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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. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. [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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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%.

  14. 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

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  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. 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.

  4. 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.

  5. Facile synthesis of rod-like Cu2-xSe and insight into its improved lithium storage property.

    PubMed

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

    2017-04-06

    A rod-like Cu2-xSe is synthesized via a facile water evaporation process. The electrochemical reaction mechanism is investigated with ex-situ X-ray diffraction (XRD) test. By adopting ether-based electrolyte instead of carbonate-based electrolyte, the electrochemical performance of Cu2-xSe electrodes improves significantly. The Cu2-xSe electrodes exhibit outstanding cycle performance, after 1000 cycles, 160 mAh g-1 can be maintained with the retention of 80.3 %. At current density of 100, 200, 500 and 1000 mA g-1, the capacity of Cu2-xSe/Li battery is 208, 202, 200 and 198 mAh 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-xSe electrodes display high specific conductivity and impressive lithium ion diffusion rate, which makes the Cu2-xSe to be a promising anode material for lithium ion batteries.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. 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.

  17. 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.

  18. 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

  19. 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

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  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. 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.

  7. 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.

  8. 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

  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. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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

  5. 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.

  6. 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.

  7. 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-)).

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  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. 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.

  18. 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

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. 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 +}.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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}.

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. Imide Modified Epoxy Matrix Resin.

    DTIC Science & Technology

    1981-02-01

    the bisimide amine cured epoxies (IME’s) were considerably lower than the state-of-the-art epoxies . The strain-to-failure of the control resin system ...nine epoxy resin systems which were prepared from tetraglycidyl methylenedianiline (MY 720) cured with a stoichiometric quantity of bisimide-amine and...graphite imide modified cured epoxy resin composites. The designation for each material is also listed in Table 1. The composition of each resin system

  16. 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

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  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. 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.

  7. 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.

  8. 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)

  9. 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.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  11. 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.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. 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

  4. 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.

  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. 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

  8. 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).

  9. 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.

  10. 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.

  11. 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

  12. 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.

  13. 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.

  14. 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.

  15. [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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  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. 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.

  3. 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

  4. 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.

  5. 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).

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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

  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. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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

  7. 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.

  8. 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.

  9. 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

  10. 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

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. 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

  16. 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.

  17. 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.

  18. [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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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

  4. 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.

  5. 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.

  6. 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

  7. 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.

  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. 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.

  10. 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.

  11. 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.

  12. 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.

  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. 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.

  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. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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).

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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

  18. 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

  19. 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

  20. 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

  1. 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.

  2. 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

    2017-04-06

    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.

  3. 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.

  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. 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.

  6. 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.

  7. 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).

  8. 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.

  9. 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.

  10. 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

  11. 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

  12. 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.

  13. 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

  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. 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.

  16. 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.

  17. Synthesis of pyrite FeS2 nanorods by simple hydrothermal method and its photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Morales-Gallardo, M. V.; Ayala, A. M.; Pal, Mou; Cortes Jacome, M. A.; Toledo Antonio, J. A.; Mathews, N. R.

    2016-09-01

    In this work, FeS2 nanorods were synthetized by hydrothermal method. The advantages of our process were the high yield, simplicity and reproducibility. The material was studied in detail using different experimental tools such as XRD, SEM, HRTEM, EDXS, XPS, Raman, and UV-vis reflectance. XRD pattern and Raman data revealed good crystalline quality for the as synthesized pyrite FeS2. SEM analysis displayed the rod-like morphologies of FeS2 which seemed to grow radially from a center giving a flower-like appearance. From TEM images the approximate length and diameter of nano-rods were determined as 275 and 15 nm respectively. The material showed excellent photocatalytic activity which was assessed from the degradation of the methlyene blue.

  18. Understanding nanocellulose chirality and structure–properties relationship at the single fibril level

    PubMed Central

    Usov, Ivan; Nyström, Gustav; Adamcik, Jozef; Handschin, Stephan; Schütz, Christina; Fall, Andreas; Bergström, Lennart; Mezzenga, Raffaele

    2015-01-01

    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. PMID:26108282

  19. The Landau-de Gennes free energy expansion of a melt of V-shaped polymer molecules.

    PubMed

    Aliev, M A; Ugolkova, E A; Kuzminyh, N Yu

    2016-08-28

    The phase behavior of a monodisperse melt of polymer molecules consisting of two rod-like segments joined at an angle α has been inspected within the Landau theory of phase transitions. The interactions between monomer units were assumed to be of the Maier-Saupe form. The Landau-de Gennes expansion of the free energy of the melt has been obtained up to the sixth order in powers of the nematic order parameter, the coefficients of this expansion have been calculated from the microscopic model of polymer molecule. The phase diagram contains the regions of stability of isotropic, prolate uniaxial, oblate uniaxial, and biaxial nematic phases. The isotropic-uniaxial nematic and uniaxial-biaxial nematic transitions are of the first and second order, respectively. We found two Landau points in the phase diagram at which continuous transition from biaxial nematic state to isotropic phase occurs.

  20. Evidence for filamentous actin in ookinetes of a malarial parasite.

    PubMed

    Siden-Kiamos, Inga; Louis, Christos; Matuschewski, Kai

    2012-02-01

    Extracellular stages of apicomplexan parasites utilize their own actin myosin motor machinery for gliding locomotion, penetration of cell barriers, and host cell invasion. Thus far, filamentous actin could not be visualized by standard microscopic techniques in vivo. Here, we describe the generation of a novel peptide antibody against the divergent amino-terminal portion of the major Plasmodium isoform, actin I. We show that our antiserum, termed Ab-actinI-I, is conformation-specific. In motile ookinetes it recognizes actin in rod-like structures, which are sensitive to inhibitors interfering with actin polymerization. The average size of the rods is 600 nm, which is considerably longer than what has been detected in in vitro studies of actin filaments.

  1. 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.

  2. 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) .

  3. Adsorption of N-(1-(2-bromophenyl)-2-(2-nitrophenyl)ethyl)-4-methylbenzenesulfonamide on silver nanoparticles: SERS investigation.

    PubMed

    Anuratha, M; Jawahar, A; Umadevi, M; Sathe, V G; Vanelle, P; Terme, T; Khoumeri, O; Meenakumari, V; Milton Franklin Benial, A

    2015-03-05

    SERS provides essential data regarding the interaction of molecules in drugs with DNA. In the present study silver nanoparticles were synthesized using a solution combustion method with urea as fuel. The prepared silver nanoparticles are rod like structure. Surface-enhanced Raman scattering (SERS) of N-(1-2-bromophenyl)-2-(2-nitrophenyl)ethyl)-4-methylbenzenesulfonamide (BrS) adsorbed on the silver nanoparticle was studied. The nRs and Raman spectral analysis reveal that the BrS adsorbed tilted orientation on the silver surface. Vibrational modes of nRs along with HF calculations are also performed to study the HOMO and LUMO behavior and vibrational features of BrS.

  4. Influence of Flexibility and Dimensions of Nanocelluloses on the Flow Properties of Their Aqueous Dispersions.

    PubMed

    Tanaka, Reina; Saito, Tsuguyuki; Hondo, Hiromasa; Isogai, Akira

    2015-07-13

    We report that the intrinsic viscosity [η] of nanocellulose dispersions can be solely expressed as a function of the aspect ratio p of the nanocellulose. Both short rod-like nanocrystalline and long spaghetti-like nanofibrillated celluloses were prepared as dispersions in water. The influence of the flexibility and dimensions of the nanocelluloses on the flow properties of their dispersions was investigated by experimental and theoretical approaches using seven nanocellulose samples with different widths (2.6-14.4 nm) and aspect ratios (23-376). As the aspect ratio of a nanocellulose increases, it becomes more flexible, and its dispersion has higher viscosity. Irrespective of the flexibility and dimensions of these nanocelluloses, the relationship between [η] and p was ρ[η] = 0.15 × p(1.9), where ρ is the density of the nanocellulose.

  5. Preparation of directionally solidified BaTi2O5-Ba6Ti17O40 eutectic by the floating zone method

    NASA Astrophysics Data System (ADS)

    Shiga, K.; Katsui, H.; Goto, T.

    2017-02-01

    The BaTi2O5-Ba6Ti17O40 eutectic (BaO-68.7 mol% TiO2) was directionally solidified by the floating zone (FZ) method and crystalline phases, microstructures and orientation were investigated. Ba6Ti17O40 with faceted rod-like shape was dispersed in the BaTi2O5 matrix. The growth directions of BaTi2O5 and Ba6Ti17O40 were parallel to the b and a axis, respectively, and the orientation relations were BaTi2O5 (010)//Ba6Ti17O40(60 2 ̅) and BaTi2O5 (001)//Ba6Ti17O40 (001).

  6. Funalichnus bhubani isp. nov. from Bhuban Formation, Surma Group (Lower -Middle Miocene) of Aizawl, Mizoram, India.

    PubMed

    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.

  7. Self-assembly of an amphiphilic macromolecule under spherical confinement: an efficient route to generate hollow nanospheres.

    PubMed

    Glagoleva, A A; Vasilevskaya, V V; Yoshikawa, K; Khokhlov, A R

    2013-12-28

    In general, bio-macromolecules are composed of hydrophilic and hydrophobic moieties and are confined within small cavities, such as cell membranes and intracellular organelles. Here, we studied the self-organization of macromolecules having groups with different affinities to solvents under spherical nano-scale confinement by means of computer modeling. It is shown that depending on the interaction parameters of monomer units composed of side- and main-chain monomer groups along a single linear macromolecule and on cavity size, such amphiphilic polymers undergo the conformational transitions between hollow nanospheres, rod-like and folded cylindrical structures, and a necklace conformation with and without a particular ordering of beads. The diagram of the conformations in the variables the incompatibility parameter of monomer units and the cavity radius is constructed.

  8. 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.

  9. 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.

  10. 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.

  11. 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

  12. 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

  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. Sol-gel synthesis of nanostructured indium tin oxide with controlled morphology and porosity

    NASA Astrophysics Data System (ADS)

    Kőrösi, László; Scarpellini, Alice; Petrik, Péter; Papp, Szilvia; Dékány, Imre

    2014-11-01

    Nanostructured indium tin oxide (ITO) powders and thin films differing in morphology and porosity were prepared by a sol-gel method. In3+ and Sn4+ were hydrolyzed in aqueous medium through the use of ethanolamine (EA) or sodium acetate (AC). X-ray diffraction measurements demonstrated that both EA and AC furnished indium tin hydroxide, which became nanocrystalline after aging for one day. The indium tin hydroxide samples calcined at 550 °C afforded ITO with a cubic crystal structure, but the morphology differed significantly, depending on the agent used for hydrolysis. Electron microscopy revealed the formation of round monodisperse nanoparticles when AC was used, whereas the application of EA led to rod-like ITO nanoparticles. Both types of nanoparticles were suitable for the preparation of transparent and conductive ITO thin films. The influence of the morphology and porosity on the optical properties is discussed.

  15. 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.

  16. Microstructure and Chemical States of Hydroxyapatite/silk Fibroin Nanocomposites Synthesized via A Wet-mechanochemical Route

    NASA Astrophysics Data System (ADS)

    Wang, Li; Nemoto, Rei; Senna, Mamoru

    2002-12-01

    Hydroxyapaptite (HAp)/silk fibroin (SF) nanocomposites were prepared via a wet-mechanochemical route at room temperature. The results reveal that the inorganic phase in the composites is carbonate-substituted HAp containing 2.9-3.1 wt% of carbonate ions. The primary HAp crystals are rod-like in shape with a typical size of 20-30 nm in length and 8-10 nm in width, and lattice parameters a = 9.423 Å, c = 6.888 Å. The self-assembled HAp crystals along their c-axes aggregate into bundles, which are connected with SF fibrils. Consequently, a three-dimensional porous network is formed in the composite, which is beneficial to inducing new bone formation in practical implantation.

  17. 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

  18. 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.

  19. Plasmonic Dimer-Like Nanoassemblies for Surface-Enhanced Raman Spectroscop

    NASA Astrophysics Data System (ADS)

    Rigo, Maria; Seo, Jaetae; Kim, Wan-Joong; Jung, Sungsoo; Hampton University Team; Etri Collaboration; Kriss Collaboration

    2011-05-01

    We report on the preparation of gold dimers in which the near-field coupling in their subwavelength gap is influenced by the individual gold nanoparticles size and the molecule's length used to assemble the dimers. The nano assemblies display plasmonic modes similar to those observed in rod-like nanoparticles. The longitudinal mode of the gold dimers shift as a function of gold nanoparticles size and concentration and it is influenced by the concentration of Rhodamine 6G (R6G), the molecule used as nanoparticle linker. We report large surface enhanced Raman scattering (SERS) enhancements for R6G when using linked-gold nano-assemblies as a SERS substrate. A discussion about the main origins for the large enhancement of molecular vibrational modes is presented. This work at Hampton University was supported by the National Science Foundation (HRD-0734635 and HRD-0630372).

  20. 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.

  1. 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.

  2. 2.0 A crystal structure of a four-domain segment of human fibronectin encompassing the RGD loop and synergy region.

    PubMed

    Leahy, D J; Aukhil, I; Erickson, H P

    1996-01-12

    We have determined the 2.0 A crystal structure of a fragment of human fibronectin encompassing the seventh through the RGD-containing tenth type III repeats (FN7-10). The structure reveals an extended rod-like molecule with a long axis of approximately 140 A and highly variable relationships between adjacent domains. An unusually small rotation between domains 9 and 10 creates a distinctive binding site, in which the RGD loop from domain 10 and the "synergy" region from domain 9 are on the same face of FN7-10 and thus easily accessible to a single integrin molecule. The cell-binding RGD loop is well-ordered in this structure and extends approximately 10 A away from the FN7-10 core.

  3. Pattern formation in transparent media using ultrashort laser pulses

    NASA Astrophysics Data System (ADS)

    Thomas, J.; Bernard, R.; Alti, K.; Dharmadhikari, A. K.; Dharmadhikari, J. A.; Bhatnagar, A.; Santhosh, C.; Mathur, D.

    2013-09-01

    We report results of a systematic study of the morphology of laser-written structures within transparent media like fused silica, borosilicate glass (BK7), and polymethylmethylacrylate (PMMA) using a high-energy, 5.1 MHz repetition rate, femtosecond laser oscillator. Depending on experimental conditions, both smooth channels as well as dot patterns can be laser-written. The periodicity of the written dots is readily controlled by the energy dose, a single parameter that encompasses laser energy, translation speed at fixed repetition rate, and focusing conditions. We discover the importance of the direction in which laser-writing is carried out: the periodicity of the dot patterns written at fixed energy dose but with opposite writing directions is significantly different. In PMMA, extremely large rod-like structures (˜200 µm) are observed whose formation is also dependent on writing direction. We quantify guidance of 632 nm and 830 nm light in structures written in BK7.

  4. Preparation, physical-chemical characterization, and cytocompatibility of polymeric calcium phosphate cements.

    PubMed

    Khashaba, Rania M; Moussa, Mervet; Koch, Christopher; Jurgensen, Arthur R; Missimer, David M; Rutherford, Ronny L; Chutkan, Norman B; Borke, James L

    2011-01-01

    Aim. Physicochemical mechanical and in vitro biological properties of novel formulations of polymeric calcium phosphate cements (CPCs) were investigated. Methods. Monocalcium phosphate, calcium oxide, and synthetic hydroxyapatite were combined with either modified polyacrylic acid, light activated polyalkenoic acid, or polymethyl vinyl ether maleic acid to obtain Types I, II, and III CPCs. Setting time, compressive and diametral strength of CPCs was compared with zinc polycarboxylate cement (control). Specimens were characterized using X-ray diffraction, scanning electron microscopy, and infrared spectroscopy. In vitro cytotoxicity of CPCs and control was assessed. Results. X-ray diffraction analysis showed hydroxyapatite, monetite, and brushite. Acid-base reaction was confirmed by the appearance of stretching peaks in IR spectra of set cements. SEM revealed rod-like crystals and platy crystals. Setting time of cements was 5-12 min. Type III showed significantly higher strength values compared to control. Type III yielded high biocompatibility. Conclusions. Type III CPCs show promise for dental applications.

  5. Electrorheological properties of polyaniline-vanadium oxide nanostructures suspended in silicone oil

    NASA Astrophysics Data System (ADS)

    Goswami, Sumita; Brehm, Tiago; Filonovich, Sergej; Cidade, Maria Teresa

    2014-10-01

    In the present work, organic/inorganic hybrid nanostructures comprised of polyaniline and vanadium oxide were synthesized via a simple hydrothermal technique. The polyaniline/vanadium oxide hybrid morphology was tailored from rods to spheres by controlling the relative concentration of the reactants. The synthesized composites were characterized by x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and field emission scanning electron microscopy (FESEM) for structural and morphological analyses. Electrorheological (ER) properties of the as-prepared nanocomposites suspended in silicone oil were investigated by a rotational viscometer under both steady and dynamic shear. The ER activity of the composite material suspensions showed higher ER effects for the product with the rod-like structures than for the product with the sphere-like structures. The typical ER behaviour showed by the polyaniline-vanadium oxide nanocomposites demonstrated their potential application as an ER smart material.

  6. Morphological characteristics of monosodium urate: a transmission electron microscopic study of intact natural and synthetic crystals.

    PubMed

    Paul, H; Reginato, A J; Schumacher, H R

    1983-02-01

    Transmission electron microscopic studies of synthetic and natural monosodium urate crystals dried on formvar coated grids showed identical internal structures in all crystals. At higher magnification the crystals' surface showed angular or wavy irregularities, and more rarely some crystals appeared to have other tiny crystals on the surface. Protein-like surface coating was not observed except in crystals from one asymptomatic patient in whom synovial fluid was loaded with monosodium urate crystals, but no inflammatory cells were present. Heated synthetic monosodium urate crystals retained the ultrastructural characteristics in their interior but they lost their needle or rod-like shape. Transmission electron microscopic study of monosodium urate crystals dried on formvar coated grids provides a quick method of investigating crystal ultrastructure.

  7. Central ions and lateral asparagine/glutamine zippers stabilize the post-fusion hairpin conformation of the SARS coronavirus spike glycoprotein

    SciTech Connect

    Duquerroy, Stephane; Rey, Felix A.

    2005-05-10

    The coronavirus spike glycoprotein is a class I membrane fusion protein with two characteristic heptad repeat regions (HR1 and HR2) in its ectodomain. Here, we report the X-ray structure of a previously characterized HR1/HR2 complex of the severe acute respiratory syndrome coronavirus spike protein. As expected, the HR1 and HR2 segments are organized in antiparallel orientations within a rod-like molecule. The HR1 helices form an exceptionally long (120 A) internal coiled coil stabilized by hydrophobic and polar interactions. A striking arrangement of conserved asparagine and glutamine residues of HR1 propagates from two central chloride ions, providing hydrogen-bonding 'zippers' that strongly constrain the path of the HR2 main chain, forcing it to adopt an extended conformation at either end of a short HR2 {alpha}-helix.

  8. Template synthesis of porous titania using cellulose nanocrystals

    SciTech Connect

    Shin, Yongsoon; Exarhos, Gregory J.

    2007-05-01

    Porous titania with anatase structure has been prepared by a template process with cellulose nanocrystal (CNXL). Air-stable titanium(IV) bis(ammonium lactate)dihydroxide (Tyzor-LA) solution forms Tyzor-LA-CNXL composite upon adding CNXL colloids through interaction between Tyzor-LA and hydroxyl groups of CNXL. The Tyzor-LA-CNXL composite shows rod-like structures of 150-200 nm in length and 5-10 nm in diameter. After calcination at 500oC in air the composite showed anatase with porous structures and 170-200 m2/g specific surface area. X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), FT-IR, scanning electron microscope (SEM), and transmission electron microscope (TEM) were employed to characterize the morphologies and porous structures of the as-prepared and calcined composite mateials.

  9. The Landau-de Gennes free energy expansion of a melt of V-shaped polymer molecules

    NASA Astrophysics Data System (ADS)

    Aliev, M. A.; Ugolkova, E. A.; Kuzminyh, N. Yu.

    2016-08-01

    The phase behavior of a monodisperse melt of polymer molecules consisting of two rod-like segments joined at an angle α has been inspected within the Landau theory of phase transitions. The interactions between monomer units were assumed to be of the Maier-Saupe form. The Landau-de Gennes expansion of the free energy of the melt has been obtained up to the sixth order in powers of the nematic order parameter, the coefficients of this expansion have been calculated from the microscopic model of polymer molecule. The phase diagram contains the regions of stability of isotropic, prolate uniaxial, oblate uniaxial, and biaxial nematic phases. The isotropic-uniaxial nematic and uniaxial-biaxial nematic transitions are of the first and second order, respectively. We found two Landau points in the phase diagram at which continuous transition from biaxial nematic state to isotropic phase occurs.

  10. 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.

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

    PubMed

    Zhou, Ling; He, Hui; Li, Mei-Chun; Song, Kunlin; Cheng, H N; Wu, Qinglin

    2016-11-20

    The present work describes the isolation of cellulose nanoparticles (CNs) with different morphologies and their influence on rheological properties of CN and CN-poly (vinyl alcohol) (PVA) suspensions. Cottonseed hulls were used for the first time to extract three types of CNs, including fibrous cellulose nanofibers, rod-like cellulose nanocrystals and spherical cellulose nanoparticles through mechanical and chemical methods. Rheology results showed that the rheological behavior of the CN suspensions was strongly dependent on CN concentration and particle morphology. For PVA/CN systems, concentration of PVA/CN suspension, morphology of CNs, and weight ratio of CN to PVA were three main factors that influenced their rheology behaviors. This research reveals the importance of CN morphology and composition concentration on the rheological properties of PVA/CN, providing new insight in preparing high performance hydrogels, fibers and films base on PVA/CN suspension systems.

  12. Morphological characteristics of monosodium urate: a transmission electron microscopic study of intact natural and synthetic crystals.

    PubMed Central

    Paul, H; Reginato, A J; Schumacher, H R

    1983-01-01

    Transmission electron microscopic studies of synthetic and natural monosodium urate crystals dried on formvar coated grids showed identical internal structures in all crystals. At higher magnification the crystals' surface showed angular or wavy irregularities, and more rarely some crystals appeared to have other tiny crystals on the surface. Protein-like surface coating was not observed except in crystals from one asymptomatic patient in whom synovial fluid was loaded with monosodium urate crystals, but no inflammatory cells were present. Heated synthetic monosodium urate crystals retained the ultrastructural characteristics in their interior but they lost their needle or rod-like shape. Transmission electron microscopic study of monosodium urate crystals dried on formvar coated grids provides a quick method of investigating crystal ultrastructure. Images PMID:6830327

  13. Effect of Minor Zn Additions on the Mechanical and Corrosion Properties of Solution-Treated AM60-2%RE Magnesium Alloy

    NASA Astrophysics Data System (ADS)

    Liu, Z. L.; Liu, Y.; Liu, X. Q.; Wang, M. M.

    2016-07-01

    The microstructure, mechanical properties, and corrosion behaviors of solution-treated AM60-2%RE magnesium alloy containing 0.2-0.8% wt.% Zn were investigated. With the increase of Zn, the volume fraction of dispersed rod-like Al4RE and granular-like Al11RE3 phases of solution-treated AM60-2%RE + x%Zn increased, which improved the mechanical properties by dispersion strengthening. With increasing Zn content, the corrosion current density decreased, and the corrosion potential and electrochemical impedance of the alloys increased, and the corrosion resistance of solution-treated AM60-2%RE + x%Zn was improved. With the increase of Zn content, the leaf-like corrosion products of the alloy became smaller and more compact, and the content of Zn, Al, Ce, and La in corrosion products increased, which was beneficial to inhibit the corrosion progress.

  14. 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

  15. 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.

  16. 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

  17. 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.

  18. Method for preparing metallated filament-wound structures

    DOEpatents

    Peterson, George R.

    1979-01-01

    Metallated graphite filament-wound structures are prepared by coating a continuous multi-filament carbon yarn with a metal carbide, impregnating the carbide coated yarn with a polymerizable carbon precursor, winding the resulting filament about a mandrel, partially curing the impregnation in air, subjecting the wound composite to heat and pressure to cure the carbon precursor, and thereafter heating the composite in a sizing die at a pressure loading of at least 1000 psi for graphitizing the carbonaceous material in the composite. The carbide in the composite coalesces into rod-like shapes which are disposed in an end-to-end relationship parallel with the filaments to provide resistance to erosion in abrasive laden atmospheres.

  19. 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.

  20. Self-assembly of an amphiphilic macromolecule under spherical confinement: An efficient route to generate hollow nanospheres

    NASA Astrophysics Data System (ADS)

    Glagoleva, A. A.; Vasilevskaya, V. V.; Yoshikawa, K.; Khokhlov, A. R.

    2013-12-01

    In general, bio-macromolecules are composed of hydrophilic and hydrophobic moieties and are confined within small cavities, such as cell membranes and intracellular organelles. Here, we studied the self-organization of macromolecules having groups with different affinities to solvents under spherical nano-scale confinement by means of computer modeling. It is shown that depending on the interaction parameters of monomer units composed of side- and main-chain monomer groups along a single linear macromolecule and on cavity size, such amphiphilic polymers undergo the conformational transitions between hollow nanospheres, rod-like and folded cylindrical structures, and a necklace conformation with and without a particular ordering of beads. The diagram of the conformations in the variables the incompatibility parameter of monomer units and the cavity radius is constructed.

  1. Morphological Control and Characterization of Monodispersed Ceria Particles

    SciTech Connect

    Minamidate, Y.; Yin, S.; Devaraju, M. K.; Sato, T.

    2010-11-24

    The morphological control of cerium oxide particles was carried out by a homogeneous precipitation followed by calcination in air at 400 deg. C. The effects of pre-aging temperature, aging time and precipitation reagents on the morphologies of final products were investigated. When urea was used as a precipitation reagent, monodispersed spherical and flake-like cerium carbonate hydroxide precursor was precipitated in the solution at 90 deg. C for 2 h after pre-aging at 25 deg. C - 50 deg. C for 24-72 h. On the other hand, monodispersed nanosize rod-like cerium hydroxide particles were obtained using triethanolamine as precipitation reagent. Ceria particles with the same morphologies and slightly smaller particle size than those of as-prepared cerium precursor could be obtained after calcination in air at 400 deg. C. Physical-chemical characteristics of the monodispersed cerium oxide particles were evaluated.

  2. 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.

  3. ZnO nanorods prepared via ablation of Zn with millisecond laser in liquid media.

    PubMed

    Honda, Mitsuhiro; Goto, Taku; Owashi, Tatsuki; Rozhin, Alex G; Yamaguchi, Shigeru; Ito, Tsuyohito; Kulinich, Sergei A

    2016-09-14

    ZnO nanomaterials with controlled size, shape and surface chemistry are required for applications in diverse areas, such as optoelectronics, photocatalysis, biomedicine and so on. Here, we report on ZnO nanostructures with rod-like and spherical shapes prepared via laser ablation in liquid using a laser with millisecond-long pulses. By changing laser parameters (such as pulse width and peak power), the size or aspect ratio of such nanostructures could be tuned. The surface chemistry and defects of the products were also strongly affected by applied laser conditions. The preparation of different structures is explained by the intense heating of liquid media caused by millisecond-long pulses and secondary irradiation of already-formed nanostructures.

  4. Revisiting Taylor Dispersion: Differential enhancement of rotational and translational diffusion under oscillatory shear

    NASA Astrophysics Data System (ADS)

    Leahy, Brian; Ong, Desmond; Cheng, Xiang; Cohen, Itai

    2013-03-01

    The idea of Taylor dispersion - enhancement of translational diffusion under shear - has found applications in fields from pharmacology to chemical engineering. Here, in a combination of experiment and simulations, we study the translational and rotational diffusion of colloidal dimers under triangle-wave oscillatory shear. We find that the rotational diffusion is enhanced, in addition to the enhanced translational diffusion. This ``rotational Taylor dispersion'' depends strongly on the strain rate (Peclet number), aspect ratio, and the shear strain, in contradistinction to translational Taylor dispersion in a shear flow, which depends only weakly on strain rate and aspect ratio. This separate tunability of translations and orientations promises important applications in mixing and self-assembly of solutions of anisometric colloids. We discuss the corresponding effect on the structure and rheology of denser suspensions of rod-like particles. B. L. acknowledges supported by the Department of Defense (DoD) through the National Defense Science & Engineering Graduate Fellowship (NDSEG) Program.

  5. Bismuth sulfide nanoflakes and nanorods as high performance photodetectors and photoelectrochemical cells

    NASA Astrophysics Data System (ADS)

    Chao, Junfeng; Xing, Shumin; Zhao, Yanchun; Gao, Suling; Song, Qinghua; Guo, Lixia; Wang, Di; Zhang, Tingliang

    2016-11-01

    Flake-like and rod-like bismuth sulfide nanostructures were synthesized via a facile polyol refluxing process. The rigid photodetectors based on both nanomaterials have the features of linear photocurrent characteristics and good sensitivity. Especially, the rigid bismuth sulfide nanoflakes photodetector has fast response time of 0.5 s and recovery time of 0.7 s. The flexible photodetectors were then fabricated on PET substrate, and this caused both the response time and the recovery time to increase by a factor of ∼2.5. Moreover, the photoelectrochemical (PEC) devices exhibited photosensitivity with the features of rapid response and recovery time, high on/off ratio and stable switching cycle performance. Our results imply that the two types of bismuth sulfide nanomaterials are prospective candidates for next generation photodetectors and optoelectronic switches.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. 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

  15. 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.

  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. 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.

  18. 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.

  19. 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.

  20. 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.

  1. Synthesis and red emission of Eu3+ doped LaBWO6 nanorods

    NASA Astrophysics Data System (ADS)

    Liu, Zhijian; Wang, Xiaoyan; Xu, Wenlu; Xia, Zhengbing

    2016-01-01

    Eu3+ ions doped LaBWO6 phosphors were synthesized by a facile hydrothermal method. The phase, morphology and luminescence properties of the obtained samples were characterized. The XRD, Raman and IR results showed that the obtained samples have the orthorhombic phase, indicating the doped Eu3+ will not change the phase of host. The TEM and SEM images showed that the obtained sample have the rod-like morphology. The excitation spectrum showed that Eu3+ ions doped LaBWO6 phosphors have excitation bands ranging from the ultraviolet region to blue region. The emission spectra showed that Eu3+ ions doped LaBWO6 phosphors emit dominate red light under 281, 394 and 464 nm excitations. And the decay of the red emission fitted well with the double exponential function.

  2. Extended structure design with simple molybdenum oxide building blocks and urea as a directing agent.

    PubMed

    Veen, Sandra J; Roy, Soumyajit; Filinchuk, Yaroslav; Chernyshov, Dmitry; Petukhov, Andrei V; Versluijs-Helder, Marjan; Broersma, Alfred; Soulimani, Fouad; Visser, Tom; Kegel, Willem K

    2008-08-04

    We report here a simple one-pot directed synthesis of an oxomolybdate urea composite in which elementary molybdenum oxide building blocks are linked together with the aid of urea. This type of directed material design resulted in large rod-like crystals of an inorganic-organic hybrid extended structure of {MoO 3(NH 2-CO-NH 2)} infinity consisting of right- and left-handed helical units. In the crystal structure urea acts both as a glue that links the inorganic molybdenum units into a helix and as a supramolecular linker for the stabilization of the crystal structure as a whole. This type of molecular topology resulted in an unexpectedly high thermal stability.

  3. Synthesis, photophysical and thin-film self-assembly properties of novel fluorescent molecules with carbon-carbon triple bonds.

    PubMed

    Niu, Qingfen; Sun, Hongjian; Li, Xiaoyan

    2014-12-10

    Three novel fluorescent molecules with carbon-carbon triple bonds 2TBEA, 2TBDA and TEPEB are successfully designed and synthesized. Their thermal, photophysical, electrochemical, electronic and thin-film self-assembly properties were characterized. Three dyes showed typical photoluminescence (PL) emission behaviors, the PL intensities firstly increased and then decreased with gradually decreasing concentration. The appealing fluorescence properties indicated that three dyes could be used as good fluorescent materials. Additionally, the thin-film self-assembly behaviors of three dyes were also investigated. The microstructures of their optical microscopy (OM) images exhibited high flexibility. Furthermore, SEM and AFM surface morphology of these self-assembly nanostructures revealed that three well-defined long-range order of rod-like and tube-like self-assembly systems exhibited interesting morphology properties. Therefore, three compounds may be of great interest for the development of organic thin-film materials.

  4. Surfactant-assisted Nanocasting Route for Synthesis of Highly Ordered Mesoporous Graphitic Carbon and Its Application in CO2 Adsorption

    NASA Astrophysics Data System (ADS)

    Wang, Yangang; Bai, Xia; Wang, Fei; Qin, Hengfei; Yin, Chaochuang; Kang, Shifei; Li, Xi; Zuo, Yuanhui; Cui, Lifeng

    2016-05-01

    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.

  5. A magnetic protein biocompass.

    PubMed

    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.

  6. Role for primary cilia as flow detectors in the cardiovascular system.

    PubMed

    Van der Heiden, Kim; Egorova, Anastasia D; Poelmann, Robert E; Wentzel, Jolanda J; Hierck, Beerend P

    2011-01-01

    The cardiovascular system is exposed to biochemical and biomechanical signals. Various sensors for these signals have been described and they contribute to cardiovascular development, maintenance of vessel integrity during adult life, and to pathogenesis. In the past 10years, primary cilia, membrane-covered, rod-like cellular protrusions, were discovered on multiple cell types of the cardiovascular system. Primary cilia are sensory organelles involved in several key (developmental) signaling pathways and in chemo- and mechanosensing on a myriad of cell types. In the embryonic and adult cardiovascular system, they have been demonstrated to function as shear stress sensors on endothelial cells and could act as strain sensors on smooth muscle cells and cardiomyocytes and as chemosensors on fibroblasts. This review will cover their occurrence and elaborate on established and possible functions of primary cilia in the cardiovascular system.

  7. Low-workfunction photocathodes based on acetylide compounds

    DOEpatents

    Terdik, Joseph Z; Spentzouris, Linda; Terry, Jr., Jeffrey H; Harkay, Katherine C; Nemeth, Karoly; Srajer, George

    2014-05-20

    A low-workfunction photocathode includes a photoemissive material employed as a coating on the photocathode. The photoemissive material includes A.sub.nMC.sub.2, where A is a first metal element, the first element is an alkali metal, an alkali-earth element or the element Al; n is an integer that is 0, 1, 2, 3 or 4; M is a second metal element, the second metal element is a transition metal or a metal stand-in; and C.sub.2 is the acetylide ion C.sub.2.sup.2-. The photoemissive material includes a crystalline structure or non-crystalline structure of rod-like or curvy 1-dimensional polymeric substructures with MC.sub.2 repeating units embedded in a matrix of A.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  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. Reinforced plastics and aerogels by nanocrystalline cellulose

    NASA Astrophysics Data System (ADS)

    Leung, Alfred C. W.; Lam, Edmond; Chong, Jonathan; Hrapovic, Sabahudin; Luong, John H. T.

    2013-05-01

    Nanocrystalline cellulose (NCC), a rigid rod-like nanoscale material, can be produced from cellulosic biomass in powder, liquid, or gel forms by acid and chemical hydrolysis. Owing to its unique and exceptional physicochemical properties, the incorporation of a small amount of NCC into plastic enhances the mechanical strength of the latter by several orders of magnitudes. Carbohydrate-based NCC poses no serious environmental concerns, providing further impetus for the development and applications of this green and renewable biomaterial to fabricate lightweight and biodegradable composites and aerogels. Surface functionalization of NCC remains the main focus of NCC research to tailor its properties for dispersion in hydrophilic or hydrophobic media. It is of uttermost importance to develop tools and protocols for imaging of NCC in a complex matrix and quantify its reinforcement effect.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. From liquid crystal models to the guiding-center theory of magnetized plasmas

    SciTech Connect

    Tronci, Cesare

    2016-08-15

    Upon combining Northrop’s picture of charged particle motion with modern liquid crystal theories, this paper provides a new description of guiding center dynamics (to lowest order). This new perspective is based on a rotation gauge field (gyrogauge) that encodes rotations around the magnetic field. In liquid crystal theory, an analogue rotation field is used to encode the rotational state of rod-like molecules. Instead of resorting to sophisticated tools (e.g. Hamiltonian perturbation theory and Lie series expansions) that still remain essential in higher-order gyrokinetics, the present approach combines the WKB method with a simple kinematical ansatz, which is then replaced into the charged particle Lagrangian. The latter is eventually averaged over the gyrophase to produce the guiding-center equations. A crucial role is played by the vector potential for the gyrogauge field. A similar vector potential is related to liquid crystal defects and is known as wryness tensor in Eringen’s micropolar theory.

  19. 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

    2017-03-17

    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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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

  5. 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.

  6. 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.

  7. Entropically dirven phase transitions in mixtures of colloidal rods and spheres.

    NASA Astrophysics Data System (ADS)

    Fraden, Seth

    2001-03-01

    We have prepared a homologous series of filamentous viruses with varying contour length using molecular cloning techniques. These viruses are monodisperse enough to form a stable smectic phase. Two systems are studied. The first system consists of viruses to which polymers are covalently attached to the virus surface. Through studies of the isotropic - cholesteric phase transition we demonstrate that covalently attached polymers alter the effective diameter of the virus and we have produced mixtures of viruses whose ratio of effective diameters varies by a factor of five. The second system is composed of mixtures of rod-like viruses and non-absorbing polymers. With this system we study the kinetics of the isotropic - smectic phase transition and describe observations of a number of novel metastable structures of unexpected complexity. Preprints are available online at www.elsie.brandeis.edu and at http://xxx.lanl.gov/abs/cond-mat/0010269.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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

  20. 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

  1. 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.

  2. 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.

  3. Investigation into the impact of sub-populations of agglomerates on the particle size distribution and flow properties of conventional microcrystalline cellulose grades.

    PubMed

    Gamble, John F; Chiu, Wing-Sin; Tobyn, Mike

    2011-10-01

    Microcrystalline cellulose (MCC) is regarded as one of the most versatile tablet filler binders, finding a wide use in both granulation and direct compression operations. It has been shown that MCC particle populations consist of a mixture of 'rod like' primary particles, and agglomerates, and that the proportion of these primary particles and agglomerates differs within the different grades of materials, contributing to the different bulk properties of these materials. However, the proportion of primary particles and agglomerates has not previously been fully elucidated, and their contribution to the performance factors such as flow explained. In this paper we use a novel microscopy-based characterization technique to demonstrate that the proportion of 'agglomerates' in the series of MCC grades between PH101 and PH200 is, by number, very low, but sufficient to perturb a volume-based particle size method by significant amounts.

  4. Intestinal epithelial culture under an air-liquid interface: a tool for studying human and mouse esophagi.

    PubMed

    Yokobori, T; Suzuki, S; Miyazaki, T; Sohda, M; Sakai, M; Tanaka, N; Ozawa, D; Hara, K; Honjo, H; Altan, B; Fukuchi, M; Ishii, H; Iwatsuki, M; Sugimachi, K; Sudo, T; Iwaya, T; Nishida, N; Mimori, K; Kuwano, H; Mori, M

    2016-10-01

    This study investigated whether an intestinal epithelial culture method can be applied to mouse and human esophageal cultures. The esophagi harvested from 1-day-old mice and adult humans were maintained in collagen gels. A commercially available culture medium for human embryonic stem cells was used for the human esophageal culture. We discovered that the intestinal epithelial culture method can be successfully applied to both mouse and human esophageal cultures. The long-term cultured esophageal organoids were rod-like luminal structures lined with myofibroblasts. We discovered that regeneration of the esophageal mucosal surface can be almost completely achieved in vitro, and the advantage of this method is that organoid cultures may be generated using host-derived fibroblasts as a niche. This method is a promising tool for mouse and human research in intestinal biology, carcinogenesis, and regenerative medicine.

  5. A Hybrid Approach for Segmentation and Tracking of Myxococcus xanthus Swarms.

    PubMed

    Chen, Jianxu; Alber, Mark S; Chen, Danny Z

    2016-03-30

    Cell segmentation and motion tracking in timelapse images are fundamental problems in computer vision, and are also crucial for various biomedical studies. Myxococcus xanthus is a type of rod-like cells with highly coordinated motion. The segmentation and tracking of M. xanthus are challenging, because cells may touch tightly and form dense swarms that are difficult to identify individually in an accurate manner. The known cell tracking approaches mainly fall into two frameworks, detection association and model evolution, each having its own advantages and disadvantages. In this paper, we propose a new hybrid framework combining these two frameworks into one and leveraging their complementary advantages. Also, we propose an active contour model based on the Ribbon Snake, which is seamlessly integrated with our hybrid framework. Evaluated by 10 different datasets, our approach achieves considerable improvement over the state-of-the-art cell tracking algorithms on identifying complete cell trajectories, and higher segmentation accuracy than performing segmentation in individual 2D images.

  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.

  7. Characterization of undoped and Co doped ZnO nanoparticles synthesized by DC thermal plasma method

    NASA Astrophysics Data System (ADS)

    Nirmala, M.; Anukaliani, A.

    2011-02-01

    ZnO nanopowders doped with 5 and 10 at% cobalt were synthesized and their antibacterial activity was studied. Cobalt doped ZnO powders were prepared using dc thermal plasma method. Crystal structure and grain size of the particles were characterized by X-ray diffractometry and optical properties were studied using UV-vis spectroscopy. The particle size and morphology was observed by SEM and HRTEM, revealing rod like morphology. The antibacterial activity of undoped ZnO and cobalt doped ZnO nanoparticles against a Gram-negative bacterium Escherichia coli and a Gram-positive bacterium Bacillus atrophaeus was investigated. Undoped ZnO and cobalt doped ZnO exhibited antibacterial activity against both E. coli and Staphylococcus aureus but it was considerably more effective in the cobalt doped ZnO.

  8. New structural types and different oxidation levels in the family of Mn6-oxime single-molecule magnets.

    PubMed

    Jones, Leigh F; Inglis, Ross; Cochrane, Martyn E; Mason, Kevin; Collins, Anna; Parsons, Simon; Perlepes, Spyros P; Brechin, Euan K

    2008-11-28

    The synthesis and magnetic properties of three new members of a family of salicyaldoxime based [Mn6] single-molecule magnets possessing new structural types, core topologies and Mn oxidation state distributions are reported. The isostructural complexes [MnIII6O2(R-sao)6(X)2(EtOH)6] (R = Et, X = Br (1); R = Me, X = I (2)) exhibit single-molecule magnet behaviour with spin Hamiltonian parameters S = 12, g = 1.98 and D = -0.36 cm(-1) in both cases. The hexametallic cluster [MnIII4MnIV2O2(OMe)(4-)(Et-sao)6(MeOH)2].MeOH (3.MeOH) possesses a planar rod-like topology and a mixed valent [MnIV4MnIII2] core, which is unprecedented in this family of [Mn6] SMMs.

  9. Directed swimming of nanoscale swimmers in an array of posts with non-circular section: modelling and shape optimization

    NASA Astrophysics Data System (ADS)

    Tong, Jiajun; Shelley, Michael

    2016-11-01

    It has been shown experimentally that swimming of nanoscale rod-like bi-metallic swimmers can be biased and guided by an array of teardrop shaped posts in the solution, giving rise to a statistically directed motion in long time. This could be useful in many applications like concentrating nanoswimmers, or separating them from non-motile particles. We pose a model to study such directed swimming, taking into account the absorption and desorption of the swimmers to the vertical walls of posts. We emphasize the role of varying curvature along the circumference of a single post on the absorption and desorption. In seeking to enhance directed swimming, we apply shape optimization to find how we can design, based on experimental data, better posts which have higher efficiency of transporting swimmers. This work was partially supported by the National Science Foundation under Award Number DMS-1463962.

  10. 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.

  11. 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)

  12. Paramagnetic behavior of Co doped TiO{sub 2} nanocrystals controlled by self-purification mechanism

    SciTech Connect

    Anitha, B.; Khadar, M. Abdul; Banerjee, Alok

    2016-07-15

    Doping in nanocrystals is a challenging process because of the self- purification mechanism which tends to segregate out the dopants resulting in a greater dopant concentration near the surface than at the interior of nanocrystals. In the present work nanocrystals of TiO{sub 2} doped with different atom % of Co were synthesized by peroxide gel method. XRD analysis confirmed the tetragonal anatase structure and HRTEM images showed the rod-like morphology of the samples. Raman modes of anatase phase of TiO{sub 2} along with weak intensity peaks of Co{sub 3}O{sub 4} for higher Co dopant concentrations were observed for the samples. EPR measurements revealed the presence of cobalt in +2 oxidation state in the TiO{sub 2} matrix. SQUID measurements indicated paramagnetic behavior of the Co doped TiO{sub 2} nanocrystals. The paramagnetic behavior is attributed to an increased concentration of Co{sup 2+} ions and an increased presence of Co{sub 3}O{sub 4} phase near the surface of the TiO{sub 2} nanocrystals due to self-purification mechanism. - Graphical abstract: Variation of the intensity ratios of XRD peaks as a function of atomic ratio of Co. Inset: variation of structure factor for (101) reflection as a function of atomic ratio of Co. Display Omitted - Highlights: • Co doped TiO{sub 2} nanocrystals were synthesized by peroxide gel method. • HRTEM images showed Co doped TiO{sub 2} nanocrystals to be rod-like. • EPR spectra showed +2 oxidation states for Co in the samples. • Co doped TiO{sub 2} nanocrystals showed paramagnetic behavior.

  13. Solution structure of copper ion-induced molecular aggregates of tyrosine melanin.

    PubMed

    Gallas, J M; Littrell, K C; Seifert, S; Zajac, G W; Thiyagarajan, P

    1999-08-01

    Melanin, the ubiquitous biological pigment, provides photoprotection by efficient filtration of light and also by its antioxidant behavior. In solutions of synthetic melanin, both optical and antioxidant behavior are affected by the aggregation states of melanin. We have utilized small-angle x-ray and neutron scattering to determine the molecular dimensions of synthetic tyrosine melanin in its unaggregated state in D(2)O and H(2)O to study the structure of melanin aggregates formed in the presence of copper ions at various copper-to-melanin molar ratios. In the absence of copper ions, or at low copper ion concentrations, tyrosine melanin is present in solution as a sheet-like particle with a mean thickness of 12.5 A and a lateral extent of approximately 54 A. At a copper-to-melanin molar ratio of 0.6, melanin aggregates to form long, rod-like structures with a radius of 32 A. At a higher copper ion concentration, with a copper-to-melanin ratio of 1.0, these rod-like structures further aggregate, forming sheet-like structures with a mean thickness of 51 A. A change in the charge of the ionizable groups induced by the addition of copper ions is proposed to account for part of the aggregation. The data also support a model for the copper-induced aggregation of melanin driven by pi stacking assisted by peripheral Cu(2+) complexation. The relationship between our results and a previous hypothesis for reduced cellular damage from bound-to-melanin redox metal ions is also discussed.

  14. Solution structure of copper ion-induced molecular aggregates of tyrosine melanin.

    PubMed Central

    Gallas, J M; Littrell, K C; Seifert, S; Zajac, G W; Thiyagarajan, P

    1999-01-01

    Melanin, the ubiquitous biological pigment, provides photoprotection by efficient filtration of light and also by its antioxidant behavior. In solutions of synthetic melanin, both optical and antioxidant behavior are affected by the aggregation states of melanin. We have utilized small-angle x-ray and neutron scattering to determine the molecular dimensions of synthetic tyrosine melanin in its unaggregated state in D(2)O and H(2)O to study the structure of melanin aggregates formed in the presence of copper ions at various copper-to-melanin molar ratios. In the absence of copper ions, or at low copper ion concentrations, tyrosine melanin is present in solution as a sheet-like particle with a mean thickness of 12.5 A and a lateral extent of approximately 54 A. At a copper-to-melanin molar ratio of 0.6, melanin aggregates to form long, rod-like structures with a radius of 32 A. At a higher copper ion concentration, with a copper-to-melanin ratio of 1.0, these rod-like structures further aggregate, forming sheet-like structures with a mean thickness of 51 A. A change in the charge of the ionizable groups induced by the addition of copper ions is proposed to account for part of the aggregation. The data also support a model for the copper-induced aggregation of melanin driven by pi stacking assisted by peripheral Cu(2+) complexation. The relationship between our results and a previous hypothesis for reduced cellular damage from bound-to-melanin redox metal ions is also discussed. PMID:10423458

  15. Chrysanthemum chlorotic mottle viroid: unusual structural properties of a subgroup of self-cleaving viroids with hammerhead ribozymes.

    PubMed

    Navarro, B; Flores, R

    1997-10-14

    The causal agent of chrysanthemum chlorotic mottle (CChM) disease has been identified, cloned, and sequenced. It is a viroid RNA (CChMVd) of 398-399 nucleotides. In vitro transcripts with the complete CChMVd sequence were infectious and induced the typical symptoms of the CChM disease. CChMVd can form hammerhead structures in both polarity strands. Plus and minus monomeric CChMVd RNAs self-cleaved during in vitro transcription and after purification as predicted by these structures, which are stable and most probably act as single hammerhead structures as in peach latent mosaic viroid (PLMVd), but not in avocado sunblotch viroid (ASBVd). Moreover, the plus CChMVd hammerhead structure also appears to be active in vivo, because the 5' terminus of the linear plus CChMVd RNA isolated from infected tissue is that predicted by the corresponding hammerhead ribozyme. Both hammerhead structures of CChMVd display some peculiarities: the plus self-cleaving domain has an unpaired A after the conserved A9 residue, and the minus one has an unusually long helix II. The most stable secondary structure predicted for CChMVd is a branched conformation that does not fulfill the rod-like or quasi-rod-like model proposed for the in vitro structure of most viroids with the exception of PLMVd, whose proposed secondary structure of lowest free energy also is branched. The unusual conformation of CChMVd and PLMVd is supported by their insolubility in 2 M LiCl, in contrast to ASBVd and a series of representative non-self-cleaving viroids that are soluble under the same high salt conditions. These results support the classification of self-cleaving viroids into two subgroups, one formed by ASBVd and the other one by PLMVd and CChMVd.

  16. Self-assembly mechanisms of nanofibers from peptide amphiphiles in solution and on substrate surfaces

    NASA Astrophysics Data System (ADS)

    Liao, Hsien-Shun; Lin, Jing; Liu, Yang; Huang, Peng; Jin, Albert; Chen, Xiaoyuan

    2016-08-01

    We report the investigation of the self-assembly mechanism of nanofibers, using a small peptide amphiphile (NapFFKYp) as a model. Combining experimental and simulation methods, we identify the self-assembly pathways in the solution and on the substrates, respectively. In the solution, peptide amphiphiles undergo the nucleation process to grow into nanofibers. The nanofibers can further twist into high-ordered nanofibers with aging. On the substrates, peptide amphiphiles form nanofibers and nanosheet structures simultaneously. This surface-induced nanosheet consists of rod-like structures, and its thickness is substrate-dependent. Most intriguingly, water can transform the nanosheet into the nanofiber. Molecular dynamic simulation suggests that hydrophobic and ion-ion interactions are dominant forces during the self-assembly process.We report the investigation of the self-assembly mechanism of nanofibers, using a small peptide amphiphile (NapFFKYp) as a model. Combining experimental and simulation methods, we identify the self-assembly pathways in the solution and on the substrates, respectively. In the solution, peptide amphiphiles undergo the nucleation process to grow into nanofibers. The nanofibers can further twist into high-ordered nanofibers with aging. On the substrates, peptide amphiphiles form nanofibers and nanosheet structures simultaneously. This surface-induced nanosheet consists of rod-like structures, and its thickness is substrate-dependent. Most intriguingly, water can transform the nanosheet into the nanofiber. Molecular dynamic simulation suggests that hydrophobic and ion-ion interactions are dominant forces during the self-assembly process. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr04672j

  17. Solution structures of {beta}-amyloid{sub 10-35} and {beta}-amyloid{sub 10-35} PEG3000 aggregates.

    SciTech Connect

    Benzinger, T. L. S.; Burkoth, T. S.; Gordon, D.; Lynn, D. G.; Meredith, S. C.; Morgan, D. M.; Seifert, S.; Thiyagarajan, P.; Urban, V.

    1999-07-02

    Small angle neutron and x-ray scattering (SANS/SAXS) studies were conducted on the structure of the aggregates formed from both the truncated model peptide {beta}-Amyloid(10-35) (A{beta}{sub 10-35}) and a block copolymer {beta}-Amyloid (10-35)-PEG3000 (A{beta}{sub 10-35}-PEG) in D{sub 2}O at pHs from 3.0 to 7.0. These studies indicate that A{beta}{sub 10-35} aggregates into rod-like particles (fibril) and their radii are strongly dependent on the Pm of the solution. The fibril-fibril association in A{beta}{sub 10-35} solutions is less of pH < 5.6, but becomes larger at higher pH. A{beta}{sub 10-35}-PEG also assembles into rod-like particles whose radius is larger by about 30 {angstrom} than that for A{beta}{sub 10-35} fibril at pH 4.2, while it is about 23 {angstrom} larger at higher pH. Contrast matching SAXS/SANS experiments that eliminate the coherent scattering from PEG reveal that PEG moiety is located at the periphery of the fibril. Also, the mass per unit length of the peptide portion is similar for both A{beta}{sub 10-35} and A{beta}{sub 10-35}-PEG fibrils at pH 5.6. The mass per unit length of the rods from SANS provides key information on the packing of A{beta}{sub 10-35} peptides in the fibril.

  18. Self-assembly of fluorescent carbon dots in a N,N-dimethylmethanamide solution via Schiff base reaction

    NASA Astrophysics Data System (ADS)

    Hu, Shengliang; Ding, Yanli; Chang, Qing; Trinchi, Adrian; Lin, Kui; Yang, Jinlong; Liu, Jun

    2015-02-01

    The transition from nanoparticles suspended in aqueous solutions into solid fluorescent structures is developed for application in solid functional devices. The presented approach enables the organization of carbon dots into rod-like shapes that can still be re-dispersed into aqueous solution. Schiff bases forming at the surface of carbon dots not only protect their surface states, but also provide sites for tethering to other carbon dots. As a consequence, the large assemblies of CDs can come together to form regular, well ordered structures whilst still maintaining their photoluminescence properties. This opens up enormous possibilities for device manufacture, as these self-assemblies could be grown or grafted onto templates forming regular structures, and find innumerable applications ranging from optoelectronic devices, light harvesting to artificial photosynthesis.The transition from nanoparticles suspended in aqueous solutions into solid fluorescent structures is developed for application in solid functional devices. The presented approach enables the organization of carbon dots into rod-like shapes that can still be re-dispersed into aqueous solution. Schiff bases forming at the surface of carbon dots not only protect their surface states, but also provide sites for tethering to other carbon dots. As a consequence, the large assemblies of CDs can come together to form regular, well ordered structures whilst still maintaining their photoluminescence properties. This opens up enormous possibilities for device manufacture, as these self-assemblies could be grown or grafted onto templates forming regular structures, and find innumerable applications ranging from optoelectronic devices, light harvesting to artificial photosynthesis. Electronic supplementary information (ESI) available: Experimental details and more characterization of carbon dot assemblies. See DOI: 10.1039/c4nr07119k

  19. Effects of Nano-CeO2 with Different Nanocrystal Morphologies on Cytotoxicity in HepG2 Cells

    PubMed Central

    Wang, Lili; Ai, Wenchao; Zhai, Yanwu; Li, Haishan; Zhou, Kebin; Chen, Huiming

    2015-01-01

    Cerium oxide nanoparticles (nano-CeO2) have been reported to cause damage and apoptosis in human primary hepatocytes. Here, we compared the toxicity of three types of nano-CeO2 with different nanocrystal morphologies (cube-, octahedron-, and rod-like crystals) in human hepatocellular carcinoma cells (HepG2). The cells were treated with the nano-CeO2 at various concentrations (6.25, 12.5, 25, 50, 100 μg/mL). The crystal structure, size and morphology of nano-CeO2 were investigated by X-ray diffractometry and transmission electron microscopy. The specific surface area was detected using the Brunauer, Emmet and Teller method. The cellular morphological and internal structure were observed by microscopy; apoptotic alterations were measured using flow cytometry; nuclear DNA, mitochondrial membrane potential (MMP), reactive oxygen species (ROS) and glutathione (GSH) in HepG2 cells were measured using high content screening technology. The scavenging ability of hydroxyl free radicals and the redox properties of the nano-CeO2 were measured by square-wave voltammetry and temperature-programmed-reduction methods. All three types of nano-CeO2 entered the HepG2 cells, localized in the lysosome and cytoplasm, altered cellular shape, and caused cytotoxicity. The nano-CeO2 with smaller specific surface areas induced more apoptosis, caused an increase in MMP, ROS and GSH, and lowered the cell’s ability to scavenge hydroxyl free radicals and antioxidants. In this work, our data demonstrated that compared with cube-like and octahedron-like nano-CeO2, the rod-like nano-CeO2 has lowest toxicity to HepG2 cells owing to its larger specific surface areas. PMID:26404340

  20. Nanomechanical Characterization of Bacillus anthracis Spores by Atomic Force Microscopy

    PubMed Central

    Burggraf, Larry W.; Xing, Yun

    2016-01-01

    ABSTRACT The study of structures and properties of bacterial spores is important to understanding spore formation and biological responses to environmental stresses. While significant progress has been made over the years in elucidating the multilayer architecture of spores, the mechanical properties of the spore interior are not known. Here, we present a thermal atomic force microscopy (AFM) study of the nanomechanical properties of internal structures of Bacillus anthracis spores. We developed a nanosurgical sectioning method in which a stiff diamond AFM tip was used to cut an individual spore, exposing its internal structure, and a soft AFM tip was used to image and characterize the spore interior on the nanometer scale. We observed that the elastic modulus and adhesion force, including their thermal responses at elevated temperatures, varied significantly in different regions of the spore section. Our AFM images indicated that the peptidoglycan (PG) cortex of Bacillus anthracis spores consisted of rod-like nanometer-sized structures that are oriented in the direction perpendicular to the spore surface. Our findings may shed light on the spore architecture and properties. IMPORTANCE A nanosurgical AFM method was developed that can be used to probe the structure and properties of the spore interior. The previously unknown ultrastructure of the PG cortex of Bacillus anthracis spores was observed to consist of nanometer-sized rod-like structures that are oriented in the direction perpendicular to the spore surface. The variations in the nanomechanical properties of the spore section were largely correlated with its chemical composition. Different components of the spore materials showed different thermal responses at elevated temperatures. PMID:26969703

  1. Ca2+-stabilized adhesin helps an Antarctic bacterium reach out and bind ice.

    PubMed

    Vance, Tyler D R; Olijve, Luuk L C; Campbell, Robert L; Voets, Ilja K; Davies, Peter L; Guo, Shuaiqi

    2014-07-04

    The large size of a 1.5-MDa ice-binding adhesin [MpAFP (Marinomonas primoryensis antifreeze protein)] from an Antarctic Gram-negative bacterium, M. primoryensis, is mainly due to its highly repetitive RII (Region II). MpAFP_RII contains roughly 120 tandem copies of an identical 104-residue repeat. We have previously determined that a single RII repeat folds as a Ca2+-dependent immunoglobulin-like domain. Here, we solved the crystal structure of RII tetra-tandemer (four tandem RII repeats) to a resolution of 1.8 Å. The RII tetra-tandemer reveals an extended (~190-Å × ~25-Å), rod-like structure with four RII-repeats aligned in series with each other. The inter-repeat regions of the RII tetra-tandemer are strengthened by Ca2+ bound to acidic residues. SAXS (small-angle X-ray scattering) profiles indicate the RII tetra-tandemer is significantly rigidified upon Ca2+ binding, and that the protein's solution structure is in excellent agreement with its crystal structure. We hypothesize that >600 Ca2+ help rigidify the chain of ~120 104-residue repeats to form a ~0.6 μm rod-like structure in order to project the ice-binding domain of MpAFP away from the bacterial cell surface. The proposed extender role of RII can help the strictly aerobic, motile bacterium bind ice in the upper reaches of the Antarctic lake where oxygen and nutrients are most abundant. Ca2+-induced rigidity of tandem Ig-like repeats in large adhesins might be a general mechanism used by bacteria to bind to their substrates and help colonize specific niches.

  2. A mechanistic study on the synthesis of β-Sialon whiskers from coal fly ash

    SciTech Connect

    Zhao, H.; Wang, P.Y.; Yu, J.L.; Zhang, J.

    2015-05-15

    Graphical abstract: The appearance of bead-like whiskers indicated that the growth mechanism of the β-Sialon whiskers was different from the conventional one, in which a chain of droplets were formed and then consumed to participate in the formation of the whiskers. - Highlights: • β-Sialon whiskers were synthesized using waste fly ash by carbothemal reduction reaction under nitrogen atmosphere. • Rod-like β-Sialon whiskers with a diameter of 100–500 nm were formed. • Bead-like whiskers as intermediate morphology of the growing β-Sialon whiskers were found with increasing sintering time. • The growth mechanism of β-Sialon whiskers was different from the conventional VLS mechanism. • A chain of droplets were formed and participated in the formation of the whiskers. - Abstract: β-Sialon whiskers were produced at 1420 °C through carbothemal reduction reaction under nitrogen atmosphere using fly ash from coal-fired power plants. The effects of sintering time on the phase formation and morphology of the products were investigated by X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive spectrometer (EDS) techniques. Rod-like β-Sialon whiskers with the diameter of 100–500 nm were successfully formed. With increasing sintering time, bead-like morphology during the growth process of the whiskers was found, and growth mechanism of β-Sialon whiskers was also discussed in detail. The growth mechanism proposed in this study was different from the conventional vapor–liquid–solid (VLS) mechanism.

  3. Microwave heating synthesis and formation mechanism of chalcopyrite structured CuInS{sub 2} nanorods in deep eutectic solvent

    SciTech Connect

    Zhang, Jianjun Chen, Jun; Li, Qiang

    2015-03-15

    Graphical abstract: Chalcopyrite structured CuInS{sub 2} nanorods were synthesized by an environmentally friendly microwave heating method in deep eutectic solvent. Results show that microwave heating time plays an important role in the formation of CuInS{sub 2} nanostructure phase. The SEM results indicated that the obtained CuInS{sub 2} nanostructures display rod-like morphology with diameters of about 40 nm and lengths of about 400 nm. The UV–vis spectrum results indicated that the CuInS{sub 2} nanorods exhibit strong absorption from the entire visible light region to the near-infrared region beyond 1100 nm. The possible growth mechanism of CuInS{sub 2} nanorods was discussed. - Abstract: Chalcopyrite structured CuInS{sub 2} nanorods were synthesized by an environmentally friendly microwave heating method in deep eutectic solvent. The as-synthesized CuInS{sub 2} nanorods were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS), respectively. The results indicated that the obtained CuInS{sub 2} nanostructures display rod-like morphology with diameters of about 40 nm and lengths of about 400 nm. The influences of microwave heating time on the formation of CuInS{sub 2} phase were discussed. Ultraviolet–visible (UV–vis) and photoluminescence (PL) spectra were utilized to investigate the optical properties of CuInS{sub 2} nanorods. The results showed that the as-synthesized CuInS{sub 2} nanorods exhibit strong absorption from the entire visible light region to the near-infrared region beyond 1100 nm. PL spectrum of the as-synthesized CuInS{sub 2} nanorods displays an emission peak centered at 580 nm under excitation wavelength of 366 nm at room temperature. The possible growth mechanism of CuInS{sub 2} nanorods was discussed.

  4. Analysis of the mechanical response of biomimetic materials with highly oriented microstructures through 3D printing, mechanical testing and modeling.

    PubMed

    de Obaldia, Enrique Escobar; Jeong, Chanhue; Grunenfelder, Lessa Kay; Kisailus, David; Zavattieri, Pablo

    2015-08-01

    Many biomineralized organisms have evolved highly oriented nanostructures to perform specific functions. One key example is the abrasion-resistant rod-like microstructure found in the radular teeth of Chitons (Cryptochiton stelleri), a large mollusk. The teeth consist of a soft core and a hard shell that is abrasion resistant under extreme mechanical loads with which they are subjected during the scraping process. Such remarkable mechanical properties are achieved through a hierarchical arrangement of nanostructured magnetite rods surrounded with α-chitin. We present a combined biomimetic approach in which designs were analyzed with additive manufacturing, experiments, analytical and computational models to gain insights into the abrasion resistance and toughness of rod-like microstructures. Staggered configurations of hard hexagonal rods surrounded by thin weak interfacial material were printed, and mechanically characterized with a cube-corner indenter. Experimental results demonstrate a higher contact resistance and stiffness for the staggered alignments compared to randomly distributed fibrous materials. Moreover, we reveal an optimal rod aspect ratio that lead to an increase in the site-specific properties measured by indentation. Anisotropy has a significant effect (up to 50%) on the Young's modulus in directions parallel and perpendicular to the longitudinal axis of the rods, and 30% on hardness and fracture toughness. Optical microscopy suggests that energy is dissipated in the form of median cracks when the load is parallel to the rods and lateral cracks when the load is perpendicular to the rods. Computational models suggest that inelastic deformation of the rods at early stages of indentation can vary the resistance to penetration. As such, we found that the mechanical behavior of the system is influenced by interfacial shear strain which influences the lateral load transfer and therefore the spread of damage. This new methodology can help to elucidate

  5. Characterization of fimbriae produced by enteropathogenic Escherichia coli.

    PubMed Central

    Girón, J A; Ho, A S; Schoolnik, G K

    1993-01-01

    Enteropathogenic Escherichia coli (EPEC) express rope-like bundles of filaments, termed bundle-forming pili (BFP) (J. A. Girón, A. S. Y. Ho, and G. K. Schoolnik, Science 254:710-713, 1991). Expression of BFP is associated with localized adherence to HEp-2 cells and the presence of the EPEC adherence factor plasmid. In this study, we describe the identification of rod-like fimbriae and fibrillae expressed simultaneously on the bacterial surface of three prototype EPEC strains. Upon fimbrial extraction from EPEC B171 (O111:NM), three fimbrial subunits with masses of 16.5, 15.5, and 14.7 kDa were separated by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. Their N-terminal amino acid sequence showed homology with F9 and F7(2) fimbriae of uropathogenic E. coli and F1845 of diffuse-adhering E. coli, respectively. The mixture of fimbrial subunits (called FB171) exhibited mannose-resistant agglutination of human erythrocytes only, and this activity was not inhibited by alpha-D-Gal(1-4)-beta-Gal disaccharide or any other described receptor analogs for P, S, F, M, G, and Dr hemagglutinins of uropathogenic E. coli, which suggests a different receptor specificity. Hemagglutination was inhibited by extracellular matrix glycoproteins, i.e., collagen type IV, laminin, and fibronectin, and to a lesser extent by gangliosides, fetuin, and asialofetuin. Scanning electron microscopic studies performed on clusters of bacteria adhering to HEp-2 cells revealed the presence of structures resembling BFP and rod-like fimbriae linking bacteria to bacteria and bacteria to the eukaryotic cell membrane. We suggest a role of these surface appendages in the interaction of EPEC with eukaryotic cells as well as in the overall pathogenesis of intestinal disease caused by EPEC. Images PMID:7901197

  6. Importance of light in temporal organization of photoreceptor proteins and melatonin-producing system in the pineal of carp Catla catla.

    PubMed

    Seth, Mohua; Maitra, Saumen Kumar

    2010-05-01

    The importance of light in the temporal organization of photoreceptor proteins and melatonin-producing system has been investigated for the first time in the pineal of a tropical fish. In this study, an identical experimental paradigm was followed during the four distinct phases of an annual cycle in adult carps (Catla catla) maintained either under natural photoperiod (NP) or continuous illumination (LL) or darkness (DD) for 30 days. At the end of each experiment, the pineal from fish in each experimental group was collected either at 06:00, 12:00, 18:00, or 24:00 in a daily cycle and assessed by Western blot analysis for pineal rod-like opsin, alpha-transducin, and AANAT. The same animals were also used for measurement of serum melatonin levels, and the serum as well as intra-pineal Ca(++) levels at each timepoint. The study revealed a daily rhythmicity with a peak at 12:00 h and nadir at 24:00 h in the band intensity of pineal rod-like opsin and alpha-transducin in NP fish, while the band intensities of these photo-pigment proteins remained high under LL and low under DD, irrespective of clock hour during the 24 h cycle. The band intensity of pineal AANAT, levels of serum melatonin, and both serum Ca(++) and intra-pineal Ca(++) were maximum at 24:00 h and minimum at 12:00h in NP fish, and they were significantly lower under LL and higher under DD at each point of study. The results showed loss of daily rhythm in each studied variable in both LL and DD carps, suggesting that their circadian organization is dependent on the external light-dark conditions, rather than an endogenous circadian oscillator in the pineal.

  7. Ca2+-stabilized adhesin helps an Antarctic bacterium reach out and bind ice

    PubMed Central

    Vance, Tyler D. R.; Olijve, Luuk L. C.; Campbell, Robert L.; Voets, Ilja K.; Davies, Peter L.; Guo, Shuaiqi

    2014-01-01

    The large size of a 1.5-MDa ice-binding adhesin [MpAFP (Marinomonas primoryensis antifreeze protein)] from an Antarctic Gram-negative bacterium, M. primoryensis, is mainly due to its highly repetitive RII (Region II). MpAFP_RII contains roughly 120 tandem copies of an identical 104-residue repeat. We have previously determined that a single RII repeat folds as a Ca2+-dependent immunoglobulin-like domain. Here, we solved the crystal structure of RII tetra-tandemer (four tandem RII repeats) to a resolution of 1.8 Å. The RII tetra-tandemer reveals an extended (~190-Å × ~25-Å), rod-like structure with four RII-repeats aligned in series with each other. The inter-repeat regions of the RII tetra-tandemer are strengthened by Ca2+ bound to acidic residues. SAXS (small-angle X-ray scattering) profiles indicate the RII tetra-tandemer is significantly rigidified upon Ca2+ binding, and that the protein's solution structure is in excellent agreement with its crystal structure. We hypothesize that >600 Ca2+ help rigidify the chain of ~120 104-residue repeats to form a ~0.6 μm rod-like structure in order to project the ice-binding domain of MpAFP away from the bacterial cell surface. The proposed extender role of RII can help the strictly aerobic, motile bacterium bind ice in the upper reaches of the Antarctic lake where oxygen and nutrients are most abundant. Ca2+-induced rigidity of tandem Ig-like repeats in large adhesins might be a general mechanism used by bacteria to bind to their substrates and help colonize specific niches. PMID:24892750

  8. The anti-tumor effect of p53 gene-loaded hydroxyapatite nanoparticles in vitro and in vivo

    NASA Astrophysics Data System (ADS)

    Zhao, Ruibo; Yang, Xinyan; Chen, Cen; Chen, Kan; Wang, Shibing; Xie, Chungang; Ren, Xiaoyuan; Kong, Xiangdong

    2014-04-01

    This research focused on anti-tumor effect of pEGFP-C1-p53 (p53) gene-loaded hydroxyapatite (HAp) nanoparticles in vitro and in vivo. Four kinds of HAp nanoparticles, spherical HAp nanoparticles (S-HAp, diameter: 50 nm), needle-like HAp nanoparticles (N-HAp, average length: 110 nm and width: 30 nm), rod-like HAp nanoparticles (R-HAp, average length: 100 nm and width: 30 nm), and short-rod-like HAp nanoparticles (SR-HAp, average length: 40 nm and width: 30 nm), were prepared initially. The HAp nanoparticles with or without being modified by PEI (named HAp and HAp-PEI, respectively) have excellent biocompatibility as shown by MTT assay and crystal violet staining tests. Then, the subsequent MTT, Hocehst staining tests, and Western blot showed that the killing effect of p53-loaded HAp-PEI (HAp-PEI-p53) was effective with fair selectivity toward Hep-3B and HuH-7 cells' cell lines. Moreover, HAp-PEI-p53 could inhibit the tumor growth in vivo, and the mechanism of tumor growth inhibition was verified by the hematoxylin and eosin staining, terminal deoxynucleotidyl transferase-mediated dUTP nick-end labeling, P53 protein immunohistochemistry, and transmission electron microscope of the tumor cell in vivo. We found that HAp-PEI-p53 has good anti-cancer effect in vitro and in vivo, especially for the S-HAp-PEI-p53. Tumor metastasis could be suppressed significantly by the S-HAp-PEI-p53 and N-HAp-PEI-p53 treatments by the in vivo imaging system. All these results lead to the conclusion that the particle sizes of HAp ranging from 100 to 200 nm are appropriate for cancer gene therapy and may be widely used in anti-cancer investigation.

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

    NASA Astrophysics Data System (ADS)

    Matsumoto, Takuya; Nishimura, Suzushi

    2013-09-01

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

  10. Effects of Nano-CeO₂ with Different Nanocrystal Morphologies on Cytotoxicity in HepG2 Cells.

    PubMed

    Wang, Lili; Ai, Wenchao; Zhai, Yanwu; Li, Haishan; Zhou, Kebin; Chen, Huiming

    2015-09-02

    Cerium oxide nanoparticles (nano-CeO₂) have been reported to cause damage and apoptosis in human primary hepatocytes. Here, we compared the toxicity of three types of nano-CeO₂ with different nanocrystal morphologies (cube-, octahedron-, and rod-like crystals) in human hepatocellular carcinoma cells (HepG2). The cells were treated with the nano-CeO₂ at various concentrations (6.25, 12.5, 25, 50, 100 μg/mL). The crystal structure, size and morphology of nano-CeO₂ were investigated by X-ray diffractometry and transmission electron microscopy. The specific surface area was detected using the Brunauer, Emmet and Teller method. The cellular morphological and internal structure were observed by microscopy; apoptotic alterations were measured using flow cytometry; nuclear DNA, mitochondrial membrane potential (MMP), reactive oxygen species (ROS) and glutathione (GSH) in HepG2 cells were measured using high content screening technology. The scavenging ability of hydroxyl free radicals and the redox properties of the nano-CeO₂ were measured by square-wave voltammetry and temperature-programmed-reduction methods. All three types of nano-CeO₂ entered the HepG2 cells, localized in the lysosome and cytoplasm, altered cellular shape, and caused cytotoxicity. The nano-CeO₂ with smaller specific surface areas induced more apoptosis, caused an increase in MMP, ROS and GSH, and lowered the cell's ability to scavenge hydroxyl free radicals and antioxidants. In this work, our data demonstrated that compared with cube-like and octahedron-like nano-CeO₂, the rod-like nano-CeO₂ has lowest toxicity to HepG2 cells owing to its larger specific surface areas.

  11. Ceria-containing uncoated and coated hydroxyapatite-based galantamine nanocomposites for formidable treatment of Alzheimer's disease in ovariectomized albino-rat model.

    PubMed

    Wahba, Sanaa M R; Darwish, Atef S; Kamal, Sara M

    2016-08-01

    This paper upraises delivery and therapeutic actions of galantamine drug (GAL) against Alzheimer's disease (AD) in rat brain through attaching GAL to ceria-containing hydroxyapatite (GAL@Ce-HAp) as well ceria-containing carboxymethyl chitosan-coated hydroxyapatite (GAL@Ce-HAp/CMC) nanocomposites. Physicochemical features of such nanocomposites were analyzed by XRD, FT-IR, Raman spectroscopy, UV-vis spectrophotometer, N2-BET, DLS, zeta-potential measurements, SEM, and HR-TEM. Limited interactions were observed in GAL@Ce-HAp with prevailed existence of dispersed negatively charged rod-like particles conjugated with ceria nanodots. On contrary, GAL@Ce-HAp/CMC was well-structured developing aggregates of uncharged tetragonal-shaped particles laden with accession of ceria quantum dots. Such nanocomposites were i.p. injected into ovariectomized AD albino-rats at galantamine dose of 2.5mg/kg/day for one month, then brain tissues were collected for biochemical and histological tests. GAL@Ce-HAp adopted as a promising candidate for AD curativeness, whereas oxidative stress markers were successfully upregulated, degenerated neurons in hippocampal and cerebral tissues were wholly recovered and Aβ-plaques were vanished. Also, optimizable in-vitro release for GAL and nanoceria were displayed from GAL@Ce-HAp, while delayed in-vitro release for those species were developed from GAL@Ce-HAp/CMC. This proof of concept work allow futuristic omnipotency of rod-like hydroxyapatite particles for selective delivery of GAL and nanoceria to AD affected brain areas.

  12. Interference between Coulombic and CT-mediated couplings in molecular aggregates: H- to J-aggregate transformation in perylene-based π-stacks

    NASA Astrophysics Data System (ADS)

    Hestand, Nicholas J.; Spano, Frank C.

    2015-12-01

    The spectroscopic differences between J and H-aggregates are traditionally attributed to the spatial dependence of the Coulombic coupling, as originally proposed by Kasha. However, in tightly packed molecular aggregates wave functions on neighboring molecules overlap, leading to an additional charge transfer (CT) mediated exciton coupling with a vastly different spatial dependence. The latter is governed by the nodal patterns of the molecular LUMOs and HOMOs from which the electron (te) and hole (th) transfer integrals derive. The sign of the CT-mediated coupling depends on the sign of the product teth and is therefore highly sensitive to small (sub-Angstrom) transverse displacements or slips. Given that Coulombic and CT-mediated couplings exist simultaneously in tightly packed molecular systems, the interference between the two must be considered when defining J and H-aggregates. Generally, such π-stacked aggregates do not abide by the traditional classification scheme of Kasha: for example, even when the Coulomb coupling is strong the presence of a similarly strong but destructively interfering CT-mediated coupling results in "null-aggregates" which spectroscopically resemble uncoupled molecules. Based on a Frenkel/CT Holstein Hamiltonian that takes into account both sources of electronic coupling as well as intramolecular vibrations, vibronic spectral signatures are developed for integrated Frenkel/CT systems in both the perturbative and resonance regimes. In the perturbative regime, the sign of the lowest exciton band curvature, which rigorously defines J and H-aggregation, is directly tracked by the ratio of the first two vibronic peak intensities. Even in the resonance regime, the vibronic ratio remains a useful tool to evaluate the J or H nature of the system. The theory developed is applied to the reversible H to J-aggregate transformations recently observed in several perylene bisimide systems.

  13. Competitive Adsorption of Naphthenic Acids and Polyaromatic Molecules at a Toluene-Water Interface.

    PubMed

    Teklebrhan, Robel B; Jian, Cuiying; Choi, Phillip; Xu, Zhenghe; Sjöblom, Johan

    2016-12-22

    The early-stage competitive co-adsorption of interfacially active naphthenic acids (NAs) and polyaromatic (PA) molecules to a toluene-water interface from the bulk toluene phase was studied using molecular dynamics (MD) simulation. The NA molecules studied had the same polar functional group but different cycloaliphatic nonpolar tails, and a perylene bisimide (PBI)-based molecule was used as a representative PA compound. The results from our simulations suggest that the size and structural features of NA molecules greatly influence the interfacial activity of PA molecules and partitioning of NA molecules at the toluene-water interface. At low concentrations of PA (∼2.3 wt %) and NA (∼0.4 wt %) molecules, NA molecules containing large cycloaliphatic rings (e.g., four rings) or with a very long aliphatic tail (e.g., carbon chain length of 14) were observed to impede the migration of PA molecules to the interface, whereas small NA molecules containing two cycloaliphatic rings had little effect on the adsorption of PA molecules at the toluene-water interface. At high NA concentrations, the adsorption of PA molecules (∼5.75-17.25 wt %) was greatly hindered by the presence of small NA molecules (∼1.6-4.8 wt %) due to the solvation of PA nanoaggregates in the bulk. Adsorption mechanisms of PA and NA molecules at toluene-water interfaces were clarified through a detailed analysis on the interactions among different species in the system. The results obtained from this work provide insights into designing appropriate chemical demulsifiers or co-demulsifiers for breaking water-in-oil emulsions of great industrial applications.

  14. (Photo)physical Properties of New Molecular Glasses End-Capped with Thiophene Rings Composed of Diimide and Imine Units

    PubMed Central

    2014-01-01

    New symmetrical arylene bisimide derivatives formed by using electron-donating–electron-accepting systems were synthesized. They consist of a phthalic diimide or naphthalenediimide core and imine linkages and are end-capped with thiophene, bithiophene, and (ethylenedioxy)thiophene units. Moreover, polymers were obtained from a new diamine, N,N′-bis(5-aminonaphthalenyl)naphthalene-1,4,5,8-dicarboximide and 2,5-thiophenedicarboxaldehyde or 2,2′-bithiophene-5,5′-dicarboxaldehyde. The prepared azomethine diimides exhibited glass-forming properties. The obtained compounds emitted blue light with the emission maximum at 470 nm. The value of the absorption coefficient was determined as a function of the photon energy using spectroscopic ellipsometry. All compounds are electrochemically active and undergo reversible electrochemical reduction and irreversible oxidation processes as was found in cyclic voltammetry and differential pulse voltammetry (DPV) studies. They exhibited a low electrochemically (DPV) calculated energy band gap (Eg) from 1.14 to 1.70 eV. The highest occupied molecular orbital and lowest unoccupied molecular orbital levels and Eg were additionally calculated theoretically by density functional theory at the B3LYP/6-31G(d,p) level. The photovoltaic properties of two model compounds as the active layer in organic solar cells in the configuration indium tin oxide/poly(3,4-(ethylenedioxy)thiophene):poly(styrenesulfonate)/active layer/Al under an illumination of 1.3 mW/cm2 were studied. The device comprising poly(3-hexylthiophene) with the compound end-capped with bithiophene rings showed the highest value of Voc (above 1 V). The conversion efficiency of the fabricated solar cell was in the range of 0.69–0.90%. PMID:24966893

  15. Self-assembly of semiconductor organogelator nanowires for photoinduced charge separation.

    PubMed

    Wicklein, André; Ghosh, Suhrit; Sommer, Michael; Würthner, Frank; Thelakkat, Mukundan

    2009-05-26

    We investigated an innovative concept of general validity based on an organogel/polymer system to generate donor-acceptor nanostructures suitable for charge generation and charge transport. An electron conducting (acceptor) perylene bisimide organogelator forms nanowires in suitable solvents during gelation process. This phenomenon was utilized for its self-assembly in an amorphous hole conducting (donor) polymer matrix to realize an interpenetrating donor-acceptor interface with inherent morphological stability. The self-assembly and interface generation were carried out either stepwise or in a single-step. Morphology of the donor-acceptor network in thin films obtained via both routes were studied by a combination of scanning electron microscopy and atomic force microscopy. Additionally, photoinduced charge separation and charge transport in these systems were tested in organic solar cells. Fabrication steps of multilayer organogel/polymer photovoltaic devices were optimized with respect to morphology and surface roughness by introducing additional smoothening layers and charge injection/blocking layers. An inverted cell geometry was used here in which electrons are collected at the bottom electrode and holes at the top electrode. The simultaneous preparation of the interface exhibits almost 3-fold improvement in device characteristics compared to the successive method. The device characteristics under AM1.5 spectral conditions and 100 mW/cm(2) for the simultaneous preparation route are short circuit current J(sc) = 0.28 mA cm(-2), open circuit voltage V(OC) = 390 mV, fill factor FF = 38%, and a power conversion efficiency eta = 0.041%.

  16. Interference between Coulombic and CT-mediated couplings in molecular aggregates: H- to J-aggregate transformation in perylene-based π-stacks

    SciTech Connect

    Hestand, Nicholas J.; Spano, Frank C.

    2015-12-28

    The spectroscopic differences between J and H-aggregates are traditionally attributed to the spatial dependence of the Coulombic coupling, as originally proposed by Kasha. However, in tightly packed molecular aggregates wave functions on neighboring molecules overlap, leading to an additional charge transfer (CT) mediated exciton coupling with a vastly different spatial dependence. The latter is governed by the nodal patterns of the molecular LUMOs and HOMOs from which the electron (t{sub e}) and hole (t{sub h}) transfer integrals derive. The sign of the CT-mediated coupling depends on the sign of the product t{sub e}t{sub h} and is therefore highly sensitive to small (sub-Angstrom) transverse displacements or slips. Given that Coulombic and CT-mediated couplings exist simultaneously in tightly packed molecular systems, the interference between the two must be considered when defining J and H-aggregates. Generally, such π-stacked aggregates do not abide by the traditional classification scheme of Kasha: for example, even when the Coulomb coupling is strong the presence of a similarly strong but destructively interfering CT-mediated coupling results in “null-aggregates” which spectroscopically resemble uncoupled molecules. Based on a Frenkel/CT Holstein Hamiltonian that takes into account both sources of electronic coupling as well as intramolecular vibrations, vibronic spectral signatures are developed for integrated Frenkel/CT systems in both the perturbative and resonance regimes. In the perturbative regime, the sign of the lowest exciton band curvature, which rigorously defines J and H-aggregation, is directly tracked by the ratio of the first two vibronic peak intensities. Even in the resonance regime, the vibronic ratio remains a useful tool to evaluate the J or H nature of the system. The theory developed is applied to the reversible H to J-aggregate transformations recently observed in several perylene bisimide systems.

  17. Probing structure-nanoaggregation relations of polyaromatic surfactants: a molecular dynamics simulation and dynamic light scattering study.

    PubMed

    Teklebrhan, Robel B; Ge, Lingling; Bhattacharjee, Subir; Xu, Zhenghe; Sjöblom, Johan

    2012-05-24

    Four synthetic perylene bisimide-based polyaromatic (PA) surfactants with a structural or functional group difference in their attached hydrophilic/hydrophobic substituent side chains were used to probe structure-nanoaggregation relations in organic media by molecular dynamics simulations and dynamic light scattering. The results from the simulated radial distribution functions and light scattering experiments indicate that variation in the structure of side chains and polarity of functional groups leads to significant variations in molecular association, dynamics of molecular nanoaggregation and structure of nanoaggregates. The aggregates of PA surfactant molecules grow to much larger sizes in heptane than in toluene. The aromatic solvent is shown to hinder molecular association by weakening π-π stacking, demonstrating the control of molecular aggregation by tuning solvent properties. In aliphatic solvent, the aggregates formed from PA surfactants of aliphatic alkyl groups and phenylalanine derivatives as a side chain usually have a higher solvent accessible surface area to accessible volume ratio (SASA:AV) than that of tryptophan derivatives in their side chains. PA surfactants with an aliphatic functional group in both side chains does not form polyaromatic π-π stacking (T-stacking) due to its strong steric hindrance in both solvents. Depending on the nature of the side chains attached, various stacking distributions, aggregation sizes, and SASA:AV ratios were obtained. In PA surfactant nanoaggregates, all of the solvent molecules were found to be excluded from the interstices of the stacked polyaromatic cores, regardless of whether the solvent molecules are aliphatic or aromatic. Although the change in the structure of side chain substituent in polyaromatic surfactants has a negligible impact on their self-diffusivity, it can strongly influence their intermolecular interactions, leading to different aggregate diffusion coefficients.

  18. Investigations into complex liquid crystal mixtures

    NASA Astrophysics Data System (ADS)

    Kirchhoff, Jennifer

    Liquid crystal phases exhibit physical characteristics that lie between those of liquid and crystal phases. The many liquid crystal sub-phases are defined based on the degree of positional and orientational ordering the molecules have and the materials that make up these liquid crystal phases. This thesis presents a study of the molecular packing and physical properties of complex liquid crystal phases using dopants to better examine the stability and packing mechanisms of these phases. It also looks at the dispersion of quantum dots in liquid crystal materials, examining the electro-optical properties of the mixtures. The main goal of this thesis is to examine the effects of dopants on the properties of liquid crystal phases using optical microscopy, differential scanning calorimetry, electro-optical measurements, and X-ray scattering. For those mixtures with quantum dots fluorescence microscopy and photoluminescence measurements were also conducted. Rod-like liquid crystals are commonly used in display applications when the material is in a nematic liquid crystal phase, which is the least ordered phase exhibiting no positional ordering. The more complicated chiral smectic liquid crystal phases, which have a one dimensional layer structure, show potential for faster and tri-stable switching. A chiral rod-like liquid crystal material is doped with both chiral and achiral rod-like liquid crystals to examine the stability of one of the chiral smectic sub-phase, the SmC* FI1 phase. This phase consists of tilted molecules rotating about the cone defined by the tilt angle with a periodicity of three layers and an overall helical structure. The SmC*FI1 phase is stabilized by the competition between antiferroelectric and ferroelectric interactions, and small amounts of the achiral dopant broadens the range of this phase by almost 5°C. Higher dopant concentrations of the achiral material result in the destabilization of not just the SmC*FI1 phase but all tilted sub

  19. Synthesis and characterization of F-doped Cs{sub 0.33}WO{sub 3−x}F{sub x} particles with improved near infrared shielding ability

    SciTech Connect

    Liu, Jingxiao; Luo, Jiayu; Shi, Fei Liu, Suhua; Fan, Chuanyan; Xu, Qiang; Shao, Guolin

    2015-01-15

    F-doped Cs{sub 0.33}WO{sub 3−x}F{sub x} particles were successfully synthesized by the hydrothermal method with hydrofluoric acid as fluorine source, and a new kind of heat insulating films were prepared from dispersion of Cs{sub 0.33}WO{sub 3−x}F{sub x} nanoparticles in polyvinyl alcohol (PVA) aqueous solution. The effects of F doping on the crystal structure and morphology of Cs{sub 0.33}WO{sub 3−x}F{sub x} particles as well as the near-infrared (NIR) shielding ability and heat insulation properties of Cs{sub 0.33}WO{sub 3−x}F{sub x} films were investigated. The results indicated that HF acid addition could promote the formation of rod-like Cs{sub 0.33}WO{sub 3−x}F{sub x} particles during hydrothermal synthesis and increase the yield of Cs{sub 0.33}WO{sub 3−x}F{sub x} powders. Moreover, the as-prepared films from dispersion solution of Cs{sub 0.33}WO{sub 3−x}F{sub x} particles exhibited higher near-infrared (NIR) shielding ability and heat insulating properties than that of the undoped Cs{sub 0.33}WO{sub 3} film. Particularly, the as-prepared Cs{sub 0.33}WO{sub 3−x}F{sub x} sample with F/W (molar ratio)=0.45 showed best NIR shielding ability and transparent heat insulating performance. The formation mechanism of nanorod-like particles and the effects of F doping on the properties of Cs{sub 0.33}WO{sub 3−x}F{sub x} products were discussed. - Graphical abstract: F-doped Cs{sub 0.33}WO{sub 3−x}F{sub x} particles were successfully synthesized by the hydrothermal method with hydrofluoric acid as fluorine source. HF acid addition in the precursor solution could increase the yield of Cs{sub 0.33}WO{sub 3−x}F{sub x} powders and promote the formation of rod-like Cs{sub 0.33}WO{sub 3−x}F{sub x} particles. Moreover, the as-prepared Cs{sub 0.33}WO{sub 3−x}F{sub x} films from dispersion solution of Cs{sub 0.33}WO{sub 3−x}F{sub x} particles exhibited higher near-infrared (NIR) shielding ability and heat insulating properties than that of the undoped

  20. Micromorphological effect of calcium phosphate coating on compatibility of magnesium alloy with osteoblast

    PubMed Central

    Hiromoto, Sachiko; Yamazaki, Tomohiko

    2017-01-01

    Abstract Octacalcium phosphate (OCP) and hydroxyapatite (HAp) coatings were developed to control the degradation speed and to improve the biocompatibility of biodegradable magnesium alloys. Osteoblast MG-63 was cultured directly on OCP- and HAp-coated Mg-3Al-1Zn (wt%, AZ31) alloy (OCP- and HAp-AZ31) to evaluate cell compatibility. Cell proliferation was remarkably improved with OCP and HAp coatings which reduced the corrosion and prevented the H2O2 generation on Mg alloy substrate. OCP-AZ31 showed sparse distribution of living cell colonies and dead cells. HAp-AZ31 showed dense and homogeneous distribution of living cells, with dead cells localized over and around corrosion pits, some of which were formed underneath the coating. These results demonstrated that cells were dead due to changes in the local environment, and it is necessary to evaluate the local biocompatibility of magnesium alloys. Cell density on HAp-AZ31 was higher than that on OCP-AZ31 although there was not a significant difference in the amount of Mg ions released in medium between OCP- and HAp-AZ31. The outer layer of OCP and HAp coatings consisted of plate-like crystal with a thickness of around 0.1 μm and rod-like crystals with a diameter of around 0.1 μm, respectively, which grew from a continuous inner layer. Osteoblasts formed focal contacts on the tips of plate-like OCP and rod-like HAp crystals, with heights of 2–5 μm. The spacing between OCP tips of 0.8–1.1 μm was wider than that between HAp tips of 0.2–0.3 μm. These results demonstrated that cell proliferation depended on the micromorphology of the coatings which governed spacing of focal contacts. Consequently, HAp coating is suitable for improving cell compatibility and bone-forming ability of the Mg alloy. PMID:28179963

  1. TiO2(B) nanoparticle-functionalized WO3 nanorods with enhanced gas sensing properties.

    PubMed

    Zhang, Hongxin; Wang, Shurong; Wang, Yanshuang; Yang, Jiedi; Gao, Xueling; Wang, Liwei

    2014-06-14

    In this work, TiO2(B) nanoparticle (NP)-functionalized WO3 nanorods (NRs) were synthesized by a two-step solution strategy, with a hydrothermal process for WO3 NRs and hydrolyzation of Ti(OBu)4 for the functionalization of TiO2(B) NPs. Various techniques, including scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), were employed to investigate the morphology, microstructure, crystalline nature and chemical composition of the prepared TiO2(B) NP-functionalized WO3 NRs. SEM and TEM results revealed that the TiO2(B)-WO3 composite showed a rod-like nanostructure with a diameter in the range from 93 to 154 nm and a rough surface, which could increase the accessible surface area and the amount of surface active sites, thus improving the properties or performance of the as-prepared composite NRs. XRD and XPS analysis clearly verified that monoclinic TiO2(B) NPs, a metastable polymorph of TiO2, were successfully supported on the WO3 NRs. Gas sensing measurement results for several common reductive organic gases such as acetone, ethanol, ether, methanol and formaldehyde demonstrated that the sensor based on the as-obtained TiO2(B) NP-functionalized WO3 NRs exhibited obviously enhanced responses compared with a pure WO3 NR based sensor, as well as fast response-recovery speeds, good reproducibility and good stability, indicating their promising application in gas sensors. The excellent gas sensing performance could be attributed to the unique 1D rod-like nanostructure with a rough surface, the existence of TiO2-WO3 heterojunctions and the catalytic effect of the TiO2(B) NPs. The as-prepared TiO2(B) NP-functionalized WO3 NRs will also have very good prospects in electrochromic devices and catalysis applications.

  2. Hard, soft, and sticky spheres for dynamical studies of disordered colloidal packings

    NASA Astrophysics Data System (ADS)

    Gratale, Matthew Daniel

    This thesis describes experiments which explore the role of interparticle interactions as a means to alter, and control, the properties of dense colloidal packings. The first set of experiments studied phonon modes in two-dimensional colloidal crystals composed of soft microgel particles with hard polystyrene particle dopants distributed randomly on the triangular lattice. By mixing hard and soft spheres we obtain close-packed lattices of spheres with random bond strength disorder, textit{i.e.,} the effective springs coupling nearest-neighbors are either very stiff, very soft, or of intermediate stiffness. Video microscopy, particle tracking, and covariance matrix techniques are employed to derive the phonon modes of the corresponding ``shadow'' crystals, thereby enabling us to study how bond strength disorder affects vibrational properties. Hard and soft particles participate equally in low frequency phonon modes, and the samples exhibit Debye-like density of states behavior characteristic of crystals at low frequency. For mid- and high-frequency phonons, the relative participation of hard versus soft particles in each mode is found to vary systematically with dopant concentration. The second set of experiments investigated depletion interaction potentials between micron-size colloidal particles induced by nanometer-scale micelles composed of the surfactant hexaethylene glycol monododecyl ether (C12E6). The strength and range of the depletion interaction is revealed to arise from variations in shape anisotropy of the rod-like surfactant micelles. This shape anisotropy increases with increasing sample temperature. By fitting the colloidal interaction potentials to theoretical models, we extract the rod-like micelle length and shape anisotropy as a function of temperature. This work introduces micelle shape anisotropy as a means to control interparticle interactions in colloidal suspensions, and shows how interparticle depletion potentials of micron-scale objects

  3. Positional isomerism-driven two 3D pillar-layered metal-organic frameworks: Syntheses, topological structures and photoluminescence properties

    SciTech Connect

    Sun, Yayong; Zhao, Siwei; Ma, Haoran; Han, Yi; Liu, Kang; Wang, Lei

    2016-06-15

    Two novel three-dimensional (3D) pillar-layered metal-organic frameworks (MOFs), namely [Zn{sub 2}(μ{sub 2}-OH)(boaba)(1,4-bmimb)]{sub n} (1) and {[Zn_5K_2(μ_2-H_2O)_2(boaba)_4(1,2-bmimb)_2(H_2O)_2]·H_2O}{sub n} (2), were prepared by hydrothermal reactions (H{sub 3}boaba=3,5-bis-oxyacetate-benzoic acid; 1,4-bmimb=1,4-bis((2-methyl-1H-imidazol-1-yl)methyl)benzene; 1,2-bmimb =1,2-bis((2-methyl-1H-imidazol-1-yl)methyl)benzene). Notably, 1 exhibits a (3,5)-connected binodal (6{sup 3})(6{sup 9}·8)-gra net with binuclear [Zn{sub 2}(μ{sub 2}-OH)(COO)]{sup 2+} clusters, while 2 shows a novel (4,4,5,9)-connected 4-nodal net constructed from the unique Zn(II)-K(I) heterometal rod-like substructures. The results indicate that the disposition of the 2-methylimidazolyl groups of bis(imidazole) ligands have a significant effect on structural diversity. Moreover, the photoluminescence properties of 1 and 2 have been investigated. - Graphical abstract: Two novel 3D pillar-layered metal-organic coordination networks with aromatic multicarboxylate anion and bis(imidazole) ligands have been synthesized and structurally characterized. Display Omitted - Highlights: • It is rarely reported that metal-organic frameworks prepared with 3,5-bis-oxyacetate-benzoic acid. • Two metal-organic frameworks based on positional isomeric ligands were synthesized and structurally characterized. • Compond 1 displays unique (3,5)-connected binodal gra topology. • Compound 2 exhibits (4,4,5,9)-connected 4-nodal topology based on the Zn(II)-K(I) heterometal rod-like substructures. • The photoluminescence properties of compound 1 and 2 have been investigated.

  4. Anisotropy in CdSe quantum rods

    SciTech Connect

    Li, Liang-shi

    2003-01-01

    The size-dependent optical and electronic properties of semiconductor nanocrystals have drawn much attention in the past decade, and have been very well understood for spherical ones. The advent of the synthetic methods to make rod-like CdSe nanocrystals with wurtzite structure has offered us a new opportunity to study their properties as functions of their shape. This dissertation includes three main parts: synthesis of CdSe nanorods with tightly controlled widths and lengths, their optical and dielectric properties, and their large-scale assembly, all of which are either directly or indirectly caused by the uniaxial crystallographic structure of wurtzite CdSe. The hexagonal wurtzite structure is believed to be the primary reason for the growth of CdSe nanorods. It represents itself in the kinetic stabilization of the rod-like particles over the spherical ones in the presence of phosphonic acids. By varying the composition of the surfactant mixture used for synthesis we have achieved tight control of the widths and lengths of the nanorods. The synthesis of monodisperse CdSe nanorods enables us to systematically study their size-dependent properties. For example, room temperature single particle fluorescence spectroscopy has shown that nanorods emit linearly polarized photoluminescence. Theoretical calculations have shown that it is due to the crossing between the two highest occupied electronic levels with increasing aspect ratio. We also measured the permanent electric dipole moment of the nanorods with transient electric birefringence technique. Experimental results on nanorods with different sizes show that the dipole moment is linear to the particle volume, indicating that it originates from the non-centrosymmetric hexagonal lattice. The elongation of the nanocrystals also results in the anisotropic inter-particle interaction. One of the consequences is the formation of liquid crystalline phases when the nanorods are dispersed in solvent to a high enough

  5. Stopped-flow kinetic studies of sphere-to-rod transitions of sodium alkyl sulfate micelles induced by hydrotropic salt.

    PubMed

    Zhang, Jingyan; Ge, Zhishen; Jiang, Xiaoze; Hassan, P A; Liu, Shiyong

    2007-12-15

    The kinetics and mechanism of sphere-to-rod transitions of sodium alkyl sulfate micelles induced by hydrotropic salt, p-toluidine hydrochloride (PTHC), were investigated by stopped-flow with light scattering detection. Spherical sodium dodecyl sulfate (SDS) micelles transform into short ellipsoidal shapes at low salt concentrations ([PTHC]/[SDS], chi(PTHC)=0.3 and 0.4). Upon stopped-flow mixing aqueous solutions of spherical SDS micelles with PTHC, the scattered light intensity gradually increases with time. Single exponential fitting of the dynamic traces leads to characteristic relaxation time, tau(g), for the growth process from spherical to ellipsoidal micelles, and it increases with increasing SDS concentrations. This suggests that ellipsoidal micelles might be produced by successive insertion of unimers into spherical micelles, similar to the case of formation of spherical micelles as suggested by Aniansson-Wall (A-W) theory. At chi(PTHC) > or = 0.5, rod-like micelles with much higher axial ratio form. The scattered light intensity exhibits an initially abrupt increase and then levels off. The dynamic curves can be well fitted with single exponential functions, and the obtained tau(g) decreases with increasing SDS concentration. Thus, the growth from spherical to rod-like micelles might proceed via fusion of spherical micelles, in agreement with mechanism proposed by Ikeda et al. At chi(PTHC)=0.3 and 0.6, the apparent activation energies obtained from temperature dependent kinetic studies for the micellar growth are 40.4 and 3.6 kJ/mol, respectively. The large differences between activation energies for the growth from spherical to ellipsoidal micelles at low chi(PTHC) and the sphere-to-rod transition at high chi(PTHC) further indicate that they should follow different mechanisms. Moreover, the sphere-to-rod transition kinetics of sodium alkyl sulfate with varying hydrophobic chain lengths (n=10, 12, 14, and 16) are also studied. The longer the carbon chain

  6. On the "tertiary structure" of poly-carbenes; self-assembly of sp3-carbon-based polymers into liquid-crystalline aggregates.

    PubMed

    Franssen, Nicole M G; Ensing, Bernd; Hegde, Maruti; Dingemans, Theo J; Norder, Ben; Picken, Stephen J; Alberda van Ekenstein, Gert O R; van Eck, Ernst R H; Elemans, Johannes A A W; Vis, Mark; Reek, Joost N H; de Bruin, Bas

    2013-08-26

    The self-assembly of poly(ethylidene acetate) (st-PEA) into van der Waals-stabilized liquid-crystalline (LC) aggregates is reported. The LC behavior of these materials is unexpected, and unusual for flexible sp(3)-carbon backbone polymers. Although the dense packing of polar ester functionalities along the carbon backbone of st-PEA could perhaps be expected to lead directly to rigid-rod behavior, molecular modeling reveals that individual st-PEA chains are actually highly flexible and should not reveal rigid-rod induced LC behavior. Nonetheless, st-PEA clearly reveals LC behavior, both in solution and in the melt over a broad elevated temperature range. A combined set of experimental measurements, supported by MM/MD studies, suggests that the observed LC behavior is due to self-aggregation of st-PEA into higher-order aggregates. According to MM/MD modeling st-PEA single helices adopt a flexible helical structure with a preferred trans-gauche syn-syn-anti-anti orientation. Unexpectedly, similar modeling experiments suggest that three of these helices can self-assemble into triple-helical aggregates. Higher-order assemblies were not observed in the MM/MD simulations, suggesting that the triple helix is the most stable aggregate configuration. DLS data confirmed the aggregation of st-PEA into higher-order structures, and suggest the formation of rod-like particles. The dimensions derived from these light-scattering experiments correspond with st-PEA triple-helix formation. Langmuir-Blodgett surface pressure-area isotherms also point to the formation of rod-like st-PEA aggregates with similar dimensions as st-PEA triple helixes. Upon increasing the st-PEA concentration, the viscosity of the polymer solution increases strongly, and at concentrations above 20 wt % st-PEA forms an organogel. STM on this gel reveals the formation of helical aggregates on the graphite surface-solution interface with shapes and dimensions matching st-PEA triple helices, in good agreement

  7. Systematic study on the influence of the morphology of α-MoO{sub 3} in the selective oxidation of propylene

    SciTech Connect

    Schuh, Kirsten; Kleist, Wolfgang; Høj, Martin; Jensen, Anker Degn; Beato, Pablo; Grunwaldt, Jan-Dierk

    2015-08-15

    A variety of morphologically different α-MoO{sub 3} samples were prepared by hydrothermal synthesis and applied in the selective oxidation of propylene. Their catalytic performance was compared to α-MoO{sub 3} 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-MoO{sub 3} after calcination at 550 °C. A one-step synthesis of α-MoO{sub 3} rods was possible starting from MoO{sub 3}·2H{sub 2}O 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. - Graphical abstract: Hydrothermal synthesis from MoO{sub 3}·2H{sub 2}O in the presence of HNO{sub 3} led to rod-shaped particles which mainly expose (1 0 0) facets which are the most active surfaces. - Highlights: • Hydrothermal synthesis of MoO3 resulted in either rod or slab shaped particles depending on pH. • At pH<0 rods stable towards calcination and catalytic activity testing were formed. • Rod shaped particles had significantly higher activity than slab shaped ones. • The rod shaped particles mainly expose the (1 0 0) facets which are the most active surfaces. • Total surface area is not main determining factor for catalytic activity.

  8. Synthesis of Co-based bimetallic nanocrystals with one-dimensional structure for selective control on syngas conversion

    NASA Astrophysics Data System (ADS)

    Ba, Rongbin; Zhao, Yonghui; Yu, Lujing; Song, Jianjun; Huang, Shuangshuang; Zhong, Liangshu; Sun, Yuhan; Zhu, Yan

    2015-07-01

    Co-based bimetallic nanocrystals with one-dimensional (1D) branches were synthesized by the heterogeneous nucleation of Co atoms onto prenucleated seeds, such as Pd or Cu, through a facile wet-chemical route. The peripheral branches (rod-like) of the Co-Pd and Co-Cu nanocrystals were outspread along the (001) direction and were enclosed by (101) facets. By switching the prenucleated metals to form robust Co-Pd or Co-Cu bimetallic nanocatalysts, the selectivity of CO hydrogenation could be adjusted purposely towards heavy paraffins, light olefins or oxygenates. The Anderson-Schulz-Flory chain-lengthening probabilities for products were up to 0.9 over Co-Pd nanocrystals, showing that long-chain hydrocarbons can be formed with high selectivity using the targeted design of Co-Pd nanocrystal catalysts. These Co-based bimetallic nanocrystals with a 1D structure exhibited superior catalytic activities over the corresponding Co-based nanoparticles for synthesis gas conversion.Co-based bimetallic nanocrystals with one-dimensional (1D) branches were synthesized by the heterogeneous nucleation of Co atoms onto prenucleated seeds, such as Pd or Cu, through a facile wet-chemical route. The peripheral branches (rod-like) of the Co-Pd and Co-Cu nanocrystals were outspread along the (001) direction and were enclosed by (101) facets. By switching the prenucleated metals to form robust Co-Pd or Co-Cu bimetallic nanocatalysts, the selectivity of CO hydrogenation could be adjusted purposely towards heavy paraffins, light olefins or oxygenates. The Anderson-Schulz-Flory chain-lengthening probabilities for products were up to 0.9 over Co-Pd nanocrystals, showing that long-chain hydrocarbons can be formed with high selectivity using the targeted design of Co-Pd nanocrystal catalysts. These Co-based bimetallic nanocrystals with a 1D structure exhibited superior catalytic activities over the corresponding Co-based nanoparticles for synthesis gas conversion. Electronic supplementary

  9. Investigating the orientational order in smectic liquid crystals

    NASA Astrophysics Data System (ADS)

    Wang, Shun

    This thesis is composed of two projects. The first one is the investigation of a reversed phase sequence, which subsequently leads to the discovery of a novel Smectic-C liquid crystal phase. The 10OHFBBB1M7 (10OHF) compound shows a reversed phase sequence with the SmC*d4 phase occurring at a higher temperature than the SmC* phase. This phase sequence is stabilized by moderate doping of 9OTBBB1M7 (C9) or 11OTBBB1M7 (C11). To further study this unique phase sequence, the mixtures of 10OHFBBB1M7 and its homologs have been characterized by optical techniques. In order to perform the resonant X-ray diffraction experiment, we have added C9 and C11 compounds to the binary mixtures and pure 10OHF. In two of the studied mixtures, a new smectic-C* liquid crystal phase with six-layer periodicity has been discovered. Upon cooling, the new phase appears between the SmC*a phase having a helical structure and the SmC*d4 phase with four-layer periodicity. The SmC*d6 phase shows a distorted clock structure. Three theoretical models have predicted the existence of a six-layer phase. However, our experimental findings are not consistent with the theories. The second project involves the mixtures of liquid crystals with different shapes. The role of different interactions in stabilizing the antiferroelectric smectic liquid crystal phases have been a long-standing questions in the community. By mixing the antiferroelectric smectic liquid crystal with achiral liquid crystal molecules with rod and hockey-stick shapes, distinct different behaviors are obtained. In the case of the mixtures of chiral smectic liquid crystals with rod-like molecules, all the smectic-C* variant phases vanish with a small amount of doping. However, the hockey-stick molecule is much less destructive compared to the rod-like molecule. This suggests that the antiferroelectric smectic liquid crystal molecules may have a shape closer to a hockey-stick rather than a rod.

  10. Surface and related bulk properties of titania nanoparticles recovered from aramid–titania hybrid films: A novel attempt

    SciTech Connect

    Al-Omani, Sara J.; Bumajdad, Ali; Al Sagheer, Fakhreia A.; Zaki, Mohamed I.

    2012-11-15

    Highlights: ► Aramid–titania hybrid films (5 and 10 wt%-TiO{sub 2}) were prepared via sol–gel processing. ► 450 °C calcination of the films yield anatase-TiO{sub 2} nanoparticles of rod-like morphology. ► The titania nanoparticle, crystal structure, high surface area are stable up to 800 °C. ► The novel approach has the advantage of nearly 100% recovery of titania. ► Increasing calcination temperature up to 1100 °C triggers anatase → rutile transition. -- Abstract: 5 and 10 wt%-TiO{sub 2}-containing aramid–titania hybrid films were prepared using sol–gel processing improved by the inclusion of 3-isocyanato-propyltriethoxysilane (ICTOS) to strengthen bonding of the titania species to the polymer backbone and, hence, lessen its agglomeration. The films were thermally degraded by heating at 450 °C in a dynamic atmosphere of air. The solid residues were found by thermogravimetry, X-ray diffractometry and electron microscopy to consist dominantly of uniformly agglomerated rod-like anatase-TiO{sub 2} nanoparticles, irrespective of the titania content of the film. The recovered titania particle morphology and surface microstructure were examined by field emission scanning and high-resolution transmission electron microscopy, respectively. Whereas, the particle surface chemistry and texture were assessed, respectively, by means of X-ray photoelectron spectroscopy and N{sub 2} sorptiometry. The recovered titanias were found, irrespective of the film content of titania, to enjoy not only a high temperature (up to 800 °C) stable nanoscopic anatase bulk structure, but also a high-temperature stable surface chemical composition (lattice Ti{sup 4+} and O{sup 2−}, and adsorbed OH/CH{sub x} species), (101)-faceted microstructure and highly accessible (145–112 m{sup 2}/g), uniform mesoporous texture with average pore diameter in the narrow range of 3.9–6.3 nm. Increasing the calcination temperature up to 1100 °C enhances an anatase → rutile

  11. Zeolite-like liquid crystals

    PubMed Central

    Poppe, Silvio; Lehmann, Anne; Scholte, Alexander; Prehm, Marko; Zeng, Xiangbing; Ungar, Goran; Tschierske, Carsten

    2015-01-01

    Zeolites represent inorganic solid-state materials with porous structures of fascinating complexity. Recently, significant progress was made by reticular synthesis of related organic solid-state materials, such as metal-organic or covalent organic frameworks. Herein we go a step further and report the first example of a fluid honeycomb mimicking a zeolitic framework. In this unique self-assembled liquid crystalline structure, transverse-lying π-conjugated rod-like molecules form pentagonal channels, encircling larger octagonal channels, a structural motif also found in some zeolites. Additional bundles of coaxial molecules penetrate the centres of the larger channels, unreachable by chains attached to the honeycomb framework. This creates a unique fluid hybrid structure combining positive and negative anisotropies, providing the potential for tuning the directionality of anisotropic optical, electrical and magnetic properties. This work also demonstrates a new approach to complex soft-matter self-assembly, by using frustration between space filling and the entropic penalty of chain extension. PMID:26486751

  12. Skeletal cubic, lamellar, and ribbon phases of bundled thermotropic bolapolyphiles.

    PubMed

    Liu, Feng; Prehm, Marko; Zeng, Xiangbing; Tschierske, Carsten; Ungar, Goran

    2014-05-14

    A series of T-shaped polyphilic molecules composed of a rigid linear biphenyl core with a polar glycerol group at each end and one swallow-tail semiperfluorinated lateral chain were synthesized and their thermotropic liquid crystalline (LC) phases were investigated by X-ray diffraction, calorimetry, and microscopy. The compounds have a long alkyl spacer between the aromatic core and the fluorinated C(n)F(2n+1) ends, where n = 4, 6, 8, and 10. Upon melting, all compounds start with lamellar LC phases, followed on heating by a rectangular columnar ribbon phase with c2mm symmetry. Unusually, a ribbon is a flat bundle of molecular cores highly aligned parallel to the ribbon axis. On further heating, for n = 8 and 10, this phase is succeeded by a bicontinuous cubic phase with Ia3d symmetry. This is a new variant of the "gyroid" phase, with axially oriented rod-like molecular cores forming the skeleton of the two infinite networks and junctions separated by exactly two molecular lengths. In this tricontinuous core-shell structure (aromatic-aliphatic-perfluoroalkyl), the polar glycerol domains of appreciable size, contained within the skeleton, can be considered as micellar.

  13. Interaction of light with hematite hierarchical structures: Experiments and simulations

    NASA Astrophysics Data System (ADS)

    Distaso, Monica; Zhuromskyy, Oleksander; Seemann, Benjamin; Pflug, Lukas; Mačković, Mirza; Encina, Ezequiel; Taylor, Robin Klupp; Müller, Rolf; Leugering, Günter; Spiecker, Erdmann; Peschel, Ulf; Peukert, Wolfgang

    2017-03-01

    Mesocrystalline particles have been recognized as a class of multifunctional materials with potential applications in different fields. However, the internal organization of nanocomposite mesocrystals and its influence on the final properties have not yet been investigated. In this paper, a novel strategy based on electrodynamic simulations is developed to shed light on how the internal structure of mesocrystals influences their optical properties. In a first instance, a unified design protocol is reported for the fabrication of hematite/PVP particles with different morphologies such as pseudo-cubes, rods-like and apple-like structures and controlled particle size distributions. The optical properties of hematite/PVP mesocrystals are effectively simulated by taking their aggregate and nanocomposite structure into consideration. The superposition T-Matrix approach accounts for the aggregate nature of mesocrystalline particles and validate the effective medium approximation used in the framework of the Mie theory and electromagnetic simulation such as Finite Element Method. The approach described in our paper provides the framework to understand and predict the optical properties of mesocrystals and more general, of hierarchical nanostructured particles.

  14. A mimic study on effects of fluoride on tooth enamel structures

    NASA Astrophysics Data System (ADS)

    Ma, Guobin; Wang, Mu; Liu, Xiang Yang

    2010-03-01

    Tooth enamel is the hardest tissue in human body, and this superior mechanical property is contributed by its unique microstructures, i.e., oriented growth of rod-like apatite crystals into basic structural units called the prisms Fluoride (F^-) has been recognized to have significant effects on the physical and chemical properties of tooth enamel. However, the role of F^- on microstructures of apatite crystals is not well understood yet. Here we report a detailed investigation on the topic. Mimic in vitro growth of tooth enamel structures is performed at the biophysical conditions in simulated body fluids, using belt-like hydroxyapatite crystals as substrates It shows that F^- on the order of 0.1 mM will dramatically change the morphology of the grown crystals from irregular slabs to nano-needles, and the needles are aligned along the substrate with an average misorientation of ˜12 . Branched growth of bundles of nano-needles occurs with further increase of F^-, and finally, growth of highly porous structures as well as microspheres takes place when the F^- concentration exceeds 5 mM. In comparison with real tooth enamel structures, the relationship between enamel microstructures and tooth caries as well as fluorosis is discussed.

  15. Determination and prediction of physical properties of cellulose nanocrystals from dynamic light scattering measurements

    NASA Astrophysics Data System (ADS)

    Khouri, Salim; Shams, Mouhamed; Tam, Kam C.

    2014-07-01

    Cellulose nanocrystal (CNC) has attracted increasing interest due to their biocompatibility, rigidity, and potential applications in biomedicine and cosmetics. A parameter estimation technique was used to calculate the average dimension of CNC with different aspect ratios, and their dynamic physical parameters denoted by the translational ( D t) and rotational diffusion (Θ) coefficients. For CNC with L/ d ratio of 17, the experimental D t and Θ values produced calculated length ( L) and diameter ( d) values that deviated from the experimental results by 0.22 and 0.27 % after 1,000 iterations, respectively. The calculated translational and rotational coefficients converged to an asymptotic value of 5.048 × 10-12 m2 s-1 and 551.9 s-1, with the latter requiring a larger number of iterations to achieve convergence. Close agreement between experimentally obtained and calculated dimensions and dynamics ( L, d, D t, and Θ) for various types of CNCs was observed using this technique. By combining the theoretical model formulated by Broersma and the computational method utilizing a Nelder-Mead simplex direct search algorithm, reliable predictions of the average sizes determined from dynamic light scattering of a CNC sample was achieved; yielding an average L = 253.5 nm and d = 15.7 nm. The proposed approach provides a convenient, simple, and robust technique to determine the length and diameter of rod-like nanoparticles, such as CNC from light scattering measurements.

  16. Effect of Osmolytes on the Binding of EGR1 Transcription Factor to DNA

    PubMed Central

    Mikles, David C.; Bhat, Vikas; Schuchardt, Brett J.; McDonald, Caleb B.; Farooq, Amjad

    2014-01-01

    Osmolytes play a key role in maintaining protein stability and mediating macromolecular interactions within the intracellular environment of the cell. Herein, we show that osmolytes such as glycerol, sucrose and PEG400 mitigate the binding of EGR1 transcription factor to DNA in a differential manner. Thus, while physiological concentrations of glycerol only moderately reduce the binding affinity, addition of sucrose and PEG400 is concomitant with a loss in the binding affinity by an order of magnitude. This salient observation suggests that EGR1 is most likely subject to conformational equilibrium and that the osmolytes exert their effect via favorable interactions with the unliganded conformation. Consistent with this notion, our analysis reveals that while EGR1 displays rather high structural stability in complex with DNA, the unliganded conformation becomes significantly destabilized in solution. In particular, while liganded EGR1 adopts a well-defined arc-like architecture, the unliganded protein samples a comparatively large conformational space between two distinct states that periodically interconvert between an elongated rod-like shape and an arc-like conformation on a sub-microsecond time scale. Consequently, the ability of osmolytes to favorably interact with the unliganded conformation so as to stabilize it could account for the negative effect of osmotic stress on EGR1-DNA interaction observed here. Taken together, our study sheds new light on the role of osmolytes in modulating a key protein-DNA interaction. PMID:25269753

  17. A-site compositional effects in Ga-doped hollandite materials of the form BaxCsyGa2x+yTi8−2x−yO16: implications for Cs immobilization in crystalline ceramic waste forms

    PubMed Central

    Xu, Yun; Wen, Yi; Grote, Rob; Amoroso, Jake; Shuller Nickles, Lindsay; Brinkman, Kyle S.

    2016-01-01

    The hollandite structure is a promising crystalline host for Cs immobilization. A series of Ga-doped hollandite BaxCsyGa2x+yTi8−2x−yO16 (x = 0, 0.667, 1.04, 1.33; y = 1.33, 0.667, 0.24, 0) was synthesized through a solid oxide reaction method resulting in a tetragonal hollandite structure (space group I4/m). The lattice parameter associated with the tunnel dimension was found to increases as Cs substitution in the tunnel increased. A direct investigation of cation mobility in tunnels using electrochemical impedance spectroscopy was conducted to evaluate the ability of the hollandite structure to immobilize cations over a wide compositional range. Hollandite with the largest tunnel size and highest aspect ratio grain morphology resulting in rod-like microstructural features exhibited the highest ionic conductivity. The results indicate that grain size and optimized Cs stoichiometry control cation motion and by extension, the propensity for Cs release from hollandite. PMID:27273791

  18. Chitosan/zinc oxide-polyvinylpyrrolidone (CS/ZnO-PVP) nanocomposite for better thermal and antibacterial activity.

    PubMed

    Karpuraranjith, M; Thambidurai, S

    2017-03-06

    A new biopolymer based ZnO-PVP nanocomposite was successfully synthesized by single step in situ precipitation method using chitosan as biosurfactant, zinc chloride as a source material, PVP as stabilizing agent and sodium hydroxide as precipitating agent. The chemical bonding and crystalline behaviors of chitosan, zinc oxide and PVP were confirmed by FT-IR and XRD analysis. The biopolymer connected ZnO particles intercalated PVP matrix was layer and rod like structure appeared in nanometer range confirmed by HR-SEM and TEM analysis. The surface topography image of CS/ZnO-PVP nanocomposite was obtained in the average thickness of 12nm was confirmed by AFM analysis. Thermal stability of cationic biopolymer based ZnO intercalated PVP has higher stability than CS-PVP and chitosan. Consequently, antimicrobial activity of chitosan/ZnO-PVP matrix acts as a better microbial inhibition activity than PVP-ZnO nanocomposite. The obtained above results demonstrate that CS and ZnO intercalated PVP matrix has better reinforced effect than other components. Therefore, Chitosan/ZnO-PVP nanocomposite may be a promising material for the biomedical applications.

  19. Site-specific electronic couplings in dyads with MLCT excited states. Intramolecular energy transfer in isomeric Ru(II)-Ru(II) cyclometalated complexes.

    PubMed

    Polson, Matthew; Chiorboli, Claudio; Fracasso, Sandro; Scandola, Franco

    2007-04-01

    The rod-like binuclear complexes [(ttpy)Ru(tpy-ph(2)-phbpy)Ru(ttpy)](4+) and [(ttpy)Ru(tpy-ph(2)-tpy)Ru(phtbpy)](4+) (for abbreviations, see text) have been synthesized and characterized. In both complexes, the polypyridine Ru(II) centers have (N--N--N)Ru(N--N--N) and (N--N--N)Ru(C--N--N) coordination environment. The two isomeric species differ in whether the cyclometalating carbon resides on the bridging or on the terminal ligand. The two complexes have virtually identical energy levels, but MLCT excited states of different (bridging or terminal) ligand localization. They are thus ideally suited to investigate possible effects of excited-state localization on intramolecular energy transfer kinetics. In fact, ultrafast spectroscopic measurements yield different energy transfer time constants for the two isomers, with the bridge-cyclometalated complex (2.7 ps) being faster than the terminal-cyclometalated one (8.0 ps). This difference can be explained in terms of different electronic factors for Dexter energy transfer. The study highlights the peculiar intricacies of intramolecular energy transfer in inorganic dyads involving MLCT excited states.

  20. Hydrothermal synthesis of zinc oxide nanoparticles using rice as soft biotemplate

    PubMed Central

    2013-01-01

    Background Rice as a renewable, abundant bio-resource with unique characteristics can be used as a bio-template to synthesize various functional nanomaterials. Therefore, the effect of uncooked rice flour as bio-template on physico-chemical properties, especially the morphology of zinc oxide nanostructures was investigated in this study. The ZnO particles were synthesized through hydrothermal-biotemplate method using zinc acetate-sodium hydroxide and uncooked rice flour at various ratios as precursors at 120°C for 18 hours. Results The results indicate that rice as a bio-template can be used to modify the shape and size of zinc oxide particles. Different morphologies, namely flake-, flower-, rose-, star- and rod-like structures were obtained with particle size at micro- and nanometer range. Pore size and texture of the resulting zinc oxide particles were found to be template-dependent and the resulting specific surface area enhanced compared to the zinc oxide synthesized without rice under the same conditions. However, optical property particularly the band gap energy is generally quite similar. Conclusion Pure zinc oxide crystals were successfully synthesized using rice flour as biotemplate at various ratios of zinc salt to rice. The size- and shape-controlled capability of rice to assemble the ZnO particles can be employed for further useful practical applications. PMID:23919386

  1. Extending calibration-free force measurements to optically-trapped rod-shaped samples.

    PubMed

    Català, Frederic; Marsà, Ferran; Montes-Usategui, Mario; Farré, Arnau; Martín-Badosa, Estela

    2017-02-21

    Optical trapping has become an optimal choice for biological research at the microscale due to its non-invasive performance and accessibility for quantitative studies, especially on the forces involved in biological processes. However, reliable force measurements depend on the calibration of the optical traps, which is different for each experiment and hence requires high control of the local variables, especially of the trapped object geometry. Many biological samples have an elongated, rod-like shape, such as chromosomes, intracellular organelles (e.g., peroxisomes), membrane tubules, certain microalgae, and a wide variety of bacteria and parasites. This type of samples often requires several optical traps to stabilize and orient them in the correct spatial direction, making it more difficult to determine the total force applied. Here, we manipulate glass microcylinders with holographic optical tweezers and show the accurate measurement of drag forces by calibration-free direct detection of beam momentum. The agreement between our results and slender-body hydrodynamic theoretical calculations indicates potential for this force-sensing method in studying protracted, rod-shaped specimens.

  2. Phase transformation and deformation behavior of NiTi-Nb eutectic joined NiTi wires

    PubMed Central

    Wang, Liqiang; Wang, Cong; Zhang, Lai-Chang; Chen, Liangyu; Lu, Weijie; Zhang, Di

    2016-01-01

    NiTi wires were brazed together via eutectic reaction between NiTi and Nb powder deposited at the wire contact region. Phase transformation and deformation behavior of the NiTi-Nb eutectic microstructure were investigated using transmission electron microscopy (TEM) and cyclic loading-unloading tests. Results show that R phase and B19′ martensite transformation are induced by plastic deformation. R phase transformation, which significantly contributes to superelasticity, preferentially occurs at the interfaces between NiTi and eutectic region. Round-shaped Nb-rich phase with rod-like and lamellar-type eutectics are observed in eutectic regions. These phases appear to affect the deformation behavior of the brazed NiTi-Nb region via five distinct stages in stress-strain curves: (I) R phase reorientation, (II) R phase transformation from parent phase, (III) elastic deformation of reoriented martensite accompanied by the plastic deformation of Nb-rich phase and lamellar NiTi-Nb eutectic, (IV) B19′ martensitic transformation, and (V) plastic deformation of the specimen. PMID:27049025

  3. A Comparative Morphological Study of the Jugal and Quadratojugal in Early Birds and Their Dinosaurian Relatives.

    PubMed

    Wang, Min; Hu, Han

    2017-01-01

    The zygoma (called jugal bar) in modern birds accounts for a large portion of the ventral margin of the cranium. As a delicate and rod-like element, the jugal bar is functionally integrated into the avian cranial kinesis, a unique property that allows the beak to be elevated or depressed with respect to the braincase and thus distinguishes birds from all other modern vertebrates. Developmental studies show that the jugal bar of modern birds is formed by the fusion of the jugal and quadratojugal that are ossified from separated centers. However, those two bones are unfused and exhibit complicated morphological variations in basal birds and their dinosaurian relatives. Moreover, the jugal and quadratojugal form rigid articulations with the postorbital and squamosal, respectively, consequently hindering the movement of the upper jaw in most non-avian dinosaurs and some basal birds. A comparative study of the jugal and quadratojugal morphology of basal birds and their close relatives such as dromaeosaurids and oviraptorids elucidates how modern birds has achieved its derived jugal bar morphology, and sheds light on the evolution of the postorbital configuration of birds. We propose that numerous morphological modifications of those two elements (morphology changes and reduced articulation with other elements) took place in early bird history, and some of them pertinent to the refinement of the cranial kinesis. Anat Rec, 300:62-75, 2017. © 2016 Wiley Periodicals, Inc.

  4. Structure and Conductivity of Semiconducting Polymer Hydrogels

    SciTech Connect

    Huber, Rachel C.; Ferreira, Amy S.; Aguirre, Jordan C.; Kilbride, Daniel; Toso, Daniel B.; Mayoral, Kenny; Zhou, Z. Hong; Kopidakis, Nikos; Rubin, Yves; Schwartz, Benjamin J.; Mason, Thomas G.; Tolbert, Sarah H.

    2016-07-07

    Poly(fluorene-alt-thiophene) (PFT) is a conjugated polyelectrolyte that self-assembles into rod-like micelles in water, with the conjugated polymer backbone running along the length of the micelle. At modest concentrations (-10 mg/mL in aqueous solutions), PFT forms hydrogels, and this work focuses on understanding the structure and intermolecular interactions in those gel networks. The network structure can be directly visualized using cryo electron microscopy. Oscillatory rheology studies further tell us about connectivity within the gel network, and the data are consistent with a picture where polymer chains bridge between micelles to hold the network together. Addition of tetrahydrofuran (THF) to the gels breaks those connections, but once the THF is removed, the gel becomes stronger than it was before, presumably due to the creation of a more interconnected nanoscale architecture. Small polymer oligomers can also passivate the bridging polymer chains, breaking connections between micelles and dramatically weakening the hydrogel network. Fits to solution-phase small-angle X-ray scattering data using a Dammin bead model support the hypothesis of a bridging connection between PFT micelles, even in dilute aqueous solutions. Finally, time-resolved microwave conductivity measurements on dried samples show an increase in carrier mobility after THF annealing of the PFT gel, likely due to increased connectivity within the polymer network.

  5. A universal route for the simultaneous extraction and functionalization of cellulose nanocrystals from industrial and agricultural celluloses

    NASA Astrophysics Data System (ADS)

    Chen, Guo-Yin; Yu, Hou-Yong; Zhang, Cai-Hong; Zhou, Ying; Yao, Ju-Ming

    2016-02-01

    A simple route was designed to extract the cellulose nanocrystals (CNCs) with formate groups from industrial and agricultural celluloses like microcrystalline cellulose (MCC), viscose fiber, ginger fiber, and bamboo fiber. The effect of reaction time on the microstructure and properties of the CNCs was investigated in detail, while microstructure and properties of different CNCs were compared. The rod-like CNCs (MCC) with hundreds of nanometers in length and about 10 nm in width, nanofibrillated CNCs (ginger fiber bamboo fiber) with average width of 30 nm and the length of 1 μm, and spherical CNCs (viscose fiber) with the width of 56 nm were obtained by one-step HCOOH/HCl hydrolysis. The CNCs with improved thermal stability showed the maximum degradation temperature ( T max) of 368.9-388.2 °C due to the introduction of formate groups (reducibility) and the increased crystallinity. Such CNCs may be used as an effective template for the synthesis of nanohybrids or reinforcing material for high-performance nanocomposites.

  6. Ultrastructural study on dynamics of lipid bodies and plastids during ripening of chili pepper fruits.

    PubMed

    Liu, Lin

    2013-03-01

    Dynamics of lipid bodies and plastids in chili pepper fruits during ripening were investigated by means of transmission electron microscopy. Mesocarp of chili pepper fruits consists of collenchyma, normal parenchyma, and huge celled parenchyma. In mature green fruits, plastids contain numerous thylakoids that are well organized into grana in collenchyma, a strikingly huge amount of starch and irregularly organized thylakoids in normal parenchyma, and simple tubes rather than thylakoids in huge celled parenchyma. These morphological features suggest that plastids are chloroplasts in collenchyma, chloroamyloplasts in normal parenchyma, proplastids in huge celled parenchyma. As fruits ripen to red, plastids in all cell types convert to chromoplasts and, concomitantly, lipid bodies accumulate in both cytoplasm and chromoplasts. Cytosolic lipid bodies are lined up in a regular layer adjacent to plasma membrane. The cytosolic lipid body consists of a core surrounded by a membrane. The core is comprised of a more electron-dense central part enclosed by a slightly less electron-dense peripheral layer. Plastidial lipid bodies in collenchyma, normal parenchyma, and endodermis initiate as plastoglobuli, which in turn convert to rod-like structures. Therefore, plastidial lipid bodies are more dynamic than cytosolic lipid bodies. Both cytosolic and plastidial lipid bodies contain rich unsaturated lipids.

  7. Characterization of STIP, a multi-domain nuclear protein, highly conserved in metazoans, and essential for embryogenesis in Caenorhabditis elegans

    SciTech Connect

    Ji Qiongmei; Huang, C.-H. . E-mail: chuang@nybloodcenter.org; Peng Jianbin; Hashmi, Sarwar; Ye Tianzhang; Chen Ying

    2007-04-15

    We report here the identification and characterization of STIP, a multi-domain nuclear protein that contains a G-patch, a coiled-coil, and several short tryptophan-tryptophan repeats highly conserved in metazoan species. To analyze their functional role in vivo, we cloned nematode stip-1 genes and determined the spatiotemporal pattern of Caenorhabditis elegans STIP-1 protein. RNA analyses and Western blots revealed that stip-1 mRNA was produced via trans-splicing and translated as a 95-kDa protein. Using reporter constructs, we found STIP-1 to be expressed at all developmental stages and in many tissue/cell types including worm oocyte nuclei. We found that STIP-1 is targeted to the nucleus and forms large polymers with a rod-like shape when expressed in mammalian cells. Using deletion mutants, we mapped the regions of STIP-1 involved in nuclear import and polymer assembly. We further showed that knockdown of C. elegans stip-1 by RNA interference arrested development and resulted in morphologic abnormalities around the 16-cell stage followed by 100% lethality, suggesting its essential role in worm embryogenesis. Importantly, the embryonic lethal phenotype could be faithfully rescued with Drosophila and human genes via transgenic expression. Our data provide the first direct evidence that STIP have a conserved essential nuclear function across metazoans from worms to humans.

  8. Nematic phase formation in suspensions of carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Zakri, Cecile; Poulin, Philippe

    This chapter describes the chemical composition, phase behavior and structure of recently investigated carbon nanotube (CNT) based liquid crystals. Because nanotubes are long and thin rigid cylinders, their phase behavior shares several similarities with many other systems such as rigid polymers and rod-like particle suspensions. CNT liquid crystals are achieved in highly concentrated suspensions comprised of raw or chemically functionalized particles. But extreme aspect ratio, rigidity, high sensitivity to interactions, optical properties and structural features of CNTs make their liquid crystalline phases unique in several ways. In particular, the chapter discusses the importance of the CNT waviness on the phase ordering and the role of excess surfactant or biomolecules used to stabilize the CNTs. The unique resonant Raman scattering of CNT allows original and accurate measurements of order parameters at a micron-scale. Highly oriented nematic tactoids could even be characterized by polarized Raman microscopy. From a more applied point of view, nematic ordering is shown to be a route towards the processing of new materials such as anisotropic conductive films and high strength fibers made of oriented carbon nanotubes. Examples of functional materials and nanocomposites achieved from CNT liquid crystals are given.

  9. Nanostructural evolution of one-dimensional BaTiO₃ structures by hydrothermal conversion of vertically aligned TiO₂ nanotubes.

    PubMed

    Muñoz-Tabares, J A; Bejtka, K; Lamberti, A; Garino, N; Bianco, S; Quaglio, M; Pirri, C F; Chiodoni, A

    2016-03-28

    The use of TiO2 nanotube (NT) arrays as templates for hydrothermal conversion of one-dimensional barium titanate (BaTiO3) structures is considered a promising synthesis approach, even though the formation mechanisms are not yet fully understood. Herein we report a nanostructural study by means of XRD and (HR)TEM of high aspect ratio TiO2-NTs hydrothermally converted into BaTiO3. The nanostructure shows two different and well-defined regions: at the top the conversion involves complete dissolution of NTs and subsequent precipitation of BaTiO3 crystals by homogeneous nucleation, followed by the growth of dendritic structures by aggregation and oriented attachment mechanisms. Instead, at the bottom, the low liquid/solid ratio, due to the limited amount of Ba solution that infiltrates the NTs, leads to the rapid crystallization of such a solution into BaTiO3, thus allowing the NTs to act as a template for the formation of highly oriented one-dimensional nanostructures. The in-depth analysis of the structural transformations that take place during the formation of the rod-like arrays of BaTiO3 could help elucidate the conversion mechanism, thus paving the way for the optimization of the synthesis process in view of new applications in energy harvesting devices, where easy and low temperature processing, controlled composition, morphology and functional properties are required.

  10. Random Packings Of Rod-Sphere Mixtures Simulated By Mechanical Contraction

    NASA Astrophysics Data System (ADS)

    Kyrylyuk, Andriy V.; Wouterse, Alan; Philipse, Albert P.

    2009-06-01

    We study the random close packing of a binary mixture of spheres and rod-like particles (spherocylinders) by the mechanical contraction computer simulation. We investigate the universality in packing of near-spheres by monitoring the position and the value of the maximum in the mixture packing density as a function of the mixture composition and the rod aspect ratio. We find that independently of the mixture composition the particles pack more efficiently/densely as the rod aspect ratio is perturbed slightly from zero and the maximum density is always reached at one unique rod aspect ratio of about 0.45. The dependence of the value of the maximum packing fraction on the mixture composition (the relative rod volume fraction) is linear, exhibiting some ideality in packing of near-spheres. This counter-intuitive finding suggests that even for high rod concentrations in a rod-sphere mixture the packing is governed by local contacts between the neighboring particles, which is usually observed for dilute colloidal suspensions and granular gases, where there is no correlation between the particles. The plausible explanation for this intriguing behavior is that the correlations between the particles are completely lost in the range of distances of several particle diameters, which can be originated from the decoupling of the orientational and translational degrees of freedom of the nearly spherical rods. This gives rise to the universality and locality of random close packing of the rod-sphere mixtures.

  11. Dynamics of Snake-like Swarming Behavior of Vibrio alginolyticus

    PubMed Central

    Böttcher, Thomas; Elliott, Hunter L.; Clardy, Jon

    2016-01-01

    Swarming represents a special case of bacterial behavior where motile bacteria migrate rapidly and collectively on surfaces. Swarming and swimming motility of bacteria has been studied well for rigid, self-propelled rods. In this study we report a strain of Vibrio alginolyticus, a species that exhibits similar collective motility but a fundamentally different cell morphology with highly flexible snake-like swarming cells. Investigating swarming dynamics requires high-resolution imaging of single cells with coverage over a large area: thousands of square microns. Researchers previously have employed various methods of motion analysis but largely for rod-like bacteria. We employ temporal variance analysis of a short time-lapse microscopic image series to capture the motion dynamics of swarming Vibrio alginolyticus at cellular resolution over hundreds of microns. Temporal variance is a simple and broadly applicable method for analyzing bacterial swarming behavior in two and three dimensions with both high-resolution and wide-spatial coverage. This study provides detailed insights into the swarming architecture and dynamics of Vibrio alginolyticus isolate B522 on carrageenan agar that may lay the foundation for swarming studies of snake-like, nonrod-shaped motile cell types. PMID:26910435

  12. Sorption of selenium(IV) and selenium(VI) onto synthetic pyrite (FeS2): spectroscopic and microscopic analyses.

    PubMed

    Han, Dong Suk; Batchelor, Bill; Abdel-Wahab, Ahmed

    2012-02-15

    Pyrite was hydrothermally synthesized and used to remove Se(IV) and Se(VI) selectively from solution. Surface analyses of pyrite before and after contact with Se(IV) and Se(VI) were conducted using X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and atomic force microscopy (AFM). All solid samples were acquired by allowing 3.1 mmol/L of Se(IV) or Se(VI) to react with 1 g/L of pyrite for 1, 15, or 30 days. The XPS spectra were fitted using the XPSPEAK program that applies a Gaussian Lorentzian function. The fitted spectra indicate that Se(IV) more strongly reacts with the surface-bound S than with the surface-bound Fe of pyrite. However, there is no apparent evidence of surface reaction with Se(VI). Specifically, fitted XPS spectra showed the presence of sulfide and tetrathionate on the surface, indicating that sulfur (S(2)(2-)) at the surface of pyrite can be both oxidized and reduced after contact with Se(IV). This occurs via surface disproportionation, possibly resulting in the formation of surface precipitates. Evidence for the formation of precipitates was seen in SEM and AFM images that showed rod-like particles and a phase image with higher voltage. In contrast, there were no important changes in the pyrite after contact with Se(VI) over a period of 30 days.

  13. Synthesis-Dependent Surface Defects and Morphology of Hematite Nanoparticles and Their Effect on Cytotoxicity in Vitro.

    PubMed

    Cardillo, Dean; Tehei, Moeava; Hossain, Md Shahriar; Islam, Md Monirul; Bogusz, Kathrin; Shi, Dongqi; Mitchell, David; Lerch, Michael; Rosenfeld, Anatoly; Corde, Stéphanie; Konstantinov, Konstantin

    2016-03-09

    In this study, we investigate the toxicity of hematite (α-Fe2O3) nanoparticles on the Madin-Darby Canine Kidney (MDCK) cell line. The oxide particles have been synthesized through two different methods and annealing conditions. These two methods, spray precipitation and precipitation, resulted in particles with rod-like and spherical morphology and feature different particle sizes, surface features, and magnetic properties. Through flow cytometry it was found that particle morphology heavily influences the degree to which the nanomaterials are internalized into the cells. It was also found that the ability of the nanoparticles to generate free radicals species is hindered by the formation of tetrahedrally coordinated maghemite-like (γ-Fe2O3) spinel defects on the surfaces of the particles. The combination of these two factors resulted in variable cytotoxic effects of the hematite nanoparticles synthesized with different conditions. This article highlights the importance on the fabrication method, materials properties, and surface characteristics on the cytotoxicity of hematite nanomaterials.

  14. Hierarchically constructed NiCo2S4@Ni(1-x)Co x (OH)2 core/shell nanoarrays and their application in energy storage

    NASA Astrophysics Data System (ADS)

    Zhou, Weiwei; Yu, Kun; Wang, Dong; Chu, Jing; Li, Jieying; Zhao, Limin; Ding, Chunyan; Du, Yu; Jia, Xingtao; Wang, Huatao; Wen, Guangwu

    2016-06-01

    We report a new type of core-shell heterostructure consisting of a rod-like NiCo2S4 (NCS) core and an urchin-like Ni(1-x)Co x (OH)2 (NCOH) shell via a simple hydrothermal route coupled with a facile electrodeposition. NCS nanorod arrays (NRAs) can not only act as excellent electrochemically active materials by themselves, but they can also serve as hierarchical porous scaffolds capable of fast electron conduction and ion diffusion for loading a large amount of additional active materials. Moreover, it is observed that the urchin-like NCOH nanosheets coating could bind the inner NCS nanorods together and thereby reinforce the whole structure mechanically. Meanwhile, more effective pathways for electrons are available in the NCS@NCOH hybrids than an individual NCS nanorod. Benefiting from both structural and compositional features, the NCS@NCOH electrode exhibits greatly improved electrochemical performance with high capacity (3.54 C cm-2 at 1 mA cm-2) and excellent cycling stability (78% capacity retention after 4000 cycles). Moreover, a battery-type device is also fabricated by using NCS@NCOH as a positive electrode and activated carbon (AC) as a negative electrode, displaying high capacity (2.51 C cm-2 at 2 mA cm-2) and good durability (88.8% capacity retention after 4000 cycles) as well.

  15. Realization of highly crystallographic three-dimensional nanosheets by a stress-induced oriented-diffusion method

    SciTech Connect

    Gharooni, M.; Hosseini, M.; Mohajerzadeh, S. Taghinejad, M.; Taghinejad, H.; Abdi, Y.

    2014-07-28

    Morphologically controlled nanostructures have been increasingly important because of their strongly shape dependent physical and chemical properties. Formation of nanoscale silicon based structures that employ high levels of strain, intentional, and unintentional twins or grain boundaries can be dramatically different from the commonly conceived bulk processes. We report, realization of highly crystallographic 3D nanosheets with unique morphology and ultra-thin thickness by a stress-induced oriented-diffusion method, based on plasma processing of metal layer deposited on Si substrate and its post deep reactive ion etching. Annealing in plasma ambient creates rod-like metal alloy precursors which induce stress at its interface with Si substrate due to the mismatch of lattice constants. This stress opens facilitated gateways for orientated-diffusion of metal atoms in 〈110〉 directions and leads to formation of NSs (nanosheets) with [111] crystalline essence. Nanosheets are mainly triangular, hexagonal, or pseudo hexagonal in shape and their thicknesses are well controlled from several to tens of nanometers. The structural and morphological evolution of features were investigated in detail using transmission electron microscope, atomic force microscope, scanning electron microscope and possible mechanism is proposed to explain the formation of the thermodynamically unfavorable morphology of nanosheets. Significant photoemission capability of NSs was also demonstrated by photoluminescence spectroscopy.

  16. Microstructural formation in a hypereutectic Mg-Si alloy

    SciTech Connect

    Pan Yichuan . E-mail: riverpan@mail.sdu.edu.cn; Liu Xiangfa; Yang Hua

    2005-09-15

    In the present work, the microstructure of an ingot metallurgy hypereutectic Mg-8 wt.% Si alloy was studied using electron probe microanalysis (EPMA) and the solidification process was discussed. The components of the alloy are Mg{sub 2}Si and Mg. The solidified microstructure of the alloy contains three constituents: Mg{sub 2}Si primary dendrites that are surrounded by Mg sub-primary particles and the Mg-Mg{sub 2}Si eutectic. The primary Mg{sub 2}Si dendrites have a secondary dendrite arm spacing d {sub 2} of approximately 17 {mu}m or show polygonal morphologies with a mean size of 30 {mu}m. An Mg phase appearing as halos surround the Mg{sub 2}Si constituents. The Mg-Mg{sub 2}Si eutectic has a regular morphology of rod-like Mg{sub 2}Si distributed in a continuous matrix of Mg having an interphase spacing r of approximately 0.8 {mu}m.

  17. Cladodes, leaf-like organs in Asparagus, show the significance of co-option of pre-existing genetic regulatory circuit for morphological diversity of plants.

    PubMed

    Nakayama, Hokuto; Yamaguchi, Takahiro; Tsukaya, Hirokazu

    2012-08-01

    Plants in the genus Asparagus have determinate leaf-like organs called cladodes in the position of leaf axils. Because of their leaf-like morphology, axillary position, and morphological variation, it has been unclear how this unusual organ has evolved and diversified. In the previous study, we have shown that cladodes in the genus Asparagus are modified axillary shoots and proposed a model that cladodes have arisen by co-option and deployment of genetic regulatory circuit (GRC) involved in leaf development. Moreover, we proposed that the alteration of the expression pattern of genes involved in establishment of adaxial/abaxial polarity has led to the morphological diversification from leaf-like to rod-like form of cladodes in the genus. Thus, these results indicated that the co-option and alteration of pre-existing GRC play an important role in acquisition and subsequent morphological diversification. Here, we present data of further expression analysis of A. asparagoides. The results suggested that only a part of the GRC involved in leaf development appears to have been co-opted into cladode development. Based on our study and several examples of the morphological diversification, we briefly discuss the importance of co-option of pre-existing GRC and its genetic modularity in the morphological diversity of plants during evolution.

  18. First experimental determination of permanent and induced electric dipolar moments of colloidal cellulose nanocrystals dispersed in apolar solvents

    NASA Astrophysics Data System (ADS)

    Frka-Petesic, Bruno; Jean, Bruno; Heux, Laurent

    2012-02-01

    Scientists and industrialists show a growing interest for cellulose nanocrystals (CNCs) since these rod-like nanoparticles display excellent mechanical properties that make them perfect candidates for the design of high performance biobased composites. Furthermore, CNCs can be obtained as colloidal suspensions in apolar solvents that form chiral nematic (cholesteric) liquid crystals. Our aim is to obtain homogeneous unidimensionnal structures to enhance the optical and/or mechanical properties of CNCs-based architectures at a macroscopic scale. Using electric fields, CNCs suspensions from either cotton or tunicate were succesfully oriented in the direction of an electric field, in both AC and DC configurations. To probe the electric field induced orientation of the CNCs, a birefringence experimental set-up has been developped. While applying short electric DC field pulses, static and transient birefringence has been measured in diluted isotropic suspensions. From these measurements, we determined both the permanent and induced electric dipolar moments of the CNCs, whose effects appeared to be of the same order of magnitude. The results are discussed regarding to the CNC type and the apolar solvent used.

  19. Photoluminescence and doping mechanism of theranostic Eu3+/Fe3+ dual-doped hydroxyapatite nanoparticles

    PubMed Central

    Chen, Min-Hua; Yoshioka, Tomohiko; Ikoma, Toshiyuki; Hanagata, Nobutaka; Lin, Feng-Huei; Tanaka, Junzo

    2014-01-01

    Theranostic nanoparticles currently have been regarded as an emerging concept of ‘personalized medicine’ with diagnostic and therapeutic dual-functions. Eu3+ doped hydroxyapatite (HAp) has been regarded as a promising fluorescent probe for in vivo imaging applications. Additionally, substitution of Ca2+ with Fe3+ in HAp crystal may endow the capability of producing heat upon exposure to a magnetic field. Here we report a preliminary study of doping mechanism and photoluminescence of Eu3+ and Fe3+ doped HAp nanoparticles (Eu/Fe:HAp). HAp with varied concentration of Eu3+ and Fe3+ doping are presented as Eu(10 mol%):HAp, Eu(7 mol%)-Fe(3 mol%):HAp, Eu(5 mol%)-Fe(5 mol%):HAp, Eu(3 mol%)-Fe(7 mol%):HAp, and Fe(10 mol%):HAp in the study. The results showed that the HAp particles, in nano-size with rod-like morphology, were successfully doped with Eu3+ and Fe3+, and the particles can be well suspended in cell culture medium. Photoluminescence analysis revealed that particles have prominent emissions at 536 nm, 590 nm, 615 nm, 650 nm and 695 nm upon excitation at a wavelength of 397 nm. Moreover, these Eu/Fe:HAp nanoparticles belonged to B-type carbonated HAp, which has been considered an effective biodegradable and biocompatible drug/gene carrier in biological applications. PMID:27877717

  20. Characteristics of ZnO thin films doped by various elements

    NASA Astrophysics Data System (ADS)

    Kahraman, S.; Çakmak, H. M.; Çetinkaya, S.; Bayansal, F.; Çetinkara, H. A.; Güder, H. S.

    2013-01-01

    We have investigated the effects of Al, K and Co dopant elements on the properties of ZnO thin films deposited by CBD method on glass substrates. Changing in morphology, structural parameters, ionization energies of impurity levels, absorption behavior and optical band gap values were investigated through scanning electron microscopy (SEM), X-Ray diffraction (XRD), resistance-temperature measurement (R-T) and ultraviolet-visible spectroscopy (UV-vis) techniques. From the SEM observations, various morphologies (rod-like, flower-like and rice-like) were observed. Those morphological variations were attributed to the change in stable growth mechanism of intrinsic ZnO, induced by different atomic radius and different electronegativity of dopants. XRD results indicated that all orientations are well indexed to hexagonal phase crystalline ZnO. The impurity level ionization energy values (ΔE) were estimated as 0.32/0.13/0.07 eV; 0.34/0.15 eV; 0.40/0.13 eV and 0.48/0.22 eV for the Al, K, Co doped samples and i-ZnO, respectively. Optical band gap values were found that the doped samples' were higher than the intrinsic one's. This increasing (blue shift) was attributed to a deterioration which occurred in the lattice of the structures after doping. This effect was also supported by the structural results.

  1. Hierarchical viscosity of aqueous solution of tilapia scale collagen investigated via dielectric spectroscopy between 500 MHz and 2.5 THz

    PubMed Central

    Kawamata, H.; Kuwaki, S.; Mishina, T.; Ikoma, T.; Tanaka, J.; Nozaki, R.

    2017-01-01

    Aqueous solutions of biomolecules such as proteins are very important model systems for understanding the functions of biomolecules in actual life processes because interactions between biomolecules and the surrounding water molecules are considered to be important determinants of biomolecules’ functions. Globule proteins have been extensively studied via dielectric spectroscopy; the results indicate three relaxation processes originating from fluctuations in the protein molecule, the bound water and the bulk water. However, the characteristics of aqueous solutions of collagens have rarely been investigated. In this work, based on broadband dielectric measurements between 500 MHz and 2.5 THz, we demonstrate that the high viscosity of a collagen aqueous solution is due to the network structure being constructed of rod-like collagen molecules surrounding free water molecules and that the water molecules are not responsible for the viscosity. We determine that the macroscopic viscosity is related to the mean lifetime of the collagen-collagen interactions supporting the networks and that the local viscosity of the water surrounded by the networks is governed by the viscosity of free water as in the bulk. This hierarchical structure in the dynamics of the aqueous solution of biomolecules has been revealed for the first time. PMID:28345664

  2. A Green Strategy to Prepare Metal Oxide Superstructure from Metal-Organic Frameworks

    PubMed Central

    Song, Yonghai; Li, Xia; Wei, Changting; Fu, Jinying; Xu, Fugang; Tan, Hongliang; Tang, Juan; Wang, Li

    2015-01-01

    Metal or metal oxides with diverse superstructures have become one of the most promising functional materials in sensor, catalysis, energy conversion, etc. In this work, a novel metal-organic frameworks (MOFs)-directed method to prepare metal or metal oxide superstructure was proposed. In this strategy, nodes (metal ions) in MOFs as precursors to form ordered building blocks which are spatially separated by organic linkers were transformed into metal oxide micro/nanostructure by a green method. Two kinds of Cu-MOFs which could reciprocally transform by changing solvent were prepared as a model to test the method. Two kinds of novel CuO with three-dimensional (3D) urchin-like and 3D rods-like superstructures composed of nanoparticles, nanowires and nanosheets were both obtained by immersing the corresponding Cu-MOFs into a NaOH solution. Based on the as-formed CuO superstructures, a novel and sensitive nonenzymatic glucose sensor was developed. The small size, hierarchical superstructures and large surface area of the resulted CuO superstructures eventually contribute to good electrocatalytic activity of the prepared sensor towards the oxidation of glucose. The proposed method of hierarchical superstructures preparation is simple, efficient, cheap and easy to mass production, which is obviously superior to pyrolysis. It might open up a new way for hierarchical superstructures preparation. PMID:25669731

  3. A new model of phycobilisome in Spirulina platensis.

    PubMed

    Zhang, Y; Chen, X; Zhou, B; Zeng, C; Liu, J; Shi, D; Pang, S

    1999-02-01

    Phycobilisomes (PBS) were isolated from blue-green alga Spirulina platensis. Scanning tunneling microscope was used to investigate the three-dimensional structure of PBS deposited on freshly cleaved highly oriented pyrolytic graphite (HOPG) in ambient condition at room temperature. The results showed that the rods of PBS radiated from the core to different directions in the space other than arrayed in one plane, which was different from the typical hemi-discoidal model structure. The diameter of PBS was up to 70 nm, and the rod was approximately 50 nm in length. Similar results were observed in Langmuir-Blodgett (LB) film of PBS. The dissociated PBS could reaggregate into rod-like structures and easily form two-dimensional membrane while being absorbed on HOPG, however, no intact PBS was observed. The filling-space model structure of PBS in Spirulina platensis with STM from three-dimensional real space at nanometer scale was found, which showed that this new structural model of PBS surely exists in blue-green algae and red algae. The function of this structural model of PBS was also discussed.

  4. Solvent-controlled preparation and photocatalytic properties of nanostructured TiO{sub 2} thin films with different morphologies

    SciTech Connect

    Ao, Yanhui Gao, Yinyin; Wang, Peifang; Wang, Chao; Hou, Jun; Qian, Jin

    2014-01-01

    Graphical abstract: Low-temperature growth of nanostructured TiO{sub 2} thin films was presented by a solvent-controlled method. Nanoparticle structured films in anatase phase have been successfully fabricated with some adjustment. The effects of the solvent were investigated and the formation mechanism was proposed. - Highlights: • Nanostructured TiO{sub 2} thin films with different morphologies were obtained at low temperature. • The effects of the solvent on the morphologies of the products were investigated. • The effects of the solvent on the phtocatalytic activity were investigated. - Abstract: A low-temperature growth method of nanostructured TiO{sub 2} thin films with different morphologies was reported. Rod-like, grass-like and nanosheet structured films have been successfully fabricated just by adjusting the ratio of different solvents. The effects of the solvent on the morphologies of the TiO{sub 2} nanostructures were investigated. The formation mechanism of different morphologies was proposed based on the experiment results. The as-prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM). The photocatalytic activity of as-prepared samples for the degradation of methylene blue (MB) in water was evaluated under UV illumination. Results showed that the solvents exhibited important effect on the morphologies and photocatalytic activity of as-prepared nanostructured titania films.

  5. Structural Lability of Barley Stripe Mosaic Virus Virions

    PubMed Central

    Semenyuk, Pavel I.; Abashkin, Dmitry A.; Kalinina, Natalya O.; Arutyunyan, Alexsandr M.; Solovyev, Andrey G.; Dobrov, Eugeny N.

    2013-01-01

    Virions of Barley stripe mosaic virus (BSMV) were neglected for more than thirty years after their basic properties were determined. In this paper, the physicochemical characteristics of BSMV virions and virion-derived viral capsid protein (CP) were analyzed, namely, the absorption and intrinsic fluorescence spectra, circular dichroism spectra, differential scanning calorimetry curves, and size distributions by dynamic laser light scattering. The structural properties of BSMV virions proved to be intermediate between those of Tobacco mosaic virus (TMV), a well-characterized virus with rigid rod-shaped virions, and flexuous filamentous plant viruses. The BSMV virions were found to be considerably more labile than expected from their rod-like morphology and a distant sequence relation of the BSMV and TMV CPs. The circular dichroism spectra of BSMV CP subunits incorporated into the virions, but not subunits of free CP, demonstrated a significant proportion of beta-structure elements, which were proposed to be localized mostly in the protein regions exposed on the virion outer surface. These beta-structure elements likely formed during virion assembly can comprise the N- and C-terminal protein regions unstructured in the non-virion CP and can mediate inter-subunit interactions. Based on computer-assisted structure modeling, a model for BSMV CP subunit structural fold compliant with the available experimental data was proposed. PMID:23613760

  6. New information on the Wukongopteridae (Pterosauria) revealed by a new specimen from the Jurassic of China.

    PubMed

    Cheng, Xin; Jiang, Shunxing; Wang, Xiaolin; Kellner, Alexander W A

    2016-01-01

    The Wukongopteridae is an important pterosaur group discovered from Yanliao Biota, because it combines character states seen in non-pterodactyloid and pterodactyloid pterosaurs. So far, the Wukongopteridae contains three genera: Wukongopterus, Darwinopterus and Kunpengopterus; representing five species. Here we report on a new specimen, IVPP V 17959, that can be undoubtedly referred to the Wukongopteridae based on the presence of a confluent nasoantorbital fenestra, elongated cervical vertebrae (convergent with Pterodactyloidea) and a long tail enclosed by rod-like bony extensions of the zygapophyses. Traits distinguishing this new specimen from other wukongopterid pterosaurs include a premaxilla with a low ossified anterodorsal crest, a nasal bearing the most elongated process known in the Wukongopteridae, and a lacrimal that has a foramen in its middle portion. The new kind of premaxillary crest preserved in IVPP V 17959 suggests that the presence or absence of a premaxillary crest might be an interspecific feature within the Wukongopteridae. A phylogenetic analysis including all wukongopterid pterosaurs recovers IVPP V 17959 in a polytomy with Wukongopterus and the species of Darwinopterus, having Kunpengopterus in a more basal position. The postcranial skeleton of IVPP V 17959 has ontogenetically mature characteristics including a completely fused scapula and coracoid, fused proximal and distal carpal series, and an ossified extensor tendon process of the first wing phalanx, allowing its classification as ontogenetic stage five. Furthermore, the atlas and axis are separated in IVPP V 17959, which indicates that these two bones probably are not fused in skeletally mature wukongopterid individuals.

  7. Determination of the pheromone-producing region that has epoxidation activity in the abdominal tip of the Japanese giant looper, Ascotis selenaria cretacea (Lepidoptera: Geometridae).

    PubMed

    Fujii, Takeshi; Suzuki, Masataka G; Kawai, Takeshi; Tsuneizumi, Kazuhide; Ohnishi, Atsushi; Kurihara, Masaaki; Matsumoto, Shogo; Ando, Tetsu

    2007-04-01

    The epoxydienyl sex pheromone of Ascotis selenaria cretacea can be detected only within a rod-like abdominal tip (RAT) of the female. To clarify which part of the RAT is the sex pheromone-producing region, the RAT was morphologically divided into three sections, defined positionally from the abdomen as sections A, B, and C. GC-MS measurements clearly showed that the sex pheromone compound levels in section B were four times greater than those of the other sections. Microscopic dissection analysis revealed that section B consists of four tissues: rectum, oviduct, musculature, and intersegmental membrane. GC-MS analysis of the individual tissues revealed that approximately 90% of the sex pheromone in section B is localized in the intersegmental membrane. A cell layer was found in the intersegmental membrane after staining with propidium iodide. Furthermore, incubation of tissues dissected from section B with a deuterated trienyl pheromone precursor revealed that the labeled epoxy pheromonal component was detected exclusively in the intersegmental membrane. We have determined that the sex pheromone-producing region of A. s. cretacea is on the terminal side of the intersegmental membrane located between the 8th and 9th abdominal segments.

  8. Extensional Rheology of Granular Staples

    NASA Astrophysics Data System (ADS)

    Franklin, Scott

    2013-03-01

    Collections of U-shaped granular materials (e.g. staples) show a surprising resistance to being pulled apart. We conduct extensional stress-strain experiments on staple piles with vary arm/spine (barb) ratio. The elongation is not smooth, with the pile growing in bursts, reminiscent of intruder motion through ordinary and rod-like granular materials. The force-distance curve shows a power-law scaling, consistent with previous intruder experiments. Surprisingly, there is significant plastic creep of the pile as particles rearrange slightly in response to the increasing force. There is a broad distribution of yield forces that does not seem to evolve as the pile lengthens, suggesting that each yield event is independent of the pile's history. The distribution of yield forces can be interpreted in the context of a Weibullian weakest-link theory that predicts the maximum pile strength to decrease sharply with increasing pile length. From this interpretation arise length and force scales that may be used to characterize the sample. This research supported in part by the NSF (CBET-#1133722) and ACS-PRF (#51438-UR10).

  9. Preparation of stripe-patterned heterogeneous hydrogel sheets using microfluidic devices for high-density coculture of hepatocytes and fibroblasts.

    PubMed

    Kobayashi, Aoi; Yamakoshi, Kenta; Yajima, Yuya; Utoh, Rie; Yamada, Masumi; Seki, Minoru

    2013-12-01

    Here we demonstrate the production of stripe-patterned heterogeneous hydrogel sheets for the high-density 3D coculture of multiple cell types, by using microchannel-combined micronozzle devices. The prepared hydrogel sheet, composed of multiple regions with varying physical stiffness, regulates the direction of proliferation of encapsulated cells and enables the formation of arrays of rod-like heterotypic organoids inside the hydrogel matrix. We successfully prepared stripe-patterned hydrogel sheets with a uniform thickness of ~100 μm and a width of several millimeters. Hepatoma cells (HepG2) and fibroblasts (Swiss 3T3) were embedded inside the hydrogel matrix and cocultured, to form heterotypic micro-organoids mimicking in vivo hepatic cord structures. The upregulation of hepatic functions by the 3D coculture was confirmed by analyzing liver-specific functions. The presented heterogeneous hydrogel sheet could be useful, as it provides relatively large, but precisely-controlled, 3-dimensional microenvironments for the high-density coculture of multiple types of cells.

  10. Surface roughness stabilizes the clustering of self-propelled triangles

    NASA Astrophysics Data System (ADS)

    Ilse, Sven Erik; Holm, Christian; de Graaf, Joost

    2016-10-01

    Self-propelled particles can spontaneously form dense phases from a dilute suspension in a process referred to as motility-induced phase separation. The properties of the out-of-equilibrium structures that are formed are governed by the specifics of the particle interactions and the strength of the activity. Thus far, most studies into the formation of these structures have focused on spherical colloids, dumbbells, and rod-like particles endowed with various interaction potentials. Only a few studies have examined the collective behavior of more complex particle shapes. Here, we increase the geometric complexity and use molecular dynamics simulations to consider the structures formed by triangular self-propelled particles with surface roughness. These triangles either move towards their apex or towards their base, i.e., they possess a polarity. We find that apex-directed triangles cluster more readily, more stably, and have a smoother cluster interface than their base-directed counterparts. A difference between the two polarities is in line with the results of Wensink et al. [Phys. Rev. E 89, 010302 (2014)]; however, we obtain the reversed result when it comes to clustering, namely, that apex-directed triangles cluster more successfully. We further show that reducing the surface roughness negatively impacts the stability of the base-directed structures, suggesting that their formation is in large part due to surface roughness. Our results lay a solid foundation for future experimental and computational studies into the effect of roughness on the collective dynamics of swimmers.

  11. Biochemical and functional properties of wheat gliadins: a review.

    PubMed

    Barak, Sheweta; Mudgil, Deepak; Khatkar, B S

    2015-01-01

    Gliadins account for 40-50% of the total storage proteins of wheat and are classified into four subcategories, α-, β-, γ-, and ω-gliadins. They have also been classified as ω5-, ω1, 2-, α/β-, and γ-gliadins on the basis of their primary structure and molecular weight. Cysteine residues of gliadins mainly form intramolecular disulfide bonds, although α-gliadins with odd numbers of cysteine residues have also been reported. Gliadins are generally regarded to possess globular protein structure, though recent studies report that the α/β-gliadins have compact globular structures and γ- and ω-gliadins have extended rod-like structures. Newer techniques such as Mass Spectrometry with the development of matrix-assisted laser desorption/ionization (MALDI) in combination with time-of-flight mass spectrometry (TOFMS) have been employed to determine the molecular weight of purified ω- gliadins and to carry out the direct analysis of bread and durum wheat gliadins. Few gliadin alleles and components, such as Gli-B1b, Gli-B2c and Gli-A2b in bread wheat cultivars, γ-45 in pasta, γ-gliadins in cookies, lower gliadin content for chapatti and alteration in Gli 2 loci in tortillas have been reported to improve the product quality, respectively. Further studies are needed in order to elucidate the precise role of gliadin subgroups in dough strength and product quality.

  12. Structural insights into the organization of the cavin membrane coat complex.

    PubMed

    Kovtun, Oleksiy; Tillu, Vikas A; Jung, WooRam; Leneva, Natalya; Ariotti, Nicholas; Chaudhary, Natasha; Mandyam, Ramya A; Ferguson, Charles; Morgan, Garry P; Johnston, Wayne A; Harrop, Stephen J; Alexandrov, Kirill; Parton, Robert G; Collins, Brett M

    2014-11-24

    Caveolae are cell-surface membrane invaginations that play critical roles in cellular processes including signaling and membrane homeostasis. The cavin proteins, in cooperation with caveolins, are essential for caveola formation. Here we show that a minimal N-terminal domain of the cavins, termed HR1, is required and sufficient for their homo- and hetero-oligomerization. Crystal structures of the mouse cavin1 and zebrafish cavin4a HR1 domains reveal highly conserved trimeric coiled-coil architectures, with intersubunit interactions that determine the specificity of cavin-cavin interactions. The HR1 domain contains a basic surface patch that interacts with polyphosphoinositides and coordinates with additional membrane-binding sites within the cavin C terminus to facilitate membrane association and remodeling. Electron microscopy of purified cavins reveals the existence of large assemblies, composed of a repeating rod-like structural element, and we propose that these structures polymerize through membrane-coupled interactions to form the unique striations observed on the surface of caveolae in vivo.

  13. Schindleria elongata, a new species of paedomorphic gobioid from the Red Sea (Teleostei: Schindleriidae).

    PubMed

    Fricke, R; Abu El-Regal, M

    2017-02-14

    A new species of paedomorphic gobioid, Schindleria elongata, from the Red Sea, is described on the basis of five specimens. The new species is characterized by its lack of body pigmentation; the body depth at pectoral-fin origin 4-5% of standard length (LS ) and at anal-fin origin 5-7% LS ; the predorsal length 66-70% LS ; pre-anal length 66-71% LS ; dorsal-fin rays 13 or 14; anal-fin rays 10 or 11; first dorsal-fin ray at myomere 20 or 21; first anal-fin ray below second to fourth dorsal-fin rays; myomeres 19 or 20 + 13 or 14 = 33 or 34 total; premaxillae and dentaries with small teeth; gas bladder located posteriorly at 56-60% LS ; males with a rod-like, flexible urogenital papilla lacking lobes, projections or accessory papillae, with distal half tapering to a broad, angular point and usually posteriorly directed. A key to the species of Schindleriidae is presented.

  14. Pseudo-Mannosylated DC-SIGN Ligands as Immunomodulants.

    PubMed

    Berzi, Angela; Ordanini, Stefania; Joosten, Ben; Trabattoni, Daria; Cambi, Alessandra; Bernardi, Anna; Clerici, Mario

    2016-10-13

    DC-SIGN, a C-type lectin mainly expressed by DCs, mediates antigen uptake and can induce specific immune responses, depending on the ligand involved. Owing to these properties, DC-SIGN is an attracting target for approaches aimed at tailoring the immune response towards specific immunologic outcomes. A multivalent DC-SIGN ligand (Polyman26), containing at its core a fluorescent "rod-like" spacer and able to inhibit DC-SIGN mediated HIV infection in nanomolar concentration, has been recently developed by our group. We investigated the internalization pattern and the ability of Polyman26 to elicit innate immune responses. Results obtained by confocal microscopy indicate that Polyman26 is internalized by DCs via receptor- mediated endocytosis and is then routed to endolysosomal compartments, thus being presented together with MHC class II molecules, with important implications for the development of vaccines. Moreover, Polyman26 up-regulated the production of β-chemokines and pro-inflammatory cytokines (including IL-1β, IL-6, IL-12, and TNFα) as well as the expression of TLR9 and CD40L. These results indicate that glycomimetic DC-SIGN ligands should be further investigated and suggest that these compounds could be used to differentially stimulate immune responses.

  15. Effects of h-BN addition on microstructures and mechanical properties of β-CaSiO3 bioceramics.

    PubMed

    Pan, Ying; Yao, Dongxu; Zuo, Kaihui; Xia, Yongfeng; Yin, Jinwei; Liang, Hanqin; Zeng, Yuping

    2016-09-01

    The main purpose of this study consists in investigating the effects of h-BN addition on the sinterability of β-CaSiO3 (β-CS) bioceramics. β-CS bioceramics with different contents of h-BN were prepared at the sintering temperature ranging from 800°C to 1100°C. The results showed that h-BN can be successfully used as sintering additive by being oxidized to form low melting point B2O3 related glassy phase and enhanced the flexural strength by the formation of rod-like β-CS grains. β-CS bioceramics with 1wt% h-BN sintered at 1000°C revealed flexural strength and fracture toughness of 182.2MPa and 2.4MPam(1/2) respectively, which were much higher than that of pure β-CS bioceramics (30.2MPa, 0.53MPam(1/2)) fabricated in the same processing condition.

  16. Environment-oriented low-cost porous mullite ceramic membrane supports fabricated from coal gangue and bauxite.

    PubMed

    Lü, Qikai; Dong, Xinfa; Zhu, Zhiwen; Dong, Yingchao

    2014-05-30

    Porous mullite ceramic supports for filtration membrane were successfully fabricated via recycling of coal gangue and bauxite at sintering temperatures from 1100 to 1500°C with corn starch as pore-forming agent. The dynamic sintering behaviors, phase evolution, shrinkage, porosity and pore size, gas permeation flux, microstructure and mechanical property were systematically studied. A unique volume-expansion stage was observed at increased temperatures from 1276 to 1481°C caused by a mullitization-crystal-growth process. During this stage, open porosity increases and pore size distributions broaden, which result in a maximum of nitrogen gas flux at 1400°C. The X-ray diffraction results reveal that secondary mullitization took place from 1100°C and the major phase is mullite with a content of ∼84.7wt.% at 1400°C. SEM images show that the as-fabricated mullite supports have a porous microstructure composed of sintered glassy particles embedded with inter-locked mullite crystals, which grew gradually with increasing temperature from rod-like into blocky-like morphologies. To obtain mullite membrane supports with sufficient porosity and acceptable mechanical strength, the relationship between porosity and mechanical strength was investigated, which was fitted using a parabolic equation.

  17. Structural Insights into SraP-Mediated Staphylococcus aureus Adhesion to Host Cells

    PubMed Central

    Zhang, Juan; Wang, Lei; Bai, Xiao-Hui; Zhang, Shi-Jie; Ren, Yan-Min; Li, Na; Zhang, Yong-Hui; Zhang, Zhiyong; Gong, Qingguo; Mei, Yide; Xue, Ting; Zhang, Jing-Ren; Chen, Yuxing; Zhou, Cong-Zhao

    2014-01-01

    Staphylococcus aureus, a Gram-positive bacterium causes a number of devastating human diseases, such as infective endocarditis, osteomyelitis, septic arthritis and sepsis. S. aureus SraP, a surface-exposed serine-rich repeat glycoprotein (SRRP), is required for the pathogenesis of human infective endocarditis via its ligand-binding region (BR) adhering to human platelets. It remains unclear how SraP interacts with human host. Here we report the 2.05 Å crystal structure of the BR of SraP, revealing an extended rod-like architecture of four discrete modules. The N-terminal legume lectin-like module specifically binds to N-acetylneuraminic acid. The second module adopts a β-grasp fold similar to Ig-binding proteins, whereas the last two tandem repetitive modules resemble eukaryotic cadherins but differ in calcium coordination pattern. Under the conditions tested, small-angle X-ray scattering and molecular dynamic simulation indicated that the three C-terminal modules function as a relatively rigid stem to extend the N-terminal lectin module outwards. Structure-guided mutagenesis analyses, in addition to a recently identified trisaccharide ligand of SraP, enabled us to elucidate that SraP binding to sialylated receptors promotes S. aureus adhesion to and invasion into host epithelial cells. Our findings have thus provided novel structural and functional insights into the SraP-mediated host-pathogen interaction of S. aureus. PMID:24901708

  18. Supramolecular Order of 2,5-Bis(dodecanoxy)phenyleneethynylene-Butadiyne Oligomers in the Solid State.

    PubMed

    Vergara, Edgar; Arias, Eduardo; Moggio, Ivana; Gallardo-Vega, Carlos; Ziolo, Ronald F; Jiménez-Barrera, Rosa M; Navarro, Damaso; Rodríguez, Oliverio; Fernández, Salvador; Herrera, Manuel

    2015-06-23

    The supramolecular order of a 2,5-bis(dodecanoxy)phenyleneethynylene-butadiyne series of rod-like oligomers with 2, 4, 6, and 8 phenyleneethynylene moieties was studied in the solid state by differential scanning calorimetry (DSC), temperature-dependent small- and wide-angle X-ray scattering (SWAXS), selected area electron diffraction (SAED), polarized optical microscopy (POM), high-resolution transmission microscopy (HRTEM), and scanning tunneling microscopy (STM). It was found that all of the oligomers self-assemble in blocks of molecules that resemble bricks that are randomly oriented. These oligomers are described as sanidic liquid crystals as a term to classify their mesomorphic behavior because of their brick or board-like structure. The strong π-π interaction that governs the package of conjugated backbones was evidenced by the reiterative distances of 0.36 ± 0.017 nm found by SWAXS and 0.32 ± 0.017 nm found by HRTEM. A STM study of a cast film of the tetramer deposited on highly oriented pyrolitic graphite (HOPG) allowed for the visualization and determination of the conjugated backbone length of 2.48 nm and a phenyl-phenyl distance of 0.34 nm, suggesting that the molecules are stacked in lamellae perpendicularly aligned to the substrate.

  19. Morphological effect of lanthanum-based supports on the catalytic performance of Pt catalysts in crotonaldehyde hydrogenation

    NASA Astrophysics Data System (ADS)

    Hou, Fengjun; Zhao, Huahua; Zhao, Jun; Yang, Jian; Yan, Liang; Song, Huangling; Chou, Lingjun

    2016-03-01

    Rod-like and particle-like La2O2CO3 and La2O3 were obtained via morphology-preserved thermal transformation of the La(OH)3 precursors. La2O2CO3- and La2O3-supported Pt catalysts were prepared by impregnation method and tested in the liquid-phase crotonaldehyde hydrogenation reaction. The textural and physicochemical properties of the samples were studied by a series of techniques including XRD, TG-DSC, N2 adsorption-desorption, TEM and HRTEM, IR spectrum, H2-TPD, and H2-TPR. Even after 600 °C reduction, Pt particles of about 0.8-2.8 nm interplayed with support surface to form Pt-doped interface, thereby preventing the catalysts from migration and affording a high dispersion of platinum. The specific exposed crystal-facets and surface oxygen species depending on the shape of the support affected the preferential deposition of Pt species and the metal-support interaction. Thus, Pt catalysts performed different physicochemical properties and catalytic performance relying on the morphology and structure of the supports. During the cycle experiment, severe deactivation was observed for NP-supported catalysts with an increased selectivity due to the aggregation and growth of Pt particles. Meantime, the NR-supported catalysts retained relatively high reactivity as a consequence of the crystal-facet confinement of rod-shaped lanthanum supports.

  20. Phase transformation and deformation behavior of NiTi-Nb eutectic joined NiTi wires.

    PubMed

    Wang, Liqiang; Wang, Cong; Zhang, Lai-Chang; Chen, Liangyu; Lu, Weijie; Zhang, Di

    2016-04-06

    NiTi wires were brazed together via eutectic reaction between NiTi and Nb powder deposited at the wire contact region. Phase transformation and deformation behavior of the NiTi-Nb eutectic microstructure were investigated using transmission electron microscopy (TEM) and cyclic loading-unloading tests. Results show that R phase and B19' martensite transformation are induced by plastic deformation. R phase transformation, which significantly contributes to superelasticity, preferentially occurs at the interfaces between NiTi and eutectic region. Round-shaped Nb-rich phase with rod-like and lamellar-type eutectics are observed in eutectic regions. These phases appear to affect the deformation behavior of the brazed NiTi-Nb region via five distinct stages in stress-strain curves: (I) R phase reorientation, (II) R phase transformation from parent phase, (III) elastic deformation of reoriented martensite accompanied by the plastic deformation of Nb-rich phase and lamellar NiTi-Nb eutectic, (IV) B19' martensitic transformation, and (V) plastic deformation of the specimen.

  1. Molecular Structures and Interactions in the Yeast Kinetochore

    PubMed Central

    Cho, U.-S.; Corbett, K.D.; Al-Bassam, J.; Bellizzi, J.J.; De Wulf, P.; Espelin, C.W.; Miranda, J.J.; Simons, K.; Wei, R.R.; Sorger, P.K.; Harrison, S.C.

    2011-01-01

    Kinetochores are the elaborate protein assemblies that attach chromosomes to spindle microtubules in mitosis and meiosis. The kinetochores of point-centromere yeast appear to represent an elementary module, which repeats a number of times in kinetochores assembled on regional centromeres. Structural analyses of the discrete protein subcomplexes that make up the budding-yeast kinetochore have begun to reveal principles of kinetochore architecture and to uncover molecular mechanisms underlying functions such as transmission of tension and establishment and maintenance of bipolar attachment. The centromeric DNA is probably wrapped into a compact organization, not only by a conserved, centromeric nucleosome, but also by interactions among various other DNA-bound kinetochore components. The rod-like, heterotetrameric Ndc80 complex, roughly 600 Å long, appears to extend from the DNA-proximal assembly to the plus end of a microtubule, to which one end of the complex is known to bind. Ongoing structural studies will clarify the roles of a number of other well-defined complexes. PMID:21467141

  2. Distinct Roles for the N- and C-terminal Regions of M-Sec in Plasma Membrane Deformation during Tunneling Nanotube Formation

    PubMed Central

    Kimura, Shunsuke; Yamashita, Masami; Yamakami-Kimura, Megumi; Sato, Yusuke; Yamagata, Atsushi; Kobashigawa, Yoshihiro; Inagaki, Fuyuhiko; Amada, Takako; Hase, Koji; Iwanaga, Toshihiko; Ohno, Hiroshi; Fukai, Shuya

    2016-01-01

    The tunneling nanotube (TNT) is a structure used for intercellular communication, and is a thin membrane protrusion mediating transport of various signaling molecules and cellular components. M-Sec has potent membrane deformation ability and induces TNT formation in cooperation with the Ral/exocyst complex. Here, we show that the N-terminal polybasic region of M-Sec directly binds phosphatidylinositol (4,5)-bisphosphate for its localization to the plasma membrane during the initial stage of TNT formation. We further report a crystal structure of M-Sec, which consists of helix bundles arranged in a straight rod-like shape, similar to the membrane tethering complex subunits. A positively charged surface in the C-terminal domains is required for M-Sec interaction with active RalA to extend the plasma membrane protrusions. Our results suggest that the membrane-associated M-Sec recruits active RalA, which directs the exocyst complex to form TNTs. PMID:27629377

  3. Synthesis of mesoporous hydroxyapatite using a modified hard-templating route

    SciTech Connect

    Xia Zhiguo; Liao Libing; Zhao Senlin

    2009-08-05

    Mesoporous polycrystals of hydroxyapatite-calcium are synthesized via a modified hard-templating route. The structure properties of hydroxyapatite-calcium are characterized by means of X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy and N{sub 2} adsorption-desorption isotherms. Wide-angle X-ray diffraction and Fourier transform infrared spectroscopy measurements reveal that the crystalline grains consist of highly crystalline pure hydroxyapatite phases. Transmission electron microscopy results show that rod-like hydroxyapatite-calcium grains with an average diameter of about 100 nm long and about 20 nm wide are uniformly distributed, which are also observed with an average pore size of 2-3 nm. Based on N{sub 2} adsorption-desorption isotherms investigation, the pore size, surface area and pore volume of mesoporous hydroxyapatite-calcium are 2.73 nm, 42.43 m{sup 2} g{sup -1} and 0.12 cm{sup 3} g{sup -1}, respectively.

  4. Continuous microwave flow synthesis of mesoporous hydroxyapatite.

    PubMed

    Akram, Muhammad; Alshemary, Ammar Z; Goh, Yi-Fan; Wan Ibrahim, Wan Aini; Lintang, Hendrik O; Hussain, Rafaqat

    2015-11-01

    We have successfully used continuous microwave flow synthesis (CMFS) technique for the template free synthesis of mesoporous hydroxyapatite. The continuous microwave flow reactor consisted of a modified 2.45GHz household microwave, peristaltic pumps and a Teflon coil. This cost effective and efficient system was exploited to produce semi-crystalline phase pure nano-sized hydroxyapatite. Effect of microwave power, retention time and the concentration of reactants on the phase purity, degree of crystallinity and surface area of the final product was studied in detail. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) were used to study the phase purity and composition of the product, while transmission electron microscopy (TEM) was used to study the effect of process parameters on the morphology of hydroxyapatite. The TEM analysis confirmed the formation of spherical particles at low microwave power; however the morphology of the particles changed to mesoporous needle and rod-like structure upon exposing the reaction mixture to higher microwave power and longer retention time inside the microwave. The in-vitro ion dissolution behavior of the as synthesized hydroxyapatite was studied by determining the amount of Ca(2+) ion released in SBF solution.

  5. Synthesis and characterization of hydroxyapatite nanofiber by chemical precipitation method using surfactants

    SciTech Connect

    Gao, Shan; Sun, Kangning; Li, Aimin; Wang, Hongyou

    2013-03-15

    Highlights: ► We succeeded in synthesizing hydroxyapatite nano fibers by a chemical method. ► The reaction temperature is only 90 °C. ► The synthetic hydroxyapatite nano fiber is single crystal. - Abstract: We report a novel chemical precipitation route for the synthesis of hydroxyapatite (Ca{sub 10}(PO{sub 4}){sub 6}(OH){sub 2}, HA) fibers using surfactants as templates. Fourier transform infrared spectroscopy (FTIR) and powder X-ray diffraction (PXRD) reveal the characteristic peaks of HA. Transmission electron microscope (TEM) and high-resolution TEM revealed the nano structure, crystallinity and morphology of the HA fibers. The morphology of the HA fibers after calcinations were characterized by scanning electron microscope (SEM). Br{sup −} ions were quickly replaced by the excess PO{sub 4}{sup 3−} ions in the solution after the addition of cetyltrime-thylammonium bromide (CTAB). Meanwhile, CTAB formed a rod-like micelles. Precursors reacted with PO{sub 4}{sup 3−} at the surface of CTAB micelles and finally formed the nanofiber structure.

  6. Amelogenin-assisted ex vivo remineralization of human enamel: Effects of supersaturation degree and fluoride concentration.

    PubMed

    Fan, Yuwei; Nelson, James R; Alvarez, Jason R; Hagan, Joseph; Berrier, Allison; Xu, Xiaoming

    2011-05-01

    The formation of organized nanocrystals that resemble enamel is crucial for successful enamel remineralization. Calcium, phosphate and fluoride ions, and amelogenin are important ingredients for the formation of organized hydroxyapatite (HAP) crystals in vitro. However, the effects of these remineralization agents on the enamel crystal morphology have not been thoroughly studied. The objective of this study was to investigate the effects of fluoride ions, supersaturation degree and amelogenin on the crystal morphology and organization of ex vivo remineralized human enamel. Extracted third molars were sliced thin and acid-etched to provide the enamel surface for immersion in different remineralization solutions. The crystal morphology and mineral phase of the remineralized enamel surface were analyzed by field emission-scanning electron microscopy, attenuated total reflection-Fourier transformed infrared and X-ray diffraction. The concentration of fluoride and the supersaturation degree of hydroxyapatite had significant effects on the crystal morphology and crystal organization, which varied from plate-like loose crystals to rod-like densely packed nanocrystal arrays. Densely packed arrays of fluoridated hydroxyapatite nanorods were observed under the following conditions: σ(HAP)=10.2±2.0 with 1.5±0.5 mg l(-1) fluoride and 40±10 μg ml(-1) amelogenin, pH 6.8±0.4. A phase diagram summarizes the conditions that form dense or loose hydroxyapatite nanocrystal structures. This study provides the basis for the development of novel dental materials for caries management.

  7. Designer ionic liquid crystals based on congruently shaped guanidinium sulfonates.

    PubMed

    Butschies, Martin; Frey, Wolfgang; Laschat, Sabine

    2012-03-05

    Ionic liquid crystals are mesogenic compounds that consist of cations and anions, usually rod-like cations and spherical anions. Herein we report a new method for the synthesis of ionic liquid crystals by using cations and anions of the same molecular shape with oppositely charged head groups. Thus, 4-alkoxyphenylpentamethylguanidinium 4-alkoxyphenylsulfonate ion pairs have been synthesised. 4-Alkoxyphenylpentamethylguanidinium iodides were also prepared to determine the influence of congruently shaped anions, in comparison with their spherical counterparts, on mesophase behaviour, which was investigated by differential scanning calorimetry (DSC), polarising optical microscopy (POM) and X-ray diffraction (XRD). All the liquid crystalline salts exhibit smectic A mesophases with strongly interdigitated bilayer structures. The guanidinium sulfonate ion pairs show mesomorphic properties from shorter alkyl chain lengths (≥C(9)) and lower melting points (≈10 K), whereas the corresponding guanidinium iodides are liquid crystalline for longer alkyl chain lengths (≥C(14)). For chains with ≥C(18), however, the mesophase range decreases for the sulfonate ion pairs, but not for the iodide salts.

  8. Ex vivo mammalian prions are formed of paired double helical prion protein fibrils

    PubMed Central

    Terry, Cassandra; Wenborn, Adam; Gros, Nathalie; Sells, Jessica; Joiner, Susan; Hosszu, Laszlo L. P.; Tattum, M. Howard; Panico, Silvia; Clare, Daniel K.; Collinge, John; Saibil, Helen R.

    2016-01-01

    Mammalian prions are hypothesized to be fibrillar or amyloid forms of prion protein (PrP), but structures observed to date have not been definitively correlated with infectivity and the three-dimensional structure of infectious prions has remained obscure. Recently, we developed novel methods to obtain exceptionally pure preparations of prions from mouse brain and showed that pathogenic PrP in these high-titre preparations is assembled into rod-like assemblies. Here, we have used precise cell culture-based prion infectivity assays to define the physical relationship between the PrP rods and prion infectivity and have used electron tomography to define their architecture. We show that infectious PrP rods isolated from multiple prion strains have a common hierarchical assembly comprising twisted pairs of short fibres with repeating substructure. The architecture of the PrP rods provides a new structural basis for understanding prion infectivity and can explain the inability to systematically generate high-titre synthetic prions from recombinant PrP. PMID:27249641

  9. Influence of constraints on axial growth reduction of cylindrical Li-ion battery electrode particles

    NASA Astrophysics Data System (ADS)

    Chakraborty, Jeevanjyoti; Please, Colin P.; Goriely, Alain; Chapman, S. Jonathan

    2015-04-01

    Volumetric expansion of silicon anode particles in a lithium-ion battery during charging may lead to the generation of undesirable internal stresses. For a cylindrical particle such growth may also lead to failure by buckling if the expansion is constrained in the axial direction due to other particles or supporting structures. To mitigate this problem, the possibility of reducing axial growth is investigated theoretically by studying simple modifications of the solid cylinder geometry. First, an annular cylinder is considered with lithiation either from the inside or from the outside. In both cases, the reduction of axial growth is not found to be significant. Next, explicit physical constraints are studied by addition of a non-growing elasto-plastic material: first, an outer annular constraint on a solid silicon cylinder, and second a rod-like inner constraint for an annular silicon cylinder. In both cases, it is found that axial growth can be reduced if the yield stress of the constraining material is significantly higher than that of silicon and/or the thickness of the constraint is relatively high. Phase diagrams are presented for both the outer and the inner constraint cases to identify desirable operating zones. Finally, to interpret the phase diagrams and isolate the key physical principles two different simplified models are presented and are shown to recover important qualitative trends of the numerical simulation results.

  10. Solvent Molding of Organic Morphologies Made of Supramolecular Chiral Polymers.

    PubMed

    Đorđević, Luka; Marangoni, Tomas; Miletić, Tanja; Rubio-Magnieto, Jenifer; Mohanraj, John; Amenitsch, Heinz; Pasini, Dario; Liaros, Nikos; Couris, Stelios; Armaroli, Nicola; Surin, Mathieu; Bonifazi, Davide

    2015-07-01

    The self-assembly and self-organization behavior of uracil-conjugated enantiopure (R)- or (S)-1,1'-binaphthyl-2,2'-diol (BINOL) and a hydrophobic oligo(p-phenylene ethynylene) (OPE) chromophore exposing 2,6-di(acetylamino)pyridine termini are reported. Systematic spectroscopic (UV-vis, CD, fluorescence, NMR, and SAXS) and microscopic studies (TEM and AFM) showed that BINOL and OPE compounds undergo triple H-bonding recognition, generating different organic nanostructures in solution. Depending on the solvophobic properties of the liquid media (toluene, CHCl3, CHCl3/CHX, and CHX/THF), spherical, rod-like, fibrous, and helical morphologies were obtained, with the latter being the only nanostructures expressing chirality at the microscopic level. SAXS analysis combined with molecular modeling simulations showed that the helical superstructures are composed of dimeric double-cable tape-like structures that, in turn, are supercoiled at the microscale. This behavior is interpreted as a consequence of an interplay among the degree of association of the H-bonded recognition, the vapor pressure of the solvent, and the solvophobic/solvophilic character of the supramolecular adducts in the different solutions under static and dynamic conditions, namely solvent evaporation conditions at room temperature.

  11. Oriented and Ordered Biomimetic Remineralization of the Surface of Demineralized Dental Enamel Using HAP@ACP Nanoparticles Guided by Glycine.

    PubMed

    Wang, Haorong; Xiao, Zuohui; Yang, Jie; Lu, Danyang; Kishen, Anil; Li, Yanqiu; Chen, Zhen; Que, Kehua; Zhang, Qian; Deng, Xuliang; Yang, Xiaoping; Cai, Qing; Chen, Ning; Cong, Changhong; Guan, Binbin; Li, Ting; Zhang, Xu

    2017-01-12

    Achieving oriented and ordered remineralization on the surface of demineralized dental enamel, thereby restoring the satisfactory mechanical properties approaching those of sound enamel, is still a challenge for dentists. To mimic the natural biomineralization approach for enamel remineralization, the biological process of enamel development proteins, such as amelogenin, was simulated in this study. In this work, carboxymethyl chitosan (CMC) conjugated with alendronate (ALN) was applied to stabilize amorphous calcium phosphate (ACP) to form CMC/ACP nanoparticles. Sodium hypochlorite (NaClO) functioned as the protease which decompose amelogenin in vivo to degrade the CMC-ALN matrix and generate HAP@ACP core-shell nanoparticles. Finally, when guided by 10 mM glycine (Gly), HAP@ACP nanoparticles can arrange orderly and subsequently transform from an amorphous phase to well-ordered rod-like apatite crystals to achieve oriented and ordered biomimetic remineralization on acid-etched enamel surfaces. This biomimetic remineralization process is achieved through the oriented attachment (OA) of nanoparticles based on non-classical crystallization theory. These results indicate that finding and developing analogues of natural proteins such as amelogenin involved in the biomineralization by natural macromolecular polymers and imitating the process of biomineralization would be an effective strategy for enamel remineralization. Furthermore, this method represents a promising method for the management of early caries in minimal invasive dentistry (MID).

  12. Characterization of Cu3P phase in Sn3.0Ag0.5Cu0.5P/Cu solder joints

    NASA Astrophysics Data System (ADS)

    Chen, Jian-xun; Zhao, Xing-ke; Zou, Xu-chen; Huang, Ji-hua; Hu, Hai-chun; Luo, Hai-lian

    2014-01-01

    This article reports the effects of phosphorus addition on the melting behavior, microstructure, and mechanical properties of Sn3.0Ag0.5Cu solder. The melting behavior of the solder alloys was determined by differential scanning calorimetry. The interfacial microstructure and phase composition of solder/Cu joints were studied by scanning electron microscopy and energy dispersive spectrometry. Thermodynamics of Cu-P phase formation at the interface between Sn3.0Ag0.5Cu0.5P solder and the Cu substrate was characterized. The results indicate that P addition into Sn3.0Ag0.5Cu solder can change the microstructure and cause the appearance of rod-like Cu3P phase which is distributed randomly in the solder bulk. The Sn3.0Ag0.5Cu0.5P joint shows a mixture of ductile and brittle fracture after shear testing. Meanwhile, the solidus temperature of Sn3.0Ag0.5Cu solder is slightly enhanced with P addition.

  13. Amelogenin-assisted ex vivo remineralization of human enamel: effects of supersaturation degree and fluoride concentration

    PubMed Central

    Fan, Yuwei; Nelson, James R.; Alvarez, Jason R.; Hagan, Joseph; Berrier, Allison; Xu, Xiaoming

    2011-01-01

    The formation of organized nanocrystals that resemble enamel is crucial for successful enamel remineralization. Calcium, phosphate and fluoride ions and amelogenin are important ingredients for the formation of organized hydroxyapatite (HAP) crystals in vitro. However, the effects of these remineralization agents on the enamel crystal morphology have not been thoroughly studied. The objective of this study was to investigate the effects of fluoride ions, supersaturation degree and amelogenin on the crystal morphology and organization of ex vivo remineralized human enamel. Extracted third molars were sliced thin and acid-etched to provide the enamel surface for immersion in different remineralization solutions. The crystal morphology and mineral phase of the remineralized enamel surface were analyzed by FE-SEM, ATR-FTIR and XRD. The concentration of fluoride and supersaturation degree of hydroxyapatite had significant effects on the crystal morphology and crystal organization, which varied from plate-like loose crystals to rod-like densely packed nanocrystal arrays. Densely packed arrays of fluoridated hydroxyapatite nanorods were observed under the following conditions: σ(HAP) = 10.2±2.0 with fluoride 1.5±0.5 mg/L and amelogenin 40±10 µg/mL, pH 6.8±0.4. A phase diagram summarized the conditions that form dense or loose hydroxyapatite nanocrystal structures. This study provides the basis for the development of novel dental materials for caries management. PMID:21256987

  14. Development of a novel electrochemical DNA biosensor based on elongated hexagonal-pyramid CdS and poly-isonicotinic acid composite film.

    PubMed

    Zheng, Delun; Wang, Qingxiang; Gao, Feng; Wang, Qinghua; Qiu, Weiwei; Gao, Fei

    2014-10-15

    Three CdS materials with different shapes (i.e., irregular, rod-like, and elongated hexagonal-pyramid) were hydrothermally synthesized through controlling the molar ratio of Cd(2+) to thiourea. Electrochemical experiments showed that the elongated hexagonal-pyramid CdS (eh-CdS) modified on glassy carbon electrode (GCE) had the higher electrical conductivity than the other two forms. Then the eh-CdS modified GCE was further modified with a layer of poly-isonicotinic acid (PIA) through electro-polymerization in IA solution to enhance the stability and functionality of the interface. The layer-by-layer modification process was characterized by atomic force microscopy and electrochemistry. Then 5'-amino functionalized DNA was immobilized on the electrode surface through coupling with the carboxylic groups derived from PIA-eh-CdS composite film. The hybridization performance of the developed biosensor was evaluated using methylene blue as redox indicator, and the results showed that the peak currents of methylene blue varied with target concentrations in a wide linear range from 1.0 × 10(-14)M to 1.0 × 10(-9)M with a low detection limit of 3.9 × 10(-15)M. The biosensor also showed high stability and good discrimination ability to the one-base, three-base mismatched and non-complementary sequence.

  15. Crystal thickness dependence of the photoinduced crystal bending of 1-(5-methyl-2-(4-(p-vinylbenzoyloxymethyl)phenyl)-4-thiazolyl)-2-(5-methyl-2-phenyl-4-thiazolyl)perfluorocyclopentene.

    PubMed

    Kitagawa, Daichi; Kobatake, Seiya

    2014-05-01

    Rod-like crystals of 1-(5-methyl-2-(4-(p-vinylbenzoyloxymethyl)phenyl)-4-thiazolyl)-2-(5-methyl-2-phenyl-4-thiazolyl)perfluorocyclopentene with lengths of over 1 mm showed photoreversible bending over 100 cycles upon irradiation with alternating ultraviolet (UV) and visible light. The crystals bent toward the incident light due to a contraction of the crystal length and a gradient of the crystal thickness, which depend on the extent of photoisomerization. It was observed that the bending speed depends on the crystal thickness, and the curvature change on changing the crystal thickness agrees well with Timoshenko's bimetal model, as well as with the observation that crystals of 1,2-bis(2-methyl-5-(4-(1-naphthoyloxymethyl)phenyl)-3-thienyl)perfluorocyclopentene bend away from the incident light due to an expansion of the crystal length and a gradient of the crystal thickness, which depend on the extent of photoisomerization. It was revealed that Timoshenko's bimetal model can be applied to photoinduced crystal bending behaviors caused by both contraction and expansion. These findings are very useful for evaluating and designing photomechanical actuators.

  16. Visualization of chromosomes in the binucleate intestinal parasite Giardia lamblia.

    PubMed

    Shen, Hai E; Cao, Lei; Li, Ji; Tian, Xi Feng; Yang, Zhi Hong; Wang, Yue; Tian, Yu Na; Lu, Si Qi

    2011-11-01

    Mitosis of Giardia lamblia is a complex and rapid event that is poorly understood at the cellular and molecular levels. Therefore, we conducted this study to determine (1) whether the two nuclei have similar or different chromosomes, (2) the number of chromosomes of G. lamblia, and (3) the morphology and karyotype of the chromosomes. Trophozoites of the C2 and WB strains of G. lamblia were grown in modified TYI-S-33 medium at 37°C. The trophozoites were collected, and sample slides were prepared for conventional light and scanning electron microscopy. Light microscopy revealed five pairs of chromosomes. The chromosomes were approximately 0.64-0.94 μm long with a short rod-like shape and were usually arranged in pairs. Scanning electron microscopy yielded similar findings, and 10 chromosomes could be seen in each nucleus. Thus, the chromosome number of G. lamblia is 2n = 10. Chromosomes in pair 1 are submetacentric chromosomes, while pairs 2-5 are telocentric chromosomes. The present study shows that G. lamblia trophozoites have typical condensed chromosomes during mitosis and contains five pairs of chromosomes. The karyogram shows good fit to the formula 2n = 10 = 2sm + 8t revealed by scanning electron microscopy.

  17. Confocal microscopy refines generic concept of a problematic taxon: rediagnosis of the genus Neoprothrix and remarks on female anatomy of eriophyoids (Acari: Eriophyoidea).

    PubMed

    Chetverikov, Philipp E; Desnitskiy, Alexey G; Navia, Denise

    2015-02-16

    Due to the higher resolution, confocal microscopy (CLSM) can be applied to refine the origin of tiny structures of the autofluorescent exoskeletons of microarthropods (mites in particular) which are hard to visualize using traditional differential interference contract light microscopy (DIC LM) and phase contrast light microscopy (PC LM). Three-dimensional (3D) reconstructions of the prodorsal shield topography of eriophyoid mites using Neoprothrix hibiscus Reis and Navia as a model, suggest that the structures originally treated as paired setae vi are two internal rod-like apodemes. Based on this, the genus Neoprothrix is excluded from the subfamily Prothricinae Amrine and transferred to the subfamily Sierraphytoptinae Keifer. Observations on partially cleared specimens of N. hibiscus showed that remnants of the central nervous system, paired glands and developing oocytes can be visualized using DIC LM and CLSM methods. New high quality microscope images are provided of recently described "flower-shaped" structures and two main components of yolk inclusions of the mature eggs inside the oviduct.

  18. Green material: ecological importance of imperative and sensitive chemi-sensor based on Ag/Ag2O3/ZnO composite nanorods

    PubMed Central

    2013-01-01

    In this report, we illustrate a simple, easy, and low-temperature growth of Ag/Ag2O3/ZnO composite nanorods with high purity and crystallinity. The composite nanorods were structurally characterized by field emission scanning electron microscopy, X-ray powder diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy which confirmed that synthesized product have rod-like morphology having an average cross section of approximately 300 nm. Nanorods are made of silver, silver oxide, and zinc oxide and are optically active having absorption band at 375 nm. The composite nanorods exhibited high sensitivity (1.5823 μA.cm−2.mM−1) and lower limit of detection (0.5 μM) when applied for the recognition of phenyl hydrazine utilizing I-V technique. Thus, Ag/Ag2O3/ZnO composite nanorods can be utilized as a redox mediator for the development of highly proficient phenyl hydrazine sensor. PMID:24011288

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  20. Self-assembly in sugar-oil complex glasses

    NASA Astrophysics Data System (ADS)

    Dave, Hiteshkumar; Gao, Feng; Lee, Jing-Huei; Liberatore, Matthew; Ho, Chia-Chi; Co, Carlos C.

    2007-04-01

    In aqueous systems, the hydrophobic effect drives the self-assembly of amphiphiles into a broad range of micellar, rod-like, bicontinuous and liquid-crystalline complex fluids. Many of these are relevant to biological matter or technological applications. However, amphiphilic self-assembly is not limited to aqueous systems. Replacement of water with supercritical carbon dioxide, for example, results in complex fluids that combine the properties of gases and liquids. Along this vein, we explore the self-assembly of surfactants in anhydrous sugars. Our study reveals that anhydrous powders of sugars and surfactants suspended in oil spontaneously form molten glasses with nanometre-size domains of sugar and liquid oil without mixing. The low cost, water solubility, low toxicity and stabilizing properties of glassy sugars make them ideal water replacements for many pharmaceutical, food and materials synthesis applications. The optical clarity and solid appearance of these glasses at room temperature belie their inclusion of more than 50% (vol.) oil, which confers liquid-like diffusivity. The unique combination of solid- and liquid-like properties may lead to applications in sensors and optical devices.

  1. Self-assembly in sugar-oil complex glasses.

    PubMed

    Dave, Hiteshkumar; Gao, Feng; Lee, Jing-Huei; Liberatore, Matthew; Ho, Chia-Chi; Co, Carlos C

    2007-04-01

    In aqueous systems, the hydrophobic effect drives the self-assembly of amphiphiles into a broad range of micellar, rod-like, bicontinuous and liquid-crystalline complex fluids. Many of these are relevant to biological matter or technological applications. However, amphiphilic self-assembly is not limited to aqueous systems. Replacement of water with supercritical carbon dioxide, for example, results in complex fluids that combine the properties of gases and liquids. Along this vein, we explore the self-assembly of surfactants in anhydrous sugars. Our study reveals that anhydrous powders of sugars and surfactants suspended in oil spontaneously form molten glasses with nanometre-size domains of sugar and liquid oil without mixing. The low cost, water solubility, low toxicity and stabilizing properties of glassy sugars make them ideal water replacements for many pharmaceutical, food and materials synthesis applications. The optical clarity and solid appearance of these glasses at room temperature belie their inclusion of more than 50% (vol.) oil, which confers liquid-like diffusivity. The unique combination of solid- and liquid-like properties may lead to applications in sensors and optical devices.

  2. Whole-genome analysis of genetic recombination of hepatitis delta virus: molecular domain in delta antigen determining trans-activating efficiency.

    PubMed

    Chao, Mei; Lin, Chia-Chi; Lin, Feng-Ming; Li, Hsin-Pai; Iang, Shan-Bei

    2015-12-01

    Hepatitis delta virus (HDV) is the only animal RNA virus that has an unbranched rod-like genome with ribozyme activity and is replicated by host RNA polymerase. HDV RNA recombination was previously demonstrated in patients and in cultured cells by analysis of a region corresponding to the C terminus of the delta antigen (HDAg), the only viral-encoded protein. Here, a whole-genome recombination map of HDV was constructed using an experimental system in which two HDV-1 sequences were co-transfected into cultured cells and the recombinants were analysed by sequencing of cloned reverse transcription-PCR products. Fifty homologous recombinants with 60 crossovers mapping to 22 junctions were identified from 200 analysed clones. Small HDAg chimeras harbouring a junction newly detected in the recombination map were then constructed. The results further indicated that the genome-replication level of HDV was sensitive to the sixth amino acid within the N-terminal 22 aa of HDAg. Therefore, the recombination map established in this study provided a tool for not only understanding HDV RNA recombination, but also elucidating the related mechanisms, such as molecular elements responsible for the trans-activation levels of the small HDAg.

  3. Effects of deposition conditions on the phase formation of YBCO films prepared by spray pyrolysis method

    NASA Astrophysics Data System (ADS)

    Kim, Ho-Jin; Joo, Jinho; Park, Shin-Geun; Hong, Suck-Kwan; Lee, Sun-Wang; Lim, Sun-Weon; Hong, Gye-Won; Lee, Hee-Gyoun

    2006-10-01

    YBa2Cu3Oy superconducting films were deposited on LaAlO3(1 0 0) single crystal substrates by spray pyrolysis method. Two types of ultrasonic and concentric nebulizer were used in order to generate fine droplets of metal-inorganic precursor solution. c-Axis oriented films were obtained at deposition temperature of 750-850 °C and at working pressures of 100 Torr and 500 Torr. In case of ultrasonic nebulizer, the films showed rough surface morphology due to the presence of enormous droplets, whereas smooth and dense films were obtained for concentric nebulizer. The good c-axis oriented YBCO films were formed at the wide range of the oxygen partial pressure. Oxygen which is generated via the decomposition of nitrate precursors is considered to participate in the formation reaction of YBCO film. Microstructures of YBCO films varied depending on oxygen partial pressure and rod-like grains were appeared when the oxygen partial pressure was lower than 30 Torr. YBCO films were deposited epitaxially on LAO(1 0 0) substrate. Δϕ of in-plane and Δω of out-of-plane texture were measured as 3.3° and 1.0°, respectively. A transport Jc value of 0.50 MA/cm2 at 77 K and self-field was achieved for the YBCO film deposited on LaAlO3(1 0 0) single crystal substrate.

  4. EM study of latent track morphology in TiO2 single crystals

    NASA Astrophysics Data System (ADS)

    O'Connell, J. H.; Skuratov, V. A.; Akilbekov, A.; Zhumazhanova, A.; Janse van Vuuren, A.

    2016-07-01

    A TEM investigation was conducted into the morphology of 167 MeV Xe (2 × 1010 cm-2 to 1014 cm-2) and 1 GeV Bi ion (2 × 1010 cm-2) induced latent tracks in single crystal TiO2 (rutile). At fluences up to 1011 cm-2 latent tracks are visible as discontinuous lines of strained crystal along the ion trajectory. From the implanted surface down to about 60-70 nm below the surface the tracks appear as continuous conical structures with a base of diameter 5-6 nm (Xe) and 8-9 nm (Bi) in contact with the surface with a mushroom shaped hillock extending outward from the surface. At fluences between 6 × 1012 cm-2 and 1013 cm-2 the crystal is amorphized but rod-like crystalline regions remain which are oriented along the ion trajectories. Amorphization extends from the surface down to 8.3 μm below suggesting an upper limit for the threshold electronic stopping power for amorphization of 7.3 keV nm-1. At 1014 cm-2 Xe the entire 8.3 μm subsurface region is rendered amorphous although some evidence of short range ordering remains.

  5. Three-dimensional architecture of collagen type VI in the human trabecular meshwork

    PubMed Central

    Koudouna, Elena; Young, Robert D.; Ueno, Morio; Kinoshita, Shigeru; Knupp, Carlo

    2014-01-01

    Purpose Type VI collagen is a primary component of the extracellular matrix of many connective tissues. It can form distinct aggregates depending on tissue structure, chemical environment, and physiology. In the current study we examine the ultrastructure and mode of aggregation of type VI collagen molecules in the human trabecular meshwork. Methods Trabecular meshwork was dissected from donor human eyes, and three-dimensional transmission electron microscopy of type VI collagen aggregates was performed. Results Electron-dense collagen structures were detected in the human trabecular meshwork and identified as collagen type VI assemblies based on the three-dimensional spatial arrangement of the type VI collagen molecules, the 105-nm axial periodicity of the assemblies themselves, and their characteristic double bands, which arose from the globular domains of the type VI collagen molecules. Sulfated proteoglycans were also seen to associate with the assemblies either with the globular domain or the inner rod-like segments of the tetramers. Conclusions No extended structural regularity in the organization of type VI collagen assemblies within the trabecular meshwork was evident, and the lateral separation of the tetramers forming the assemblies varied, as did the angle formed by the main axes of adjacent tetramers. This is potentially reflective of the specific nature of the trabecular meshwork environment, which facilitates aqueous outflow from the eye, and we speculate that extracellular matrix ions and proteins might prevent a more tight packing of type VI collagen tetramers that form the assemblies. PMID:24868138

  6. Controlling the growth and shape of chiral supramolecular polymers in water

    PubMed Central

    Besenius, Pol; Portale, Giuseppe; Bomans, Paul H. H.; Janssen, Henk M.; Palmans, Anja R. A.; Meijer, E. W.

    2010-01-01

    A challenging target in the noncovalent synthesis of nanostructured functional materials is the formation of uniform features that exhibit well-defined properties, e.g., precise control over the aggregate shape, size, and stability. In particular, for aqueous-based one-dimensional supramolecular polymers, this is a daunting task. Here we disclose a strategy based on self-assembling discotic amphiphiles that leads to the control over stack length and shape of ordered, chiral columnar aggregates. By balancing out attractive noncovalent forces within the hydrophobic core of the polymerizing building blocks with electrostatic repulsive interactions on the hydrophilic rim we managed to switch from elongated, rod-like assemblies to small and discrete objects. Intriguingly this rod-to-sphere transition is expressed in a loss of cooperativity in the temperature-dependent self-assembly mechanism. The aggregates were characterized using circular dichroism, UV and 1H-NMR spectroscopy, small angle X-ray scattering, and cryotransmission electron microscopy. In analogy to many systems found in biology, mechanistic details of the self-assembly pathways emphasize the importance of cooperativity as a key feature that dictates the physical properties of the produced supramolecular polymers. PMID:20921365

  7. Identification of extensin protein associated with sugar beet pectin.

    PubMed

    Nuñez, Alberto; Fishman, Marshall L; Fortis, Laurie L; Cooke, Peter H; Hotchkiss, Arland T

    2009-11-25

    Several studies have suggested that the emulsification properties associated with pectin obtained from sugar beet (Beta vulgaris) are due to the presence of a protein-pectin complex. Nevertheless, the identity of the protein has remained elusive. Pectin, extracted from sugar beet pulp by microwave-assisted extraction, and a commercial sample were both subjected to protease digestion with trypsin. The resulting peptides were separated from the pectin solution by ultrafiltration using a 3 kDa molecular weight cutoff (MWCO) membrane and analyzed using matrix-assisted laser desorption ionization with tandem time-of-flight mass spectrometry. The partial sequences derived from the mass spectrometry analyses of the resulting tryptic peptides are found to be highly consistent with extensin protein matched from the B. vulgaris Genetic Index database and also correspond to previously reported extensin peptides found in sugar beet cell suspension cultures. Further attempts were made to disassociate the protein from pectin using 1 M NaCl and a 100 kDa MWCO membrane; however, no peptides were observed following trypsin digestion of the permeate solution. This evidence suggests the existence of a complex between the pectin and extensin that is not due to ionic interactions. Trypsin digestion of commercial sugar beet pectin also produced the peptide profile observed with the microwave-assisted extracted pectin sample. Atomic force microscopy established that the number of rod-like elements decreased following protease treatment compared to the untreated sample.

  8. Characteristics of zinc sulphide nanostructures grown onsilica modified-polyaniline with polymerization time-dependent

    NASA Astrophysics Data System (ADS)

    Potestas, M.; Alguno, A.; Vequizo, R.; Sambo, B. R.; Odarve, M. K.

    2015-06-01

    Growth of zinc sulphide (ZnS) nanostructures on silica modified-polyaniline (SM- PAni) with polymerization time-dependent was prepared using chemical bath deposition (CBD) technique. The grown samples were characterized by scanning electron microscopy (SEM) equipped with energy dispersive x-ray spectroscopy (EDS) and fourier transform infrared spectroscopy (FTIR). SEM images revealed that polyaniline rod-like nanostructures and ZnS nanospheres were successfully grown. The average diameter of the grown ZnS nanospheres did not significantly change by changing the growth time of the polyaniline. However, ZnS nanospheres grown with longer polymerization time of PAni is less dense and loosely bound as compared to shorter polymerization time of PAni. The less density of ZnS nanostructures with longer polymerization time of PAni may be due to the presence of PAni agglomerates that hinders the growth of ZnS nanospheres. Furthermore, FTIR spectra confirmed that the grown polyaniline is of emeraldine salt oxidation state which is the most conductive state of PAni.

  9. Haplosporidium sp. (Alveolata: Haplosporidia) associated with mortalities among rock oysters Saccostrea cuccullata in north Western Australia.

    PubMed

    Hine, P M; Thorne, Tina

    2002-08-29

    Haplosporidium sp. is described from rock oysters Saccostrea cuccullata Born, 1778 experiencing epizootics on the northwestern coast of Western Australia. All stages were observed as focal infections in the connective tissue of the gills, or as disseminated infections in the mantle and around digestive diverticulae. Haplosporidium sp. occurred between epithelial cells of the gut, in focal lesions in the gills, but not in the epithelium of the digestive diverticulae, and sporulation was confined to the connective tissue. Plasmodia developed into sporonts and sporocysts in a loose syncytium that gave rise to binucleate and uninucleate sporoblasts from which spores developed. Spores were flask-shaped, 5.6-6.7 x 3.3-4.0 microm, with a characteristic operculum, a few filamentous wrappings and rod-like structures in the posterior sporoplasm. Mature spores had a wall comprising inner (90 nm wide), middle (30 nm wide) and outer (130 nm wide) layers, and a surface coat of microtubules giving them a furry appearance. Oysters with empty gonad follicles were most heavily infected, and oyster condition and mortality appeared to be related to degree of infection.

  10. Assembly of phage phi 29 genome with viral protein p6 into a compact complex.

    PubMed Central

    Gutiérrez, C; Freire, R; Salas, M; Hermoso, J M

    1994-01-01

    The formation of a multimeric nucleoprotein complex by the phage phi 29 dsDNA binding protein p6 at the phi 29 DNA replication origins, leads to activation of viral DNA replication. In the present study, we have analysed protein p6-DNA complexes formed in vitro along the 19.3 kb phi 29 genome by electron microscopy and micrococcal nuclease digestion, and estimated binding parameters. Under conditions that greatly favour protein-DNA interaction, the saturated phi 29 DNA-protein p6 complex appears as a rigid, rod-like, homogeneous structure. Complex formation was analysed also by a psoralen crosslinking procedure that did not disrupt complexes. The whole phi 29 genome appears, under saturating conditions, as an irregularly spaced array of complexes approximately 200-300 bp long; however, the size of these complexes varies from approximately 2 kb to 130 bp. The minimal size of the complexes, confirmed by micrococcal nuclease digestion, probably reflects a structural requirement for stability. The values obtained for the affinity constant (K(eff) approximately 10(5) M-1) and the cooperativity parameter (omega approximately 100) indicate that the complex is highly dynamic. These results, together with the high abundance of protein p6 in infected cells, lead us to propose that protein p6-DNA complexes could have, at least at some stages, during infection, a structural role in the organization of the phi 29 genome into a nucleoid-type, compact nucleoprotein complex. Images PMID:8306969

  11. Imaging of the World's Fastest Biological Spring Vorticella Convallaria Via Atomic Force Micoscopy

    NASA Astrophysics Data System (ADS)

    Bras, Rafael; Upadhyaya, Arpita; van Oudenaarden, Alexander; Ortiz, Christine

    2002-03-01

    The rod-like, contractile stalk (25-300 micron length, 4 micron diameter) of the single-celled peritrich Vorticella Convallaria can collapse into a tightly coiled helix in > 1/60 second. The stalk consists of membranes stiffened by an assembly of protein bundles (batonets) surrounding the spasmoneme, an asymmetrically located bundle of negatively charged polyelectrolytic spasmin protein. It is thought that contraction results from the entropic collapse of spasmin via Ca2+ screening of electrostatic repulsion. After culturing, an aqueous solution containing detached cells was filtered and placed on freshly cleaved mica substrates to dry in air for 30min. The samples were imaged via contact mode atomic force microscopy. The following was clearly visualized; the helicity of the stalk, the spasmonene (1.3-2.4 micron diameter), batonets (230-300nm), the outer stalk membrane morphology, and organelles in the stalk. The circular stalk "foot" (2.8 micron diameter) where the organism attached itself to substrates was also imaged, which may be the biological "glue" used for surface attachment.

  12. Molecular recognition by van der Waals interaction between polymers with sequence-specific polarizabilities.

    PubMed

    Lu, Bing-Sui; Naji, Ali; Podgornik, Rudolf

    2015-06-07

    We analyze van der Waals interactions between two rigid polymers with sequence-specific, anisotropic polarizabilities along the polymer backbones, so that the dipole moments fluctuate parallel to the polymer backbones. Assuming that each polymer has a quenched-in polarizability sequence which reflects, for example, the polynucleotide sequence of a double-stranded DNA molecule, we study the van der Waals interaction energy between a pair of such polymers with rod-like structure for the cases where their respective polarizability sequences are (i) distinct and (ii) identical, with both zero and non-zero correlation length of the polarizability correlator along the polymer backbones in the latter case. For identical polymers, we find a novel r(-5) scaling behavior of the van der Waals interaction energy for small inter-polymer separation r, in contradistinction to the r(-4) scaling behavior of distinct polymers, with furthermore a pronounced angular dependence favoring attraction between sufficiently aligned identical polymers. Such behavior can assist the molecular recognition between polymers.

  13. Kinetics of light-induced ordering and deformation in LC azobenzene-containing materials.

    PubMed

    Toshchevikov, Vladimir; Petrova, Tatiana; Saphiannikova, Marina

    2017-04-12

    Azobenzene-containing smart materials are able to transform the energy of light into directional mechanical stress. We develop a theory of time-dependent light-induced ordering and deformation in azobenzene materials starting from the kinetic equations of photoisomerization. The liquid crystalline (LC) interactions between rod-like trans-isomers are taken into account. Angular selectivity of the photoisomerization known as an "angular hole burning" or the Weigert effect leads to the light-induced ordering and deformation of the azobenzene materials. The time evolution of ordering and deformation is found as a function of intensity of light depending on the opto-mechanical characteristics of the materials, such as probabilities of the optical excitation of trans- and cis-isomers, angular jump during the single isomerization event, viscosity of the materials, strength of the LC interactions in both the isotropic and LC materials, and the angular distribution of chromophores in polymer chains. Established structural-property relationships are in agreement with a number of experiments and can be used for the construction of light-controllable smart materials for practical applications.

  14. Reduced graphene oxide composites with water soluble copolymers having tailored lower critical solution temperatures and unique tube-like structure

    PubMed Central

    Namvari, Mina; Biswas, Chandra S.; Galluzzi, Massimiliano; Wang, Qiao; Du, Bing; Stadler, Florian J.

    2017-01-01

    Nanohybrids of graphene with water soluble polymer were synthesized using ‘grafting from’ method. GO, prepared by modified Hummers’ method, was first reacted with sodium azide. Alkyne-terminated RAFT-CTA was synthesized by reaction of propargyl alcohol and S-1-dodecyl-S’-(α,α‘-dimethyl-α”-acetic acid) trithiocarbonate. RAFT-CTA was grafted onto the GO sheets by facile click-reaction and subsequently, N-isopropylacrylamide (NIPAM) and N-ethyleacrylamide (NEAM) were polymerized on graphene sheets via RAFT polymerization method. The respective copolymers with different ratios were also prepared. The nanohybrids were characterized by FTIR, XRD, TGA, Raman, SEM, and AFM. Both SEM and AFM clearly showed rod-like structures for rGO-PNEAM. XRD showed a small peak at 2θ = 19.21°, corresponding to d-spacing ≈ 4.6 Å. In addition, the nanohybrids showed a very broad temperature range for the LCST in water between ca. 30 and 70 °C. PMID:28291225

  15. Effects of PEGylated paclitaxel nanocrystals on breast cancer and its lung metastasis

    NASA Astrophysics Data System (ADS)

    Zhang, Hua; Hu, Hongxiang; Zhang, Haoran; Dai, Wenbing; Wang, Xinglin; Wang, Xueqing; Zhang, Qiang

    2015-06-01

    As an attractive strategy developed rapidly in recent years, nanocrystals are used to deliver insoluble drugs. PEGylation may further prolong the circulation time of nanoparticles and improve the therapeutic outcome of drugs. In this study, paclitaxel (PTX) nanocrystals (PTX-NCs) and PEGylated PTX nanocrystals (PEG-PTX-NCs) were prepared using antisolvent precipitation augmented by probe sonication. The characteristics and antitumor efficacy of nanocrystals were investigated. The results indicated that the nanocrystals showed rod-like morphology, and the average particle size was 240 nm and 330 nm for PTX-NCs and PEG-PTX-NCs, respectively. The PEG molecules covered the surface of nanocrystals with an 11.54 nm fixed aqueous layer thickness (FALT), much higher than that of PTX-NCs (0.2 nm). PEG-PTX-NCs showed higher stability than PTX-NCs under both storage and physiological conditions. In breast cancer xenografted mice, PEG-PTX-NCs showed significantly better tumor inhibition compared to saline (p < 0.001) and PTX-NC groups (p < 0.05) after intravenous administration. In a model of lung tumor metastasis quantified by the luciferase activity, the PEG-PTX-NCs group showed higher anticancer efficacy not only than saline and PTX-NCs groups, but also than Taxol®, achieving an 82% reduction at the end of the experiment. These studies suggested the potential advantages of PEGylated PTX nanocrystals as alternative drug delivery systems for anticancer therapy.

  16. Propulsion at low Reynolds number via beam extrusion

    NASA Astrophysics Data System (ADS)

    Gosselin, Frederick; Neetzow, Paul

    2014-03-01

    We present experimental and theoretical results on the extrusion of a slender beam in a viscous fluid. We are particularly interested in the force necessary to extrude the beam as it buckles with large amplitude due to viscous friction. The problem is inspired by the propulsion of Paramecium via trichocyst extrusion. Self-propulsion in micro-organisms is mostly achieved through the beating of flagella or cilia. However, to avoid a severe aggression, unicellular Paramecium has been observed to extrude trichocysts in the direction of the aggression to burst away. These trichocysts are rod-like organelles which, upon activation, grow to about 40 μm in length in 3 milliseconds before detaching from the animal. The drag force created by these extruding rods pushing against the viscous fluid generates thrust in the opposite direction. We developed an experimental setup to measure the force required to push a steel piano wire into an aquarium filled with corn syrup. This setup offers a near-zero Reynolds number, and allows studying deployments for a range of constant extrusion speeds. The experimental results are reproduced with a numerical model coupling a large amplitude Euler-Bernoulli beam theory with a fluid load model proportional to the local beam velocity. This study was funded in part by the The Natural Sciences and Engineering Research Council of Canada.

  17. Daunorubicin-Loaded DNA Origami Nanostructures Circumvent Drug-Resistance Mechanisms in a Leukemia Model.

    PubMed

    Halley, Patrick D; Lucas, Christopher R; McWilliams, Emily M; Webber, Matthew J; Patton, Randy A; Kural, Comert; Lucas, David M; Byrd, John C; Castro, Carlos E

    2016-01-20

    Many cancers show primary or acquired drug resistance due to the overexpression of efflux pumps. A novel mechanism to circumvent this is to integrate drugs, such as anthracycline antibiotics, with nanoparticle delivery vehicles that can bypass intrinsic tumor drug-resistance mechanisms. DNA nanoparticles serve as an efficient binding platform for intercalating drugs (e.g., anthracyclines doxorubicin and daunorubicin, which are widely used to treat acute leukemias) and enable precise structure design and chemical modifications, for example, for incorporating targeting capabilities. Here, DNA nanostructures are utilized to circumvent daunorubicin drug resistance at clinically relevant doses in a leukemia cell line model. The fabrication of a rod-like DNA origami drug carrier is reported that can be controllably loaded with daunorubicin. It is further directly verified that nanostructure-mediated daunorubicin delivery leads to increased drug entry and retention in cells relative to free daunorubicin at equal concentrations, which yields significantly enhanced drug efficacy. Our results indicate that DNA origami nanostructures can circumvent efflux-pump-mediated drug resistance in leukemia cells at clinically relevant drug concentrations and provide a robust DNA nanostructure design that could be implemented in a wide range of cellular applications due to its remarkably fast self-assembly (≈5 min) and excellent stability in cell culture conditions.

  18. Effect of Zn2+ Substitution on the Structure and Magnetic Properties of Co0.5Cu0.5Fe2O4 Synthesized by Solvothermal Method

    NASA Astrophysics Data System (ADS)

    Huang, Xusheng; Zhou, Yuan; Wu, Wenwei; Xu, Jiawei; Liu, Shangqian; Liu, Dongsheng; Wu, Juan

    2016-06-01

    A series of Zn2+ doped Co-Cu ferrites with the formula Co0.5Cu0.5- x Zn x Fe2O4 (0.0 ≤ x ≤ 0.3) have been successfully synthesized using the solvothermal method. X-ray diffraction and scanning electron microscopy results indicate that a high-crystallized cubic Co0.5Cu0.5- x Zn x Fe2O4 with rod-like structure is obtained when the precursor is calcined at 800°C in air for 3 h. The lattice parameters increase with the increase of Zn2+ additional amount, attributed to the larger ionic radius of the substituted ion Zn2+ than Cu2+ ionic radius. Zn2+ substitution can improve the magnetic properties of Co0.5Cu0.5- x Zn x Fe2O4. Co0.5Cu0.4Zn0.1Fe2O4 obtained at 800°C has the highest specific saturation magnetization (73.7 ± 0.9 emu/g) and magnetic moment (3.13 ± 0.04 B.M.).

  19. Free-Standing Optically Switchable Chiral Plasmonic Photonic Crystal Based on Self-Assembled Cellulose Nanorods and Gold Nanoparticles.

    PubMed

    Chu, Guang; Wang, Xuesi; Yin, Hang; Shi, Ying; Jiang, Haijing; Chen, Tianrui; Gao, Jianxiong; Qu, Dan; Xu, Yan; Ding, Dajun

    2015-10-07

    Photonic crystals incorporating with plasmonic nanoparticles have recently attracted considerable attention due to their novel optical properties and potential applications in future subwavelength optics, biosensing and data storage device. Here we demonstrate a free-standing chiral plasmonic film composed of entropy-driven self-co-assembly of gold nanoparticles (GNPs) and rod-like cellulose nanocrystals (CNCs). The CNCs-GNPs composite films not only preserve the photonic ordering of the CNCs matrix but also retain the plasmonic resonance of GNPs, leading to a distinct plasmon-induced chiroptical activity and a strong resonant plasmonic-photonic coupling that is confirmed by the stationary and ultrafast transient optical response. Switchable optical activity can be obtained by either varying the incidence angle of lights, or by taking advantage of the responsive feature of the CNCs matrix. Notably, an angle-dependent plasmon resonance in chiral nematic hybrid film has been observed for the first time, which differs drastically from that of the GNPs embed in three-dimensional photonic crystals, revealing a close relation with the structure of the host matrix. The current approach for fabricating device-scale, macroscopic chiral plasmonic materials from abundant CNCs with robust chiral nematic matrix may enable the mass production of functional optical metamaterials.

  20. Effect of aluminium doping on structural and optical properties of ZnO thin films by sol-gel method

    SciTech Connect

    Vijayaprasath, G.; Murugan, R.; Ravi, G. E-mail: gravicrc@gmail.com; Hayakawa, Y.

    2015-06-24

    We systematically investigated the structural, morphological and optical properties of 0.05 mol % Al doped ZnO (Al:ZnO) thin films deposited on glass substrates by sol-gel spin coating method. The influences of Al doping in ZnO thin films are characterized by Powder X-ray diffraction study. ZnO and Al:ZnO thin films have showed hexagonal wurtzite structure without any secondary phase in c-axis (002) orientation. The SEM images also proved the hexagonal rod like morphologies for both films. All the films exhibited transmittance of 70-80% in the visible range up to 800 nm and cut-off wavelength observed at ∼390 nm corresponding to the fundamental absorption of ZnO. The band gap of the ZnO thin films slightly widened with the Al doping. The photoluminescence properties have been studied for Al: ZnO thin films and the results are presented in detail.