,Fe)3(Al,Mn) precipitates occurred at two main locations: uniformly within the matrix and at the periphery of the (Ni,Fe)3Ti particles. We relate this latter mode of precipitation to the Mn-Al segregation.

  8. Observation of Precipitation Evolution in Fe-Ni-Mn-Ti-Al Maraging Steel using Atom Probe Tomography

    SciTech Connect

    Pereloma, E. V.; Stohr, R A; Miller, Michael K; Ringer, S. P.

    2009-01-01

    We describe the full decomposition sequence in an Fe-Ni-Mn-Ti-Al maraging steel during isothermal annealing at 550 C. Following significant pre-precipitation clustering reactions within the supersaturated martensitic solid solution, (Ni,Fe){sub 3}Ti and (Ni,Fe){sub 3}(Al,Mn) precipitates eventually form after isothermal aging for {approx}60 seconds. The morphology of the (Ni,Fe){sub 3}Ti particles changes gradually during aging from predominantly plate-like to rod-like, and, importantly, Mn and Al were observed to segregate to these precipitate/matrix interfaces. The (Ni,Fe){sub 3}(Al,Mn) precipitates occurred at two main locations: uniformly within the matrix and at the periphery of the (Ni,Fe){sub 3}Ti particles. We relate this latter mode of precipitation to the Mn-Al segregation.

  9. Facile synthesis of SrCO3 nanostructures in methanol/water solution without additives

    PubMed Central

    2012-01-01

    Highly dispersive strontium carbonate (SrCO3) nanostructures with uniform dumbbell, ellipsoid, and rod-like morphologies were synthesized in methanol solution without any additives. These SrCO3 were characterized by X-ray diffraction, field emission scanning electron microscopy, and N2 adsorption-desorption. The results showed that the reaction temperature and the methanol/water ratio had important effects on the morphologies of SrCO3 particles. The dumbbell-like SrCO3 exhibited a Broader-Emmett-Teller surface area of 14.9 m2 g−1 and an average pore size of about 32 nm with narrow pore size distribution. The formation mechanism of the SrCO3 crystal was preliminary presented. PMID:22704526

  10. Empty liquid phase of colloidal ellipsoids: the role of shape and interaction anisotropy.

    PubMed

    Varga, Szabolcs; Meneses-Júarez, Efrain; Odriozola, Gerardo

    2014-04-07

    We study the effect of anisotropic excluded volume and attractive interactions on the vapor-liquid phase transition of colloidal ellipsoids. In our model, the hard ellipsoid is embedded into an ellipsoidal well, where both the shape of the hard ellipsoid and that of the added enclosing ellipsoidal well can be varied independently. The bulk properties of these particles are examined by means of a van der Waals type perturbation theory and validated with replica exchange Monte Carlo simulations. It is shown that both the critical volume fraction (ηc) and the critical temperature (Tc) of the vapor-liquid phase transition vanish with increasing shape anisotropy for oblate shapes, while ηc → 0 and Tc ≠ 0 are obtained for very elongated prolate shapes. These results suggest that the chance to stabilize empty liquids (a liquid phase with vanishing density) is higher in suspensions of rod-like colloidal ellipsoids than in those of plate-like ones.

  11. The dopant dependent photocatalytic activity of polyaniline towards the degradation of Rose Bengal dye

    NASA Astrophysics Data System (ADS)

    Chatterjee, Mukulika Jana; Banerjee, Dipali; Ghosh, Amrita; Mondal, Anup

    2016-05-01

    Polyaniline (PANI) with two different dopants, hydrochloric acid (HCl) and bismuth nitrate (Bi (NO3)3), were synthesized to investigate the effect of dopant on photocatalytic degradation of Rose Bengal, an organic dye, in presence of sunlight. PANI, synthesized by in situ polymerization was characterized by FESEM images, FTIR and UV-Vis spectra. FESEM images show rod like structures obtained for both the dopants. FTIR spectra confirms the formation of conducting PANI with the presence of C=N, C=C stretching modes in quinoid and benzenoid units. Band gap of PANI has been obtained from UV-Vis spectrum. Doped polyaniline exhibited a fast degradation of dye by 98.62 % & 98.12 % within 5 min & 8 min under visible light illumination for the dopant HCl & Bi (NO3)3 respectively.

  12. Characterization of a trimeric MPER containing HIV-1 gp41 antigen

    SciTech Connect

    Hinz, Andreas; Schoehn, Guy; Quendler, Heribert; Hulsik, David Lutje; Stiegler, Gabi; Katinger, Hermann; Seaman, Michael S.; Montefiori, David; Weissenhorn, Winfried

    2009-08-01

    The membrane-proximal external region (MPER) of gp41 is considered as a prime target for the induction of neutralizing antibodies, since it contains the epitopes for three broadly neutralizing antibodies (2F5, 4E10 and Z13). Here we present a novel gp41 construct (HA-gp41) comprising gp41 HR2 and MPER fused to two triple-stranded coiled-coil domains at both ends. HA-gp41 is trimeric, has a high helical content in solution and forms rod-like structures as revealed by negative staining electron microscopy. Immunization of rabbits with HA-gp41 induced antibodies directed against MPER, which failed to exert significant neutralization capacity against envelopes from primary isolates. Thus trimerisation of MPER regions does not suffice to induce a potent neutralizing antibody response specific for conserved regions within gp41.

  13. Synthesis and characterization of Nb2O5@C core-shell nanorods and Nb2O5nanorods by reacting Nb(OEt)5via RAPET (reaction under autogenic pressure at elevated temperatures) technique

    PubMed Central

    George, PP; Pol, VG

    2007-01-01

    The reaction of pentaethoxy niobate, Nb(OEt)5, at elevated temperature (800 °C) under autogenic pressure provides a chemical route to niobium oxide nanorods coated with amorphous carbon. This synthetic approach yielded nanocrystalline particles of Nb2O5@C. As prepared Nb2O5@C core-shell nanorods is annealed under air at 500 °C for 3 h (removing the carbon coating) results in neat Nb2O5nanorods. According to the TEM measurements, the Nb2O5crystals exhibit particle sizes between 25 nm and 100 nm, and the Nb2O5crystals display rod-like shapes without any indication of an amorphous character. The optical band gap of the Nb2O5nanorods was determined by diffuse reflectance spectroscopy (DRS) and was found to be 3.8 eV.

  14. Synthesis of zeolite Li-ABW from fly ash by fusion method.

    PubMed

    Yao, Z T; Xia, M S; Ye, Y; Zhang, L

    2009-10-30

    The zeolite Li-ABW was synthesized by fusion method using fly ash as raw material. It comprised alkaline fusion followed by hydrothermal treatment in LiOH x H2O medium. Crystallinity of zeolite as high as 97.8% was attained under the following conditions: LiOH x H2O concentration, 3M; hydrothermal temperature, 180 degrees C; the corresponding aging time, 12 h. The content of Li-ABW increased at the expense of lithium aluminum silicate or quartz with an increase of LiOH x H2O concentration. With increasing hydrothermal temperature and aging time, the soluble species re-crystallized and crystalline phase transformation between different zeolites was observed. Scanning electron microscopy (SEM) observation revealed that the obtained zeolite Li-ABW was a rod-like crystal. The pore size distribution curve indicated the presence of mesopores.

  15. Co-axial capillaries microfluidic device for synthesizing size- and morphology-controlled polymer core-polymer shell particles.

    PubMed

    Chang, Zhenqi; Serra, Christophe A; Bouquey, Michel; Prat, Laurent; Hadziioannou, Georges

    2009-10-21

    An easy assembling-disassembling co-axial capillaries microfluidic device was built up for the production of double droplets. Uniform polymer core-polymer shell particles were synthesized by polymerizing the two immiscible monomer phases composing the double droplet. Thus poly(acrylamide) core-poly(tri(propylene glycol) diacrylate) shell particles with controlled core diameter and shell thickness were simply obtained by adjusting operating parameters. An empirical law was extracted from experiments to predict core and shell sizes. Additionally uniform and predictable non-spherical polymer objects were also prepared without adding shape-formation procedures in the experimental device. An empirical equation for describing the lengths of rod-like polymer particles is also presented.

  16. Biaxial ferromagnetic liquid crystal colloids

    PubMed Central

    Liu, Qingkun; Ackerman, Paul J.; Lubensky, Tom C.; Smalyukh, Ivan I.

    2016-01-01

    The design and practical realization of composite materials that combine fluidity and different forms of ordering at the mesoscopic scale are among the grand fundamental science challenges. These composites also hold a great potential for technological applications, ranging from information displays to metamaterials. Here we introduce a fluid with coexisting polar and biaxial ordering of organic molecular and magnetic colloidal building blocks exhibiting the lowest symmetry orientational order. Guided by interactions at different length scales, rod-like organic molecules of this fluid spontaneously orient along a direction dubbed “director,” whereas magnetic colloidal nanoplates order with their dipole moments parallel to each other but pointing at an angle to the director, yielding macroscopic magnetization at no external fields. Facile magnetic switching of such fluids is consistent with predictions of a model based on competing actions of elastic and magnetic torques, enabling previously inaccessible control of light. PMID:27601668

  17. Density functional theory and simulations of colloidal triangular prisms.

    PubMed

    Marechal, Matthieu; Dussi, Simone; Dijkstra, Marjolein

    2017-03-28

    Nanopolyhedra form a versatile toolbox to investigate the effect of particle shape on self-assembly. Here we consider rod-like triangular prisms to gauge the effect of the cross section of the rods on liquid crystal phase behavior. We also take this opportunity to implement and test a previously proposed version of fundamental measure density functional theory (0D-FMT). Additionally, we perform Monte Carlocomputer simulations and we employ a simpler Onsager theory with a Parsons-Lee correction. Surprisingly and disappointingly, 0D-FMT does not perform better than the Tarazona and Rosenfeld's version of fundamental measure theory (TR-FMT). Both versions of FMT perform somewhat better than the Parsons-Lee theory. In addition, we find that the stability regime of the smectic phase is larger for triangular prisms than for spherocylinders and square prisms.

  18. Sodium acetate assisted hydrothermal growth of dumbbell-like β -NaGdF4 nanobundles: Morphology control and products transformation

    NASA Astrophysics Data System (ADS)

    Wu, Kelu; Wang, Yi-Yan; Xia, Tian-Long

    2017-08-01

    Hierarchical β -NaGdF4 nanobundles are synthesized through a facile hydrothermal method with the use of sodium acetate (NaAc). A NaGdF4-GdF3-NaGdF4 products transformation with the increase of fluoride source (NaF) is observed. Results show that NaAc is the key factor in the synthesis of β -NaGdF4 at a low NaF/Gd3+ ratio and NaAc also plays a significant role in the formation of the hierarchical morphology. Meanwhile, the size of nanobundles increases with the increased ratio of NaF/NaAc. With altering the ratio of reactants, dumbbell-like, urchin-like or rod-like β -NaGdF4 nanobundles are obtained. The photoluminescent properties of β -NaGdF4: 2%Eu3+ are also measured.

  19. Microfluidic techniques for the study of self-assembly of soft materials

    NASA Astrophysics Data System (ADS)

    Aguade Cabanas, Rafael

    This research is an approach to the study of soft condensed matter where the use of new microfluidic technology plays a central role. Often, in the study of soft matter, the sample volumes are very small, of the order of nanoliters. Therefore to quantitatively measure the equilibrium or non-equilibrium phase behavior requires microfluidics. Presented here are (1) a new way of producing aqueous drops of order 1 nl volume, in oil, (2) a new fabrication protocol to make microfluidic devices out of epoxy glue, and (3) a new microfluidic flow cell to study colloidal self-assembly. Also presented here is a new kind of colloidal particle, consisting of single strands of DNA linked to the surface of fd virus. This new particle may serve as a liquid crystalline colloid with a temperature dependent tunable potential. The fabrication process is the first step in the study of the self-assembly of rod-like particles with a temperature dependent potential.

  20. Structural constraints on the evolution of the collagen fibril: convergence on a 1014-residue COL domain

    PubMed Central

    Slatter, David Anthony; Farndale, Richard William

    2015-01-01

    Type I collagen is the fundamental component of the extracellular matrix. Its α1 gene is the direct descendant of ancestral fibrillar collagen and contains 57 exons encoding the rod-like triple-helical COL domain. We trace the evolution of the COL domain from a primordial collagen 18 residues in length to its present 1014 residues, the limit of its possible length. In order to maintain and improve the essential structural features of collagen during evolution, exons can be added or extended only in permitted, non-random increments that preserve the position of spatially sensitive cross-linkage sites. Such sites cannot be maintained unless the twist of the triple helix is close to 30 amino acids per turn. Inspection of the gene structure of other long structural proteins, fibronectin and titin, suggests that their evolution might have been subject to similar constraints. PMID:25994354