Soot superaggregates from flaming wildfires and their direct radiative forcing.

PubMed

Chakrabarty, Rajan K; Beres, Nicholas D; Moosmüller, Hans; China, Swarup; Mazzoleni, Claudio; Dubey, Manvendra K; Liu, Li; Mishchenko, Michael I

2014-07-01

Wildfires contribute significantly to global soot emissions, yet their aerosol formation mechanisms and resulting particle properties are poorly understood and parameterized in climate models. The conventional view holds that soot is formed via the cluster-dilute aggregation mechanism in wildfires and emitted as aggregates with fractal dimension Df ≈ 1.8 mobility diameter Dm ≤ 1 μm, and aerodynamic diameter Da ≤ 300 nm. Here we report the ubiquitous presence of soot superaggregates (SAs) in the outflow from a major wildfire in India. SAs are porous, low-density aggregates of cluster-dilute aggregates with characteristic Df ≈ 2.6, Dm > 1 μm, and Da ≤ 300 nm that form via the cluster-dense aggregation mechanism. We present additional observations of soot SAs in wildfire smoke-laden air masses over Northern California, New Mexico, and Mexico City. At 550 nm wavelength, [corrected] we estimate that SAs contribute, per unit optical depth, up to 35% less atmospheric warming than freshly-emitted (D(f) ≈ 1.8) [corrected] aggregates, and ≈90% more warming than the volume-equivalent spherical soot particles simulated in climate models.

Soot superaggregates from flaming wildfires and their direct radiative forcing

PubMed Central

Chakrabarty, Rajan K.; Beres, Nicholas D.; Moosmüller, Hans; China, Swarup; Mazzoleni, Claudio; Dubey, Manvendra K.; Liu, Li; Mishchenko, Michael I.

2014-01-01

Wildfires contribute significantly to global soot emissions, yet their aerosol formation mechanisms and resulting particle properties are poorly understood and parameterized in climate models. The conventional view holds that soot is formed via the cluster-dilute aggregation mechanism in wildfires and emitted as aggregates with fractal dimension Df ≈ 1.8 mobility diameter Dm ≤ 1 μm, and aerodynamic diameter Da ≤ 300 nm. Here we report the ubiquitous presence of soot superaggregates (SAs) in the outflow from a major wildfire in India. SAs are porous, low-density aggregates of cluster-dilute aggregates with characteristic Df ≈ 2.6, Dm > 1 μm, and Da ≤ 300 nm that form via the cluster-dense aggregation mechanism. We present additional observations of soot SAs in wildfire smoke-laden air masses over Northern California, New Mexico, and Mexico City. We estimate that SAs contribute, per unit optical depth, up to 35% less atmospheric warming than freshly-emitted (Df ≈ 1.8) aggregates, and ≈90% more warming than the volume-equivalent spherical soot particles simulated in climate models. PMID:24981204

Relaxation times and modes of disturbed aggregate distribution in micellar solutions with fusion and fission of micelles

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

Zakharov, Anatoly I.; Adzhemyan, Loran Ts.; Shchekin, Alexander K., E-mail: akshch@list.ru

2015-09-28

We have performed direct numerical calculations of the kinetics of relaxation in the system of surfactant spherical micelles under joint action of the molecular mechanism with capture and emission of individual surfactant molecules by molecular aggregates and the mechanism of fusion and fission of the aggregates. As a basis, we have taken the difference equations of aggregation and fragmentation in the form of the generalized kinetic Smoluchowski equations for aggregate concentrations. The calculations have been made with using the droplet model of molecular surfactant aggregates and two modified Smoluchowski models for the coefficients of aggregate-monomer and aggregate-aggregate fusions which takemore » into account the effects of the aggregate size and presence of hydrophobic spots on the aggregate surface. A full set of relaxation times and corresponding relaxation modes for nonequilibrium aggregate distribution in the aggregation number has been found. The dependencies of these relaxation times and modes on the total concentration of surfactant in the solution and the special parameter controlling the probability of fusion in collisions of micelles with other micelles have been studied.« less

Recording ion channels across soy-extracted lecithin bilayer generated by water-soluble quantum dots

NASA Astrophysics Data System (ADS)

Sarma, Runjun; Mohanta, Dambarudhar

2014-02-01

We report on the quantum dot (QD)-induced ion channels across a soya-derived lecithin bilayer supported on a laser drilled of ~100 μm aperture of cellulose acetate substrate that separates two electrolytic chambers. Adequate current bursts were observed when the bilayer was subjected to a gating voltage. The voltage-dependent current fluctuation, across the bilayer, was attributed to the insertion of ~20 nm sized water-soluble CdSe QDs, forming nanopores due to their spontaneous aggregation. Apart from a closed state, the first observable conductance levels were found as 6.3 and 11 nS, as for the respective biasing voltages of -10 and -20 mV. The highest observable conductance states, at corresponding voltages were ~14.3 and 21.1 nS. Considering two simplified models, we predict that the non-spherical pores (dnspore) can be a better approximation over spherical nanopores (dspore) for exhibiting a definite conductance level. At times, even dnspore ≤ 4dspore and that the non-spherical nanopores were associated with a smaller No. of QDs than the case for spherical nanopores, for a definite conductance state. It seems like the current events are partly stochastic, possibly due to thermal effects on the aggregated QDs that would form nanopores. The dwell time of the states was predicted in the range of 384-411 μs. The ion channel mechanism in natural phospholipid bilayers over artificial ones will provide a closer account to understand ion transport mechanism in live cells and signaling activity including labelling with fluorescent QDs.

Formation and shape-control of hierarchical cobalt nanostructures using quaternary ammonium salts in aqueous media

PubMed Central

Deshmukh, Ruchi; Mehra, Anurag

2017-01-01

Aggregation and self-assembly are influenced by molecular interactions. With precise control of molecular interactions, in this study, a wide range of nanostructures ranging from zero-dimensional nanospheres to hierarchical nanoplates and spindles have been successfully synthesized at ambient temperature in aqueous solution. The nanostructures reported here are formed by aggregation of spherical seed particles (monomers) in presence of quaternary ammonium salts. Hydroxide ions and a magnetic moment of the monomers are essential to induce shape anisotropy in the nanostructures. The cobalt nanoplates are studied in detail, and a growth mechanism based on collision, aggregation, and crystal consolidation is proposed based on a electron microscopy studies. The growth mechanism is generalized for rods, spindles, and nearly spherical nanostructures, obtained by varying the cation group in the quaternary ammonium hydroxides. Electron diffraction shows different predominant lattice planes on the edge and on the surface of a nanoplate. The study explains, hereto unaddressed, the temporal evolution of complex magnetic nanostructures. These ferromagnetic nanostructures represent an interesting combination of shape anisotropy and magnetic characteristics. PMID:28326240

Cohesion, granular solids, granular liquids, and their connection to small near-Earth objects

NASA Astrophysics Data System (ADS)

Sánchez, P.; Scheeres, D.

2014-07-01

During the last 15 years or so, the Planetary Sciences community has been using Discrete Element Method (DEM) simulation codes to study small near-Earth objects (NEOs). In general, these codes treat gravitational aggregates as conglomerates of spherical particles; a good approximation given that many asteroids are self-gravitating granular media. Unfortunately, the degree of sophistication of these codes, and our own understanding, has not been high enough as to appropriately represent realistic physical properties of granular matter. In particular, angles of friction (θ) and cohesive strength (σ_c) of the aggregates were rarely taken in consideration and this could have led to unrealistic dynamics, and therefore, unrealistic conclusions about the dynamical evolution of small NEOs. In our research, we explore the failure mechanics of spherical (r=71 m) and ellipsoidal (r_1=92 m) self-gravitating aggregates with different angles of friction and values for their cohesive strength, in order to better understand the geophysics of rubble-pile asteroids. In particular we focused on the deformation and different disruption modes provoked by an always increasing angular velocity (spin rate). Scaling arguments allow us to regard simulations with the same aggregate size and different σ_c as equivalent to simulations of aggregates of different size and the same σ_c. We use a computational code that implements a Soft-Sphere DEM. The aggregates are composed by 3,000 spherical solid spheres (7--10 m) with 6 degrees of freedom. The code calculates normal, as well as, frictional (tangential) contact forces by means of soft potentials and the aggregate as a whole mimics the effect of non- spherical particles through the implementation of rolling friction. Cohesive forces, and a cohesive stress, are calculated as the net effect of the sum of the van der Waals forces between the smaller regolith, sand and dust (powder) that are present in real asteroids [1]. These finer materials form a matrix of sorts that holds the bigger boulders together. The aggregates were slowly spun up to disruption controlling for angle of friction, cohesion and global shape. Systems with no frictional forces had θ≈ 12° and are in effect granular liquids in the best case scenario. Systems with only surface-surface friction had θ≈ 25°, which is typical in laboratory experiments with spherical glass beads. Systems that also implemented rolling friction had θ≈ 35°, which is typical of non-cohesive granular media on the Earth. How much each aggregate deformed before disruption was directly related to the angle of friction. The greater θ allowed for much less deformation before disruption. Cohesive forces on the other hand controlled the mode of disruption and maximum spin rate and showed that the change from shedding to fission is continuous and therefore, they should not be seen as different disruption processes. The figure shows the deformation and disruption of three initially spherical aggregates (left) and three initially ellipsoidal aggregates (right) with increasing cohesive strength from left to right (θ≈ 35°). Through scaling arguments we could also see these aggregates as having the exact same σ_c=25 Pa but different sizes. If we do that, the aggregates measure about 1.6 km, 5 km, and 22 km, and the particles, or groups of particles being detached now have similar sizes. This has now become a problem of resolution, i.e., the number and size of particles used in a simulation. These results start to raise fundamental questions regarding the difference between shedding and fission. Is it shedding when it is dust grain by dust grain ejection from the main body or when it is in groups of 10, 100, or 100,000 dust particles? Is it fission when a 1-m piece of the asteroid detaches or when it splits in the middle? Which values of θ and σ_c are realistic? These and other questions will be explored.

Aggregation behavior of sodium lauryl ether sulfate with a positively bicharged organic salt and effects of the mixture on fluorescent properties of conjugated polyelectrolytes.

PubMed

Tang, Yongqiang; Liu, Zhang; Zhu, Linyi; Han, Yuchun; Wang, Yilin

2015-02-24

The aggregation behavior of anionic single-chain surfactant sodium lauryl ether sulfate containing three ether groups (SLE3S) with positively bicharged organic salt 1,2-bis(2-benzylammoniumethoxy)ethane dichloride (BEO) has been investigated in aqueous solution, and the effects of the BEO/SLE3S aggregate transitions on the fluorescent properties of anionic conjugated polyelectrolyte MPS-PPV with a larger molecular weight and cationic conjugated oligoelectrolyte DAB have been evaluated. Without BEO, SLE3S does not affect the fluorescent properties of MPS-PPV and only affects the fluorescent properties of DAB at a higher SLE3S concentration. With the addition of BEO, SLE3S and BEO form gemini-like surfactant (SLE3S)2-BEO. When the BEO/SLE3S molar ratio is fixed at 0.25, with increasing the BEO/SLE3S concentration, the BEO/SLE3S mixture forms large, loosely arranged aggregates and then transforms to closely packed spherical aggregates and finally to long thread-like micelles. The photoluminescence (PL) intensity of MPS-PPV varies with the morphologies of the BEO/SLE3S aggregates, while the PL intensity of DAB is almost independent of the aggregate morphologies. The results demonstrate that gemini-like surfactants formed through intermolecular interactions can effectively adjust the fluorescent properties of conjugated polyelectrolytes.

Polymersomes from dual responsive block copolymers: drug encapsulation by heating and acid-triggered release.

PubMed

Qiao, Zeng-Ying; Ji, Ran; Huang, Xiao-Nan; Du, Fu-Sheng; Zhang, Rui; Liang, De-Hai; Li, Zi-Chen

2013-05-13

A series of well-defined thermoresponsive diblock copolymers (PEO45-b-PtNEAn, n=22, 44, 63, 91, 172) were prepared by the atom transfer radical polymerization of trans-N-(2-ethoxy-1,3-dioxan-5-yl) acrylamide (tNEA) using a poly(ethylene oxide) (PEO45) macroinitiator. All copolymers are water-soluble at low temperature, but upon quickly heating to 37 °C, laser light scattering (LLS) and transmission electron microscopy (TEM) characterizations indicate that these copolymers self-assemble into aggregates with different morphologies depending on the chain length of PtNEA and the polymer concentration; the morphologies gradually evolved from spherical solid nanoparticles to a polymersome as the degree of polymerization ("n") of PtNEA block increased from 22 to 172, with the formation of clusters with rod-like structure at the intermediate PtNEA length. Both the spherical nanoparticle and the polymersome are stable at physiological pH but susceptible to the mildly acidic medium. Acid-triggered hydrolysis behaviors of the aggregates were investigated by LLS, Nile red fluorescence, TEM, and (1)H NMR spectroscopy. The results revealed that the spherical nanoparticles formed from PEO45-b-PtNEA44 dissociated faster than the polymersomes of PEO45-b-PtNEA172, and both aggregates showed an enhanced hydrolysis under acidic conditions. Both the spherical nanoparticle and polymersome are able to efficiently load the hydrophobic doxorubicin (DOX), and water-soluble fluorescein isothiocyanate-lysozyme (FITC-Lys) can be conveniently encapsulated into the polymersome without using any organic solvent. Moreover, FITC-Lys and DOX could be coloaded in the polymersome. The drugs loaded either in the polymersome or in the spherical nanoparticle could be released by acid triggering. Finally, the DOX-loaded assemblies display concentration-dependent cytotoxicity to HepG2 cells, while the copolymers themselves are nontoxic.

Anti-fibrillogenic properties of phthalocyanines: effect of the out-of-plane ligands.

PubMed

Kovalska, V; Cherepanov, V; Losytskyy, M; Chernii, S; Senenko, A; Chernii, V; Tretyakova, I; Yarmoluk, S; Volkov, S

2014-12-15

The axially-coordinated phthalocyanines were previously reported as agents possessing strong anti-fibrillogenic properties. In the presented study we used the atomic force microscopy to investigate the intermediates and the products of insulin aggregation reaction formed in the presence of Zr and Hf phthalocyanine complexes that contain out-of-plane ligands of different size and nature. It is shown that while phthalocyanine-free insulin generated mostly amyloid fibrils with a diameter of 2-8nm and a length of up to 5μm, the presence of phthalocyanines with spatial bulky ligands (PcZrDbm2) leads to the redirection of the fibrillization reaction to the formation of the spherical oligomer aggregates with a diameter of 4-12nm. At the same time the phthalocyanine complex PcHfCl2 having the small-volume ligands induces the formation of large size insulin aggregates with a height of about 100nm that are supposed to be amorphous species. The study of the aggregation intermediates showed the certain similarity of the reaction passing for phthalocyanine-free insulin and insulin in the presence of PcZrDbm2. The large-size amorphous species were observed at the beginning of reaction, later they dissociated, leading to the formation and growth of the smaller size particles. The amyloid-sensitive cyanine dye 7519 demonstrates the strong fluorescent response both in the presence of fibrils and spherical oligomers, while it is non-sensitive to amorphous aggregates. Copyright © 2014 Elsevier Ltd. All rights reserved.

Stable J-aggregation enabled dual photoacoustic and fluorescence nanoparticles for intraoperative cancer imaging

NASA Astrophysics Data System (ADS)

Shakiba, Mojdeh; Ng, Kenneth K.; Huynh, Elizabeth; Chan, Harley; Charron, Danielle M.; Chen, Juan; Muhanna, Nidal; Foster, F. Stuart; Wilson, Brian C.; Zheng, Gang

2016-06-01

J-aggregates display nanoscale optical properties which enable their use in fluorescence and photoacoustic imaging applications. However, control over their optical properties in an in vivo setting is hampered by the conformational lability of the J-aggregate structure in complex biological environments. J-aggregating nanoparticles (JNP) formed by self-assembly of bacteriopheophorbide-lipid (Bchl-lipid) in lipid nanovesicles represents a novel strategy to stabilize J-aggregates for in vivo bioimaging applications. We find that 15 mol% Bchl-lipid embedded within a saturated phospholipid bilayer vesicle was optimal in terms of maximizing Bchl-lipid dye loading, while maintaining a spherical nanoparticle morphology and retaining spectral properties characteristic of J-aggregates. The addition of cholesterol maintains the stability of the J-aggregate absorption band for up to 6 hours in the presence of 90% FBS. In a proof-of-concept experiment, we successfully applied JNPs as a fluorescence contrast agent for real-time intraoperative detection of metastatic lymph nodes in a rabbit head-and-neck cancer model. Lymph node metastasis delineation was further verified by visualizing the JNP within the excised lymph node using photoacoustic imaging. Using JNPs, we demonstrate the possibility of using J-aggregates as fluorescence and photoacoustic contrast agents and may potentially spur the development of other nanomaterials that can stably induce J-aggregation for in vivo cancer bioimaging applications.J-aggregates display nanoscale optical properties which enable their use in fluorescence and photoacoustic imaging applications. However, control over their optical properties in an in vivo setting is hampered by the conformational lability of the J-aggregate structure in complex biological environments. J-aggregating nanoparticles (JNP) formed by self-assembly of bacteriopheophorbide-lipid (Bchl-lipid) in lipid nanovesicles represents a novel strategy to stabilize J-aggregates for in vivo bioimaging applications. We find that 15 mol% Bchl-lipid embedded within a saturated phospholipid bilayer vesicle was optimal in terms of maximizing Bchl-lipid dye loading, while maintaining a spherical nanoparticle morphology and retaining spectral properties characteristic of J-aggregates. The addition of cholesterol maintains the stability of the J-aggregate absorption band for up to 6 hours in the presence of 90% FBS. In a proof-of-concept experiment, we successfully applied JNPs as a fluorescence contrast agent for real-time intraoperative detection of metastatic lymph nodes in a rabbit head-and-neck cancer model. Lymph node metastasis delineation was further verified by visualizing the JNP within the excised lymph node using photoacoustic imaging. Using JNPs, we demonstrate the possibility of using J-aggregates as fluorescence and photoacoustic contrast agents and may potentially spur the development of other nanomaterials that can stably induce J-aggregation for in vivo cancer bioimaging applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/C5NR08165C

Soot Superaggregates from Flaming Wildfires and Their Direct Radiative Forcing

NASA Technical Reports Server (NTRS)

Chakrabarty, Rajan K.; Beres, Nicholas D.; Moosmuller,Hans; China, Swarup; Mazzoleni, Claudio; Dubey, Manvendra K.; Liu, Li; Mishchenko, Michael I.

2014-01-01

Wildfires contribute significantly to global soot emissions, yet their aerosol formation mechanisms and resulting particle properties are poorly understood and parameterized in climate models. The conventional view holds that soot is formed via the cluster-dilute aggregation mechanism in wildfires and emitted as aggregates with fractal dimension D(sub f) approximately equals 1.8 mobility diameter D(sub m) (is) less than or equal to 1 micron, and aerodynamic diameter D(sub a) (is) less than or equal to 300 nm. Here we report the ubiquitous presence of soot superaggregates (SAs) in the outflow from a major wildfire in India. SAs are porous, low-density aggregates of cluster-dilute aggregates with characteristic D(sub f) approximately equals 2.6,D(sub m) (is) greater than 1 micron, and D(sub a) is less than or equal to 300 nm that form via the cluster-dense aggregation mechanism.We present additional observations of soot SAs in wildfire smoke-laden air masses over Northern California, New Mexico, and Mexico City. We estimate that SAs contribute, per unit optical depth, up to 35% less atmospheric warming than freshly-emitted (D(sub f) approximately equals 1.8) aggregates, and approximately equals 90% more warming than the volume-equivalent spherical soot particles simulated in climate models.

Transient shear viscosity of weakly aggregating polystyrene latex dispersions

NASA Astrophysics Data System (ADS)

de Rooij, R.; Potanin, A. A.; van den Ende, D.; Mellema, J.

1994-04-01

The transient behavior of the viscosity (stress growth) of a weakly aggregating polystyrene latex dispersion after a step from a high shear rate to a lower shear rate has been measured and modeled. Single particles cluster together into spherical fractal aggregates. The steady state size of these aggregates is determined by the shear stresses exerted on the latter by the flow field. The restructuring process taking place when going from a starting situation with monodisperse spherical aggregates to larger monodisperse spherical aggregates is described by the capture of primary fractal aggregates by growing aggregates until a new steady state is reached. It is assumed that the aggregation mechanism is diffusion limited. The model is valid if the radii of primary aggregates Rprim are much smaller than the radii of the growing aggregates. Fitting the model to experimental data at two volume fractions and a number of step sizes in shear rate yielded physically reasonable values of Rprim at fractal dimensions 2.1≤df≤2.2. The latter range is in good agreement with the range 2.0≤df≤2.3 obtained from steady shear results. The experimental data have also been fitted to a numerical solution of the diffusion equation for primary aggregates for a cell model with moving boundary, also yielding 2.1≤df≤2.2. The range for df found from both approaches agrees well with the range df≊2.1-2.2 determined from computer simulations on diffusion-limited aggregation including restructuring or thermal breakup after formation of bonds. Thus a simple model has been put forward which may capture the basic features of the aggregating model dispersion on a microstructural level and leads to physically acceptable parameter values.

DDA Computations of Porous Aggregates with Forsterite Crystals: Effects of Crystal Shape and Crystal Mass Fraction

NASA Technical Reports Server (NTRS)

Wooden, Diane H.; Lindsay, Sean S.; Harker, David; Woodward, Charles; Kelley, Michael S.; Kolokolova, Ludmilla

2015-01-01

Porous aggregate grains are commonly found in cometary dust samples and are needed to model cometary IR spectral energy distributions (SEDs). Models for thermal emissions from comets require two forms of silicates: amorphous and crystalline. The dominant crystal resonances observed in comet SEDs are from Forsterite (Mg2SiO4). The mass fractions that are crystalline span a large range from 0.0 < or = fcrystal < or = 0.74. Radial transport models that predict the enrichment of the outer disk (>25 AU at 1E6 yr) by inner disk materials (crystals) are challenged to yield the highend-range of cometary crystal mass fractions. However, in current thermal models, Forsterite crystals are not incorporated into larger aggregate grains but instead only are considered as discrete crystals. A complicating factor is that Forsterite crystals with rectangular shapes better fit the observed spectral resonances in wavelength (11.0-11.15 microns, 16, 19, 23.5, 27, and 33 microns), feature asymmetry and relative height (Lindley et al. 2013) than spherically or elliptically shaped crystals. We present DDA-DDSCAT computations of IR absorptivities (Qabs) of 3 micron-radii porous aggregates with 0.13 < or = fcrystal < or = 0.35 and with polyhedral-shaped Forsterite crystals. We can produce crystal resonances with similar appearance to the observed resonances of comet Hale- Bopp. Also, a lower mass fraction of crystals in aggregates can produce the same spectral contrast as a higher mass fraction of discrete crystals; the 11micron and 23 micron crystalline resonances appear amplified when crystals are incorporated into aggregates composed otherwise of spherically shaped amorphous Fe-Mg olivines and pyroxenes. We show that the optical properties of a porous aggregate is not linear combination of its monomers, so aggregates need to be computed. We discuss the consequence of lowering comet crystal mass fractions by modeling IR SEDs with aggregates with crystals, and the implications for radial transport models of our protoplanetary disk.

Atomic force microscope characterization of self-assembly behaviors of cyclo[8] pyrrole on solid substrates

NASA Astrophysics Data System (ADS)

Xu, Hai; Zhao, Siqi; Xiong, Xiang; Jiang, Jinzhi; Xu, Wei; Zhu, Daoben; Zhang, Yi; Liang, Wenjie; Cai, Jianfeng

2017-04-01

Cyclo [8] pyrrole (CP) is a porphyrin analogue containing eight α-conjugated pyrrole units which are arranged in a nearly coplanar conformation. The π-π interactions between CP molecules lead to regular aggregations through a solution casting process. Using tapping mode atomic force microscope (AFM), we investigated the morphology of self-assembled aggregates formed by deposition of different CP solutions on different substrates. We found that in the n-butanol solution, nanofibrous structures could be formed on the silicon or mica surface. Interestingly, on the highly oriented pyrolytic graphite (HOPG) surface, or silicon and mica surface with a toluene solution, only irregular spherical structures were identified. The difference in the nanomorphology may be attributed to distinct interactions between molecule-molecule, molecule-solvent and molecule-substrate.

Tunable Porosities and Shapes of Fullerene-Like Spheres

PubMed Central

Dielmann, Fabian; Fleischmann, Matthias; Heindl, Claudia; Peresypkina, Eugenia V; Virovets, Alexander V; Gschwind, Ruth M; Scheer, Manfred

2015-01-01

The formation of reversible switchable nanostructures monitored by solution and solid-state methods is still a challenge in supramolecular chemistry. By a comprehensive solid state and solution study we demonstrate the potential of the fivefold symmetrical building block of pentaphosphaferrocene in combination with CuI halides to switch between spheres of different porosity and shape. With increasing amount of CuX, the structures of the formed supramolecules change from incomplete to complete spherically shaped fullerene-like assemblies possessing an Ih-C80 topology at one side and to a tetrahedral-structured aggregate at the other. In the solid state, the formed nano-sized aggregates reach an outer diameter of 3.14 and 3.56 nm, respectively. This feature is used to reversibly encapsulate and release guest molecules in solution. PMID:25759976

Structure Analyses of Highly Symmetric Superstructures Formed by Rodlike Mesogen

NASA Astrophysics Data System (ADS)

Saito, Kazuya; Kutsumizu, Shoichi

Process of structure determination of liquid-crystalline superstructures formed in a mesogenic series, bis(n-alkoxybenzoyl)hydrazine[BABH(n) ; n, the number of carbon atoms in the alkoxy group], is described. The chain-length (n) dependence of relative diffraction intensities from the Ia3d phase resolves the phase problem, leading to the structural description that the molecular centers are on the rods forming two interpenetrating jungle gyms. Theoretical consideration on the stability of superstructures and systematic MEM analysis reveal the coexistence of two aggregation modes (rods forming an extending jungle gym and closed sheets forming spherical shells) for the Im3m phase.

A mechanistic model for the evolution of multicellularity

NASA Astrophysics Data System (ADS)

Amado, André; Batista, Carlos; Campos, Paulo R. A.

2018-02-01

Through a mechanistic approach we investigate the formation of aggregates of variable sizes, accounting mechanisms of aggregation, dissociation, death and reproduction. In our model, cells can produce two metabolites, but the simultaneous production of both metabolites is costly in terms of fitness. Thus, the formation of larger groups can favor the aggregates to evolve to a configuration where division of labor arises. It is assumed that the states of the cells in a group are those that maximize organismal fitness. In the model it is considered that the groups can grow linearly, forming a chain, or compactly keeping a roughly spherical shape. Starting from a population consisting of single-celled organisms, we observe the formation of groups with variable sizes and usually much larger than two-cell aggregates. Natural selection can favor the formation of large groups, which allows the system to achieve new and larger fitness maxima.

Biogenic formation and growth of uraninite (UO₂).

PubMed

Lee, Seung Yeop; Baik, Min Hoon; Choi, Jong Won

2010-11-15

Biogenic UO₂ (uraninite) nanocrystals may be formed as a product of a microbial reduction process in uranium-enriched environments near the Earth's surface. We investigated the size, nanometer-scale structure, and aggregation state of UO₂ formed by iron-reducing bacterium, Shewanella putrefaciens CN32, from a uranium-rich solution. Characterization of biogenic UO₂ precipitates by high-resolution transmission electron microscopy (HRTEM) revealed that the UO₂ nanoparticles formed were highly aggregated by organic polymers. Nearly all of the nanocrystals were networked in more or less 100 nm diameter spherical aggregates that displayed some concentric UO₂ accumulation with heterogeneity. Interestingly, pure UO₂ nanocrystals were piled on one another at several positions via UO₂-UO₂ interactions, which seem to be intimately related to a specific step in the process of growing large single crystals. In the process, calcium that was easily complexed with aqueous uranium(VI) appeared not to be combined with bioreduced uranium(IV), probably due to its lower binding energy. However, when phosphate was added to the system, calcium was found to be easily associated with uranium(IV), forming a new uranium phase, ningyoite. These results will extend the limited knowledge of microbial uraniferous mineralization and may provide new insights into the fate of aqueous uranium complexes.

Spherical and hyperspherical harmonics representation of van der Waals aggregates

NASA Astrophysics Data System (ADS)

Lombardi, Andrea; Palazzetti, Federico; Aquilanti, Vincenzo; Grossi, Gaia; Albernaz, Alessandra F.; Barreto, Patricia R. P.; Cruz, Ana Claudia P. S.

2016-12-01

The representation of the potential energy surfaces of atom-molecule or molecular dimers interactions should account faithfully for the symmetry properties of the systems, preserving at the same time a compact analytical form. To this aim, the choice of a proper set of coordinates is a necessary precondition. Here we illustrate a description in terms of hyperspherical coordinates and the expansion of the intermolecular interaction energy in terms of hypersherical harmonics, as a general method for building potential energy surfaces suitable for molecular dynamics simulations of van der Waals aggregates. Examples for the prototypical case diatomic-molecule-diatomic-molecule interactions are shown.

Gelling Mechanism of Aluminum Di-Soaps in Oils

NASA Astrophysics Data System (ADS)

Wang, Xiaorong; Rackaitis, Mindaugas

2009-03-01

This work demonstrates that aluminum di-soaps form nano-sized spherical micelles in the oils and that the aggregation of these micelles forms a network that gives rise to a gel formation -- thereby refuting a long-held belief that the gel formation was the result of linear polymeric chains of aluminum association. The discovery of such aluminum nano-particles could expand application of these materials to new technologies because these materials are chemically inert, odorless and nontoxic, and have been widely used in greases, paints, gels, cosmetics, drugs and foods.

Shear-induced aggregation or disaggregation in edible oils: Models, computer simulation, and USAXS measurements

NASA Astrophysics Data System (ADS)

Townsend, B.; Peyronel, F.; Callaghan-Patrachar, N.; Quinn, B.; Marangoni, A. G.; Pink, D. A.

2017-12-01

The effects of shear upon the aggregation of solid objects formed from solid triacylglycerols (TAGs) immersed in liquid TAG oils were modeled using Dissipative Particle Dynamics (DPD) and the predictions compared to experimental data using Ultra-Small Angle X-ray Scattering (USAXS). The solid components were represented by spheres interacting via attractive van der Waals forces and short range repulsive forces. A velocity was applied to the liquid particles nearest to the boundary, and Lees-Edwards boundary conditions were used to transmit this motion to non-boundary layers via dissipative interactions. The shear was created through the dissipative forces acting between liquid particles. Translational diffusion was simulated, and the Stokes-Einstein equation was used to relate DPD length and time scales to SI units for comparison with USAXS results. The SI values depended on how large the spherical particles were (250 nm vs. 25 nm). Aggregation was studied by (a) computing the Structure Function and (b) quantifying the number of pairs of solid spheres formed. Solid aggregation was found to be enhanced by low shear rates. As the shear rate was increased, a transition shear region was manifested in which aggregation was inhibited and shear banding was observed. Aggregation was inhibited, and eventually eliminated, by further increases in the shear rate. The magnitude of the transition region shear, γ˙ t, depended on the size of the solid particles, which was confirmed experimentally.

In-vivo observations of a spherical aggregate of endoplasmic reticulum and of Golgi vesicles in the tip of fast-growing Chara rhizoids.

PubMed

Bartnik, E; Sievers, A

1988-11-01

In-vivo differential interference contrast microscopy was used to detect individual Golgi vesicles and a new structure in the tip of fast-growing rhizoids of Chara fragilis Desvaux. This structure is a spherical clear zone which is free of Golgi vesicles, has a diameter of 5 μm and is positioned in the center of the apical Golgi-vesicle accumulation ("Spitzenkörper"). After glutaraldehyde fixation and osmium tetroxide-potassium ferricyanide staining of the rhizoid, followed by serial sectioning and three-dimensional reconstruction, the spherical zone shows a tight accumulation of anastomosing endoplasmic reticulum (ER) membranes. The ER membranes radiate from this aggregate towards the apical plasmalemma and to the membranes of the statolith compartments. Upon gravistimulation the ER aggregate changes its position according to the new growth direction, indicating its participation in growth determination. After treatment of the rhizoid with cytochalasin B or phalloidin the ER aggregate disappears and the statoliths sediment. It is concluded that the integrity of the ER aggregate is actin-dependent and that it is related to the polar organisation of the gravitropically growing cell tip.

Amyloid fibril formation by the chain B subunit of monellin occurs by a nucleation-dependent polymerization mechanism.

PubMed

Sabareesan, A T; Udgaonkar, Jayant B

2014-02-25

Proteins possessing very different structures, or even no structure, form amyloid fibrils that are very similar in internal structure. This suggests that the mechanisms by which amyloid fibrils form might be very similar, irrespective of whether the fibrils are associated with disease or with normal cellular function, or even if they have no physiological importance. In this context, it is important to have a model protein system whose amyloid fibril formation is robust in its reproducibility, which can reveal the fundamentals of the amyloid fibril reaction that may be applicable to all proteins. In this study, the aggregation mechanism of amyloid fibril formation by chain B of the heterodimeric protein monellin has been elucidated in detail. It is shown that the aggregation reaction meets all the stringent kinetic criteria of a homogeneous nucleation-dependent polymerization mechanism, which is valid over a wide range of protein concentrations. Quantitative analyses of the kinetic data using one approach based on features of the entire kinetic curve, and another based on only the initial rate of aggregation, indicate that the thermodynamic nucleus is a dimer. Spherical oligomers are observed by atomic force microscopy to form transiently early during fibril formation but are off-pathway to the direct fibril formation pathway. It is shown that amyloid fibril formation can be prevented by the addition of chain A of monellin at early stages of chain B aggregation: the two free chains combine to form native monellin, which leads to the dissociation of early aggregates.

Self-assembly and omniphobic property of fluorinated unit end-functionalized poly(methyl methacrylate)

NASA Astrophysics Data System (ADS)

Junyan, Liang; Pingdi, Xu; Jingxian, Bao; Ling, He; Nan, Zhu

2018-03-01

The self-assembly behavior of fluorinated unit end-functionalized poly(methyl methacrylate) (PDFHM-ef-PMMA) in solution and its influence on the surface microstructure, elemental composition and omniphobic property of cast film was investigated in this work. Specifically, three mixed solutions of tetrahydrofuran (THF)/methanol (MeOH), THF/H2O and THF/H2O/MeOH in various compositions were employed separately as the selective solvents. In THF/MeOH solution, the aggregate morphologies of PDFHM-ef-PMMA changed gradually from core-shell spheres to worm, and then to elliptical vesicles as MeOH content increased. In THF/H2O solution, spherical and bowl-shaped aggregates with significantly larger sizes than those in THF/MeOH solution were favored despite lower H2O content. The further addition of MeOH to THF/H2O mixture could reduce the size of aggregate but hardly change original aggregate morphology. During the film formation process, those self-assembled aggregates in THF/MeOH solution fused with one another to form a smooth surface. When such surface was fully covered by fluorinated segments, the outstanding hexadecane and water slide-off properties and ink-resistant property required for antifouling application were demonstrated. Instead, the aggregates formed in THF/H2O/MeOH mixture were subjected to secondary aggregation of PDFHM-ef-PMMA chains during solvent evaporation, leading to the formation of a particulate film with poor adhesion towards glass plate and hexadecane-repellent property.

Artificial Loading of ASC Specks with Cytosolic Antigens

PubMed Central

Sahillioğlu, Ali Can; Özören, Nesrin

2015-01-01

Inflammasome complexes form upon interaction of Nod Like Receptor (NLR) proteins with pathogen associated molecular patterns (PAPMS) inside the cytosol. Stimulation of a subset of inflammasome receptors including NLRP3, NLRC4 and AIM2 triggers formation of the micrometer-sized spherical supramolecular complex called the ASC speck. The ASC speck is thought to be the platform of inflammasome activity, but the reason why a supramolecular complex is preferred against oligomeric platforms remains elusive. We observed that a set of cytosolic proteins, including the model antigen ovalbumin, tend to co-aggregate on the ASC speck. We suggest that co-aggregation of antigenic proteins on the ASC speck during intracellular infection might be instrumental in antigen presentation. PMID:26258904

Investigation of Microtubular Ceramic Structures

DTIC Science & Technology

1979-02-01

25 Experiments 05x - Excel ŗ-5 CAL" (Powder D). 25 Experiments 06x - Excel ŗ-5 CAL" (Powder D). 26 Experiments 07x - Stabilized Zirconia ( Powder E...an extremely fine particle size (- 0. 4 jim) for satisfactory sintering. With zirconia powder of this particle size, spherical aggregates formed...firm" packing pressure, sustained large additions (15 to--9 gm/cycle) occurred. Experiments 07x - Stabilized Zirconia ( Powder E) The 07x experiments

Metal-enhanced fluorescence of dye-doped silica nano particles.

PubMed

Gunawardana, Kalani B; Green, Nathaniel S; Bumm, Lloyd A; Halterman, Ronald L

2015-03-01

Recent advancements in metal-enhanced fluorescence (MEF) suggest that it can be a promising tool for detecting molecules at very low concentrations when a fluorophore is fixed near the surface of metal nanoparticles. We report a simple method for aggregating multiple gold nanoparticles (GNPs) on Rhodamine B (RhB)-doped silica nanoparticles (SiNPs) utilizing dithiocarbamate (DTC) chemistry to produce MEF in solution. Dye was covalently incorporated into the growing silica framework via co-condensation of a 3-aminopropyltriethoxysilane (APTES) coupled RhB precursor using the Stöber method. Electron microscopy imaging revealed that these mainly non-spherical particles were relatively large (80 nm on average) and not well defined. Spherical core-shell particles were prepared by physisorbing a layer of RhB around a small spherical silica particle (13 nm) before condensing an outer layer of silica onto the surface. The core-shell method produced nanospheres (~30 nm) that were well defined and monodispersed. Both dye-doped SiNPs were functionalized with pendant amines that readily reacted with carbon disulfide (CS2) under basic conditions to produce DTC ligands that have exhibited a high affinity for gold surfaces. GNPs were produced via citrate reduction method and the resulting 13 nm gold nanospheres were then recoated with an ether-terminated alkanethiol to provide stability in ethanol. Fluorescent enhancement was observed when excess GNPs were added to DTC coated dye-doped SiNPs to form nanoparticle aggregates. Optimization of this system gave a fluorescence brightness enhancement of over 200 fold. Samples that gave fluorescence enhancement were characterized through Transmission Emission Micrograph (TEM) to reveal a pattern of multiple aggregation of GNPs on the dye-doped SiNPs.

Clay-clast aggregates: A new textural evidence for seismic fault sliding?

NASA Astrophysics Data System (ADS)

Boutareaud, Sébastien; Calugaru, Dan-Gabriel; Han, Raehee; Fabbri, Olivier; Mizoguchi, Kazuo; Tsutsumi, Akito; Shimamoto, Toshihiko

2008-03-01

To determine the processes responsible for slip-weakening in clayey gouge zones, rotary-shear experiments were conducted at seismic slip rates (equivalent to 0.9 and 1.3 m/s) at 0.6 MPa normal stress on a natural clayey gouge for saturated and non-saturated initial conditions. The mechanical behavior of the simulated faults shows a reproducible slip-weakening behavior, whatever initial moisture conditions. Examination of gouge obtained at the residual friction stage in saturated and non-saturated initial conditions allows the definition of two types of microstructures: a foliated type reflecting strain localization, and a non-foliated type composed of spherical aggregates. Friction experiments demonstrate that liquid-vapor transition of water within gouge due to frictional heating has a high capacity to explain the formation of spherical aggregates in the first meters of displacement. This result suggests that the occurrence of spherical aggregates in natural clayey fault gouges can constitute a new textural evidence for shallow depth pore water phase transition at seismic slip velocity and consequently for past seismic fault sliding.

Genipin-crosslinked microcarriers mediating hepatocellular aggregates formation and functionalities.

PubMed

Lau, Ting Ting; Wang, Chunming; Png, Sze Wei; Su, Kai; Wang, Dong-An

2011-01-01

In engineered regenerative medicine, various types of scaffolds have been customized to pursue the optimal environment for different types of therapeutic cells. In liver therapeutic research, hepatocytes require attachment to solid anchors for survival and proliferation before they could grow into cellular aggregates with enhanced functionalities. Among the various biomaterials scaffolds and vehicles, microspherical cell carriers are suited to these requirements. Individual spheres may provide two-dimensional (2D) cell-affinitive surfaces for cell adhesion and spreading; whereas multiple microcarriers may form three-dimensional (3D) matrices with inter-spherical space for cell expansion and multicellular aggregation. In this study, we culture human liver carcinoma cell line (HepG2) cells on genipin-crosslinked gelatin microspheres of two different sizes. Results suggest that both microcarriers support cell adhesion, proliferation, and spontaneous formation of hepatocellular aggregates, among which the spheres with bigger size (200-300 μm) seem more favorable than the smaller ones in terms of aggregate formation and liver specific functionalities. These findings suggest that the genipin-crosslinked microcarrier is a competent vehicle for liver cell delivery. Copyright © 2010 Wiley Periodicals, Inc.

How the morphology of dusts influences packing density in small solar system bodies

NASA Astrophysics Data System (ADS)

Zangmeister, C.; Radney, J. G.; Zachariah, M. R.

2014-12-01

Large planetary seedlings, comets, and nanoscale soot particles are made from rigid, aggregated subunits that are compacted under low compression into larger structures spanning over 10 orders of magnitude in dimensional space. Here, we demonstrate that the packing density (Φf) of compacted rigid aggregates is independent of spatial scale for systems under weak compaction, a regime that includes small solar system bodies. The Φf of rigid aggregated structures across 6 orders of magnitude were measured using nanoscale spherical soot aerosol composed of aggregates with ≈ 17 nm monomeric subunits and aggregates made from uniform monomeric 6 mm spherical subunits at the macroscale. We find Φf = 0.36 ± 0.02 at both the nano- and macroscale. These values are remarkably similar to qf observed for comet nuclei and measured values of other rigid aggregated systems across a wide variety of spatial and formative conditions. We present a packing model that incorporates the aggregate morphology and show that Φf is independent of both monomer and aggregate size. These observations suggest thatqf of rigid aggregates is independent of spatial dimension across varied formative conditions ranging from interstellar space to pharmaceutical manufacturing.

On the radiative properties of soot aggregates - Part 2: Effects of coating

NASA Astrophysics Data System (ADS)

Liu, Fengshan; Yon, Jérôme; Bescond, Alexandre

2016-03-01

The effects of weakly absorbing material coating on soot have attracted considerable research attention in recent years due to the significant influence of such coating on soot radiative properties and the large differences predicted by different numerical models. Soot aggregates were first numerically generated using the diffusion limited cluster aggregation algorithm to produce fractal aggregates formed by log-normally distributed polydisperse spherical primary particles in point-touch. These aggregates were then processed by adding a certain amount of primary particle overlapping and necking to simulate the soot morphology observed from transmission electron microscopy images. After this process, a layer of WAM coating of different thicknesses was added to these more realistic soot aggregates. The radiative properties of these coated soot aggregates over the spectral range of 266-1064 nm were calculated by the discrete dipole approximation (DDA) using the spectrally dependent refractive index of soot for four aggregates containing Np=1, 20, 51 and 96 primary particles. The considered coating thicknesses range from 0% (no coating) up to 100% coating in terms of the primary particle diameter. Coating enhances both the particle absorption and scattering cross sections, with much stronger enhancement to the scattering one, as well as the asymmetry factor and the single scattering albedo. The absorption enhancement is stronger in the UV than in the visible and the near infrared. The simple corrections to the Rayleigh-Debye-Gans fractal aggregates theory for uncoated soot aggregates are found not working for coated soot aggregates. The core-shell model significantly overestimates the absorption enhancement by coating in the visible and the near infrared compared to the DDA results of the coated soot particle. Treating an externally coated soot aggregate as an aggregate formed by individually coated primary particles significantly underestimates the absorption enhancement by coating in the visible and the near infrared.

Morphological classification of bioaerosols from composting using scanning electron microscopy

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

Tamer Vestlund, A.; FIRA International Ltd., Maxwell Road, Stevenage, Herts SG1 2EW; Al-Ashaab, R.

2014-07-15

Highlights: • Bioaerosols were captured using the filter method. • Bioaerosols were analysed using scanning electron microscope. • Bioaerosols were classified on the basis of morphology. • Single small cells were found more frequently than aggregates and larger cells. • Smaller cells may disperse further than heavier aggregate structures. - Abstract: This research classifies the physical morphology (form and structure) of bioaerosols emitted from open windrow composting. Aggregation state, shape and size of the particles captured are reported alongside the implications for bioaerosol dispersal after release. Bioaerosol sampling took place at a composting facility using personal air filter samplers. Samplesmore » were analysed using scanning electron microscopy. Particles were released mainly as small (<1 μm) single, spherical cells, followed by larger (>1 μm) single cells, with aggregates occurring in smaller proportions. Most aggregates consisted of clusters of 2–3 particles as opposed to chains, and were <10 μm in size. No cells were attached to soil debris or wood particles. These small single cells or small aggregates are more likely to disperse further downwind from source, and cell viability may be reduced due to increased exposure to environmental factors.« less

Direct Deposition of Gas Phase Generated Aerosol Gold Nanoparticles into Biological Fluids - Corona Formation and Particle Size Shifts

PubMed Central

Svensson, Christian R.; Messing, Maria E.; Lundqvist, Martin; Schollin, Alexander; Deppert, Knut; Pagels, Joakim H.; Rissler, Jenny; Cedervall, Tommy

2013-01-01

An ongoing discussion whether traditional toxicological methods are sufficient to evaluate the risks associated with nanoparticle inhalation has led to the emergence of Air-Liquid interface toxicology. As a step in this process, this study explores the evolution of particle characteristics as they move from the airborne state into physiological solution. Airborne gold nanoparticles (AuNP) are generated using an evaporation-condensation technique. Spherical and agglomerate AuNPs are deposited into physiological solutions of increasing biological complexity. The AuNP size is characterized in air as mobility diameter and in liquid as hydrodynamic diameter. AuNP:Protein aggregation in physiological solutions is determined using dynamic light scattering, particle tracking analysis, and UV absorption spectroscopy. AuNPs deposited into homocysteine buffer form large gold-aggregates. Spherical AuNPs deposited in solutions of albumin were trapped at the Air-Liquid interface but was readily suspended in the solutions with a size close to that of the airborne particles, indicating that AuNP:Protein complex formation is promoted. Deposition into serum and lung fluid resulted in larger complexes, reflecting the formation of a more complex protein corona. UV absorption spectroscopy indicated no further aggregation of the AuNPs after deposition in solution. The corona of the deposited AuNPs shows differences compared to AuNPs generated in suspension. Deposition of AuNPs from the aerosol phase into biological fluids offers a method to study the protein corona formed, upon inhalation and deposition in the lungs in a more realistic way compared to particle liquid suspensions. This is important since the protein corona together with key particle properties (e.g. size, shape and surface reactivity) to a large extent may determine the nanoparticle effects and possible translocation to other organs. PMID:24086363

Alpha-helix to beta-sheet transition in long-chain poly-l-lysine: Formation of alpha-helical fibrils by poly-l-lysine.

PubMed

Cieślik-Boczula, Katarzyna

2017-06-01

The temperature-induced α-helix to β-sheet transition in long-chain poly-l-lysine (PLL), accompanied by the gauche-to-trans isomerization of CH 2 groups in the hydrocarbon side chains of Lys amino acid residues, and formation of β-sheet as well as α-helix fibrillar aggregates of PLL have been studied using Fourier-transform infrared (FT-IR) and vibrational circular dichroism (VCD) spectroscopy, and transmission electron microscopy (TEM). In a low-temperature alkaline water solution or in a methanol-rich water mixture, the secondary structure of PLL is represented by α-helical conformations with unordered and gauche-rich hydrocarbon side chains. Under these conditions, PLL molecules aggregate into α-helical fibrils. PLLs dominated by extended antiparallel β-sheet structures with highly ordered trans-rich hydrocarbon side chains are formed in a high-temperature range at alkaline pD and aggregate into fibrillar, protofibrillar, and spherical forms. Presented data support the idea that fibrillar aggregation is a varied phenomenon possible in repetitive structural elements with not only a β-sheet-rich conformation, but also an α-helical-rich conformation. Copyright © 2017 Elsevier B.V. and Société Française de Biochimie et Biologie Moléculaire (SFBBM). All rights reserved.

How Do the Size, Charge and Shape of Nanoparticles Affect Amyloid β Aggregation on Brain Lipid Bilayer?

NASA Astrophysics Data System (ADS)

Kim, Yuna; Park, Ji-Hyun; Lee, Hyojin; Nam, Jwa-Min

2016-01-01

Here, we studied the effect of the size, shape, and surface charge of Au nanoparticles (AuNPs) on amyloid beta (Aβ) aggregation on a total brain lipid-based supported lipid bilayer (brain SLB), a fluid platform that facilitates Aβ-AuNP aggregation process. We found that larger AuNPs induce large and amorphous aggregates on the brain SLB, whereas smaller AuNPs induce protofibrillar Aβ structures. Positively charged AuNPs were more strongly attracted to Aβ than negatively charged AuNPs, and the stronger interactions between AuNPs and Aβ resulted in fewer β-sheets and more random coil structures. We also compared spherical AuNPs, gold nanorods (AuNRs), and gold nanocubes (AuNCs) to study the effect of nanoparticle shape on Aβ aggregation on the brain SLB. Aβ was preferentially bound to the long axis of AuNRs and fewer fibrils were formed whereas all the facets of AuNCs interacted with Aβ to produce the fibril networks. Finally, it was revealed that different nanostructures induce different cytotoxicity on neuroblastoma cells, and, overall, smaller Aβ aggregates induce higher cytotoxicity. The results offer insight into the roles of NPs and brain SLB in Aβ aggregation on the cell membrane and can facilitate the understanding of Aβ-nanostructure co-aggregation mechanism and tuning Aβ aggregate structures.

Cultivation of recombinant Chinese hamster ovary cells grown as suspended aggregates in stirred vessels.

PubMed

Han, Yi; Liu, Xing-Mao; Liu, Hong; Li, Shi-Chong; Wu, Ben-Chuan; Ye, Ling-Ling; Wang, Qu-Wei; Chen, Zhao-Lie

2006-11-01

Recombinant Chinese hamster ovary (rCHO) cells capable of producing a prourokinase mutant (mPro-uk) grown as suspended aggregates in stirred vessels were described and characterized. The addition of chitosan to a mixture of DMEM and Ham's F12 (D-MEM/F-12) medium promoted cell aggregation and spheroid formation efficiently. Multicellular aggregates formed immediately after the rCHO cells were inoculated into the chitosan-added medium, and the mean diameter of the cell aggregates reflecting the aggregate size increased with culture time, shifting from 65 to 163 mum after 2 and 9 d of culture in spinner flasks. No significant difference in the metabolism performance of the rCHO cells was observed between suspended aggregates and anchored monolayers. However, the cells cultured as suspended aggregates showed a marked decrease in growth rate as evaluated from specific growth rate (mu). Replacing D-MEM/F-12 medium with CD 293 medium caused compact spherical cell aggregates to dissociate into small irregular aggregates and single cells without apparent effects on cell performance in subcultures. The perfusion culture of the rCHO cells grown as suspended aggregates in a 2-l stirred tank bioreactor for 15 d resulted in a maximum viable cell density of 5.6 x 10(6) cells ml(-1) and an mPro-uk concentration of about 2.6 x 10(3) IU ml(-1), and cell viability was remained at roughly 90% during the entire run.

Modification of SiO2 nanowires with metallic nanocrystals from supercritical CO2.

PubMed

Ye, Xiang-Rong; Zhang, Hai-Feng; Lin, Yuehe; Wang, Lai-Sheng; Wai, Chien M

2004-01-01

Through hydrogen reduction of metal precursors in supercritical CO2, Cu, and Pd, nanocrystals were deposited onto SiO2 nanowires to form different types of nanostructured materials, including nanocrystal-nanowire, spherical aggregation-nanowire, shell-nanowire composites, and "mesoporous" metals supported by the framework of nanowires. This supercritical fluid deposition technique is an attractive approach for modifying nanowires because of its generality and simplicity; the modified nanowires could be useful as catalysts and for further fabrication of multifunctional composites.

Morphology-Variable Aggregates Prepared from Cholesterol-Containing Amphiphilic Glycopolymers: Their Protein Recognition/Adsorption and Drug Delivery Applications

PubMed Central

Wang, Zhao; Luo, Ting; Cao, Amin; Sun, Jingjing; Jia, Lin

2018-01-01

In this study, a series of diblock glycopolymers, poly(6-O-methacryloyl-d-galactopyranose)-b-poly(6-cholesteryloxyhexyl methacrylate) (PMAgala-b-PMAChols), with cholesterol/galactose grafts were prepared through a sequential reversible addition-fragmentation chain transfer (RAFT) polymerization and deprotection process. The glycopolymers could self-assemble into aggregates with various morphologies depending on cholesterol/galactose-containing block weight ratios, as determined by transmission electronic microscopy (TEM) and dynamic laser light scattering (DLS). In addition, the lectin (Ricinus communis agglutinin II, RCA120) recognition and bovine serum albumin (BSA) adsorption of the PMAgala-b-PMAChol aggregates were evaluated. The SK-Hep-1 tumor cell inhibition properties of the PMAgala-b-PMAChol/doxorubicin (DOX) complex aggregates were further examined in vitro. Results indicate that the PMAgala-b-PMAChol aggregates with various morphologies showed different interaction/recognition features with RCA120 and BSA. Spherical aggregates (d ≈ 92 nm) possessed the highest RCA120 recognition ability and lowest BSA protein adsorption. In addition, the DOX-loaded spherical complex aggregates exhibited a better tumor cell inhibition property than those of nanofibrous complex aggregates. The morphology-variable aggregates derived from the amphiphilic glycopolymers may serve as multifunctional biomaterials with biomolecular recognition and drug delivery features. PMID:29495614

Numerical Simulations of Single and Multiple Scattering by Fractal Ice Clusters

NASA Technical Reports Server (NTRS)

Dlugach, Janna M.; Mishchenko, Michael I.; Mackowski, Daniel W.

2011-01-01

We consider the scattering model in the form of a vertically and horizontally homogeneous particulate slab of an arbitrary optical thickness composed of widely separated fractal aggregates built of small spherical ice monomers. The aggregates are generated by applying three different approaches, including simulated cluster-cluster aggregation (CCA) and diffusion-limited aggregation (DLA) procedures. Having in mind radar remote-sensing applications, we report and analyze the results of computations of the backscattering circular polarization ratio obtained using efficient superposition T-matrix and vector radiative-transfer codes. The computations have been performed at a wavelength of 12.6 cm for fractal aggregates with the following characteristics: monomer refractive index m=1.78+i0.003, monomer radius r=1 cm, monomer packing density p=0.2, overall aggregate radii R in the range 4<=R<=10 cm and fractal dimensions D(sub f) 2.5 and 3. We show that for aggregates generated with simulated CCA and DLA procedures, the respective values of the backscattering circular polarization ratio differ weakly for D(sub f) 2.5, but the differences can increase somewhat for D(sub f)3, especially in case of an optically semi-infinite medium. For aggregates with a spheroidal overall shape, the dependence of the circular polarization ratio on the cluster morphology can be quite significant and increases with increasing the aspect ratio of the circumscribing spheroid.

Bead-Level Characterization of Early-Stage Amyloid β42 Aggregates: Nuclei and Ionic Concentration Effects.

PubMed

Hu, Dingkun; Zhao, Wei; Zhu, Yong; Ai, Hongqi; Kang, Baotao

2017-11-16

A growing body of evidence shows that soluble β-amyloid (Aβ) aggregates, oligomers, and even protofibrils, may be more neurotoxic than fibrils. Here, we employ a coarse grain model to investigate the aggregation of 75mer Aβ 42 oligomers and the salt effect, the cornerstone of fibril evolution. We find that the oligomer morphologies generated by seventy-five monomers or mixed by both fifty monomers and five preset pentameric nuclei are different (spherical vs. bar-/disk-shaped) and are characterize by a full of coil content (former) and >70 % β-turn content (latter), indicating a novel role of the nuclei played in the early aggregation stage. The aggregation for the former oligomer adopts a master-nucleus mechanism, whereas for the latter combination of monomers and pentamers a multi-nuclei one is found. The random salt ions will distribute around the aggregates to form several ion shells as the aggregation develops. A unique two-fold gap between the shells is observed in the system containing 100 mm NaCl, endowing the physiological salt concentration with special implications. Meanwhile, an accurate ion-solute cutoff distance (0.66 nm) is predicted, and recommended to apply to many other aggregated biomolecular systems. The present distribution scenario of ions can be generalized to other aggregated systems, although it is strictly dependent on the identity of a specific aggregate, such as its charge and composition. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

C{sub 60}-dyad aggregates: Self-organized structures in aqueous solutions

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

Guskova, O. A., E-mail: guskova@ipfdd.de, E-mail: s.raovaranasi@uq.edu.au; Varanasi, S. R., E-mail: guskova@ipfdd.de, E-mail: s.raovaranasi@uq.edu.au; Sommer, J.-U.

2014-10-14

Extensive full-atomistic molecular dynamics simulations are performed to study the self-organization of C{sub 60}-fullerene dyad molecules in water, namely phenyl-C{sub 61}-butyric acid methyl ester and fulleropyrrolidines, which have two elements of ordering, the hydrophobic fullerene cage and the hydrophilic/ionic group. While pristine fullerene or phenyl-C{sub 61}-butyric acid methyl ester forms spherical droplets in order to minimize the surface tension, the amphiphilic nature of charged solute molecules leads to the formation of supramolecular assemblies having cylindrical shape driven by charge repulsion between the ionic groups located on the surface of the aggregates. We show that formation of non-spherical micelles is themore » geometrical consequence if the fullerene derivatives are considered as surfactants where the ionized groups are only hydrophilic unit. The agglomeration behavior of fullerenes is evaluated by determining sizes of the clusters, solvent accessible surface areas, and shape parameters. By changing the size of the counterions from chloride over iodide to perchlorate we find a thickening of the cylinder-like structures which can be explained by stronger condensation of larger ions and thus partial screening of the charge repulsion on the cluster surface. The reason for the size dependence of counterion condensation is the formation of a stronger hydration shell in case of small ions which in turn are repelled from the fullerene aggregates. Simulations are also in good agreement with the experimentally observed morphologies of decorated C{sub 60}-nanoparticles.« less

Experimental aggregation of volcanic ash: the role of liquid bonding

NASA Astrophysics Data System (ADS)

Mueller, S.; Kueppers, U.; Jacob, M.; Ayris, P. M.; Dingwell, D. B.

2015-12-01

Explosive volcanic eruptions may release vast quantities of ash. Because of its size, it has the greatest dispersal potential and can be distributed globally. Ash may pose severe risks for 1) air traffic, 2) human and animal health, 3) agriculture and 4) infrastructure. Such ash particles can however cluster and form ash aggregates that range in size from millimeters to centimeters. During their growth, weight and aerodynamic properties change. This leads to significantly changed transport and settling behavior. The physico-chemical processes involved in aggregation are quantitatively poorly constrained. We have performed laboratory ash aggregation experiments using the ProCell Lab System® of Glatt Ingenieurtechnik GmbH. Solid particles are set into motion in a fluidized bed over a range of well-controlled boundary conditions (e.g., air flow rate, gas temperature, humidity, liquid composition). In this manner we simulate the variable gas-particle flow conditions expected in eruption plumes and pyroclastic density currents. We have used 1) soda-lime glass beads as an analogue material and 2) natural volcanic ash from Laacher See Volcano (Germany). In order to influence form, size, stability and the production rate of aggregates, a range of experimental conditions (e.g., particle concentration, degree of turbulence, temperature and moisture in the process chamber and the composition of the liquid phase) have been employed. We have successfully reproduced several features of natural ash aggregates, including round, internally structured ash pellets up to 3 mm in diameter. These experimental results help to constrain the boundary conditions required for the generation of spherical, internally-structured ash aggregates that survive deposition and are preserved in the volcanological record. These results should also serve as input parameters for models of ash transport and ash mass distribution.

Entropic effects, shape, and size of mixed micelles formed by copolymers with complex architectures

NASA Astrophysics Data System (ADS)

Kalogirou, Andreas; Gergidis, Leonidas N.; Moultos, Othonas; Vlahos, Costas

2015-11-01

The entropic effects in the comicellization behavior of amphiphilic A B copolymers differing in the chain size of solvophilic A parts were studied by means of molecular dynamics simulations. In particular, mixtures of miktoarm star copolymers differing in the molecular weight of solvophilic arms were investigated. We found that the critical micelle concentration values show a positive deviation from the analytical predictions of the molecular theory of comicellization for chemically identical copolymers. This can be attributed to the effective interactions between copolymers originated from the arm size asymmetry. The effective interactions induce a very small decrease in the aggregation number of preferential micelles triggering the nonrandom mixing between the solvophilic moieties in the corona. Additionally, in order to specify how the chain architecture affects the size distribution and the shape of mixed micelles we studied star-shaped, H-shaped, and homo-linked-rings-linear mixtures. In the first case the individual constituents form micelles with preferential and wide aggregation numbers and in the latter case the individual constituents form wormlike and spherical micelles.

Entropic effects, shape, and size of mixed micelles formed by copolymers with complex architectures.

PubMed

Kalogirou, Andreas; Gergidis, Leonidas N; Moultos, Othonas; Vlahos, Costas

2015-11-01

The entropic effects in the comicellization behavior of amphiphilic AB copolymers differing in the chain size of solvophilic A parts were studied by means of molecular dynamics simulations. In particular, mixtures of miktoarm star copolymers differing in the molecular weight of solvophilic arms were investigated. We found that the critical micelle concentration values show a positive deviation from the analytical predictions of the molecular theory of comicellization for chemically identical copolymers. This can be attributed to the effective interactions between copolymers originated from the arm size asymmetry. The effective interactions induce a very small decrease in the aggregation number of preferential micelles triggering the nonrandom mixing between the solvophilic moieties in the corona. Additionally, in order to specify how the chain architecture affects the size distribution and the shape of mixed micelles we studied star-shaped, H-shaped, and homo-linked-rings-linear mixtures. In the first case the individual constituents form micelles with preferential and wide aggregation numbers and in the latter case the individual constituents form wormlike and spherical micelles.

Aqueous formation and manipulation of the iron-oxo Keggin ion

NASA Astrophysics Data System (ADS)

Sadeghi, Omid; Zakharov, Lev N.; Nyman, May

2015-03-01

There is emerging evidence that growth of synthetic and natural phases occurs by the aggregation of prenucleation clusters, rather than classical atom-by-atom growth. Ferrihydrite, an iron oxyhydroxide mineral, is the common form of Fe3+ in soils and is also in the ferritin protein. We isolated a 10 angstrom discrete iron-oxo cluster (known as the Keggin ion, Fe13) that has the same structural features as ferrihydrite. The stabilization and manipulation of this highly reactive polyanion in water is controlled exclusively by its counterions. Upon dissolution of Fe13 in water with precipitation of its protecting Bi3+-counterions, it rapidly aggregates to ~22 angstrom spherical ferrihydrite nanoparticles. Fe13 may therefore also be a prenucleation cluster for ferrihydrite formation in natural systems, including by microbial and cellular processes.

Composition, buoyancy regulation and fate of ice algal aggregates in the Central Arctic Ocean.

PubMed

Fernández-Méndez, Mar; Wenzhöfer, Frank; Peeken, Ilka; Sørensen, Heidi L; Glud, Ronnie N; Boetius, Antje

2014-01-01

Sea-ice diatoms are known to accumulate in large aggregates in and under sea ice and in melt ponds. There is recent evidence from the Arctic that such aggregates can contribute substantially to particle export when sinking from the ice. The role and regulation of microbial aggregation in the highly seasonal, nutrient- and light-limited Arctic sea-ice ecosystem is not well understood. To elucidate the mechanisms controlling the formation and export of algal aggregates from sea ice, we investigated samples taken in late summer 2011 and 2012, during two cruises to the Eurasian Basin of the Central Arctic Ocean. Spherical aggregates densely packed with pennate diatoms, as well as filamentous aggregates formed by Melosira arctica showed sign of different stages of degradation and physiological stoichiometries, with carbon to chlorophyll a ratios ranging from 110 to 66700, and carbon to nitrogen molar ratios of 8-35 and 9-40, respectively. Sub-ice algal aggregate densities ranged between 1 and 17 aggregates m(-2), maintaining an estimated net primary production of 0.4-40 mg C m(-2) d(-1), and accounted for 3-80% of total phototrophic biomass and up to 94% of local net primary production. A potential factor controlling the buoyancy of the aggregates was light intensity, regulating photosynthetic oxygen production and the amount of gas bubbles trapped within the mucous matrix, even at low ambient nutrient concentrations. Our data-set was used to evaluate the distribution and importance of Arctic algal aggregates as carbon source for pelagic and benthic communities.

Composition, Buoyancy Regulation and Fate of Ice Algal Aggregates in the Central Arctic Ocean

PubMed Central

Fernández-Méndez, Mar; Wenzhöfer, Frank; Peeken, Ilka; Sørensen, Heidi L.; Glud, Ronnie N.; Boetius, Antje

2014-01-01

Sea-ice diatoms are known to accumulate in large aggregates in and under sea ice and in melt ponds. There is recent evidence from the Arctic that such aggregates can contribute substantially to particle export when sinking from the ice. The role and regulation of microbial aggregation in the highly seasonal, nutrient- and light-limited Arctic sea-ice ecosystem is not well understood. To elucidate the mechanisms controlling the formation and export of algal aggregates from sea ice, we investigated samples taken in late summer 2011 and 2012, during two cruises to the Eurasian Basin of the Central Arctic Ocean. Spherical aggregates densely packed with pennate diatoms, as well as filamentous aggregates formed by Melosira arctica showed sign of different stages of degradation and physiological stoichiometries, with carbon to chlorophyll a ratios ranging from 110 to 66700, and carbon to nitrogen molar ratios of 8–35 and 9–40, respectively. Sub-ice algal aggregate densities ranged between 1 and 17 aggregates m−2, maintaining an estimated net primary production of 0.4–40 mg C m−2 d−1, and accounted for 3–80% of total phototrophic biomass and up to 94% of local net primary production. A potential factor controlling the buoyancy of the aggregates was light intensity, regulating photosynthetic oxygen production and the amount of gas bubbles trapped within the mucous matrix, even at low ambient nutrient concentrations. Our data-set was used to evaluate the distribution and importance of Arctic algal aggregates as carbon source for pelagic and benthic communities. PMID:25208058

The synthesis, self-assembling, and biocompatibility of a novel O-carboxymethyl chitosan cholate decorated with glycyrrhetinic acid.

PubMed

Du, Hongliang; Yang, Xiaoye; Pang, Xin; Zhai, Guangxi

2014-10-13

O-carboxymethyl chitosan (OCMC) was firstly decorated with cholic acid (CA) to acquire an amphiphilic polymer under alkaline condition. Then glycyrrhetinic acid (GA) was conjugated to the polymer via a succinate linker and finally treated with NaCO3 solution to obtain new conjugates for potential liver targeted delivery. These conjugates formed uniform aggregates with low critical aggregation concentrations (0.028-0.079 mg/mL) in PBS. The average diameter of cholic acid modified carboxymethyl chitosan (CMCA) aggregates (110-257 nm) decreased with the increase of CA substitution degree and became slightly larger after GA modification. Negative zeta potential (-15 mV) of GA decorated CMCA (GA-CMCA) revealed that the formation of negatively charged shells and spherical morphology was observed under transmission electron microscopy. Furthermore, hemolysis test, in vitro cytotoxicity assay and cellular uptake study all demonstrated the safety and feasibility of these conjugates as a promising carrier for liver targeted drug delivery. Copyright © 2014 Elsevier Ltd. All rights reserved.

Observation of Moon Jellyfish Spatial Distribution Using a Scientific Echo Sounder and Underwater Camera

NASA Astrophysics Data System (ADS)

Mano, T.; Guo, X.; Fujii, N.; Yoshie, N.; Takeoka, H.

2016-02-01

Jellyfishes often form dense aggregation that causes a variety of social problems such as clogging seawater intake of power plant, breaking fisheries net and more. Understanding on jellyfish aggregation is not sufficient due to the difficulty of observation on this phenomenon. In this study, high-resolution observations using scientific echo sounder and underwater camera were carried out to reveal the fine structure of moon jellyfish distribution in a 3D space, as well as its abundance and temporal variation. In addition, water temperature, salinity and current speed were also measured for inferring formation mechanisms of jellyfish aggregation. The field observations with a target on moon jellyfish were carried out in August 2013 and August 2014, in a semi-enclosed bay in Japan. The ship equipped with scientific echo sounder was cruised over the entire bay to reveal the distribution and the form of the moon jellyfish aggregation. In August 2013, the jellyfish aggregations present a high density (maximum: 70 ind. /m3) and their outline shows spherical or zonal shape with a hollow structure. In August 2014, the jellyfish aggregations present a low density (maximum: 20 ind./m3) and the jellyfishes distributed in a layer structure over a wide area. The depth of jellyfish aggregation was consistent with thermocline. During three days of observations in 2014, the average population density of jellyfish reduced by one-tenth, showing a possibility that the jellyfish abundance in a bay may vary significantly in a short timescale of several days. Not only the active swimming of jellyfishes but also the ambient flow field associated with internal waves or Langmuir circulation may contribute to the jellyfish aggregations. In order to clarify the mechanisms for the formation of high density patchy aggregation, we plan to perform more detailed observations and numerical simulations that are able to capture the fine structure of these physical processes in the future.

Authigenic kaolinite and associated pyrite in chalk of the Cretaceous Niobrara Formation, Eastern Colorado.

USGS Publications Warehouse

Pollastro, R.M.

1981-01-01

Cores from the Smoky Hill Chalk Member of the Cretaceous Niobrara Formation have several zones containing authigenic kaolinite as spherical, moldic, polycrystalline aggregates that occur within single or multichambered foraminiferal tests and are commonly associated with framboidal pyrite. Such kaolinite is inferred to result from volcanic ash deposited during chalk sedimentation. Shortly after burial, a colloidal aluminous gel or solution formed from the unstable ash and moved into organic-rich foraminiferal tests, where sulfate-reducing bacteria created a favorable microenvironment for the simultaneous crystallization of kaolinite and pyrite. -Author

A Method for Identifying Small-Molecule Aggregators Using Photonic Crystal Biosensor Microplates

PubMed Central

Chan, Leo L.; Lidstone, Erich A.; Finch, Kristin E.; Heeres, James T.; Hergenrother, Paul J.; Cunningham, Brian T.

2010-01-01

Small molecules identified through high-throughput screens are an essential element in pharmaceutical discovery programs. It is now recognized that a substantial fraction of small molecules exhibit aggregating behavior leading to false positive results in many screening assays, typically due to nonspecific attachment to target proteins. Therefore, the ability to efficiently identify compounds within a screening library that aggregate can streamline the screening process by eliminating unsuitable molecules from further consideration. In this work, we show that photonic crystal (PC) optical biosensor microplate technology can be used to identify and quantify small-molecule aggregation. A group of aggregators and nonaggregators were tested using the PC technology, and measurements were compared with those gathered by three alternative methods: dynamic light scattering (DLS), an α-chymotrypsin colorimetric assay, and scanning electron microscopy (SEM). The PC biosensor measurements of aggregation were confirmed by visual observation using SEM, and were in general agreement with the α-chymotrypsin assay. DLS measurements, in contrast, demonstrated inconsistent readings for many compounds that are found to form aggregates in shapes, very different from the classical spherical particles assumed in DLS modeling. As a label-free detection method, the PC biosensor aggregation assay is simple to implement and provides a quantitative direct measurement of the mass density of material adsorbed to the transducer surface, whereas the microplate-based sensor format enables compatibility with high-throughput automated liquid-handling methods used in pharmaceutical screening. PMID:20930952

Starch-assisted synthesis and optical properties of ZnS nanoparticles

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

Tian, Xiuying, E-mail: xiuyingt@yahoo.com; Wen, Jin; Wang, Shumei

Highlights: • ZnS spherical nanostructure was prepared via starch-assisted method. • The crystalline lattice structure, morphologies, chemical and optical properties of ZnS nanoparticles. • The forming mechanism of ZnS nanoparticles. • ZnS spherical nano-structure can show blue emission at 460–500 nm. - Abstract: ZnS nanoparticles are fabricated via starch-assisted method. The effects of different starch amounts on structure and properties of samples are investigated, and the forming mechanism of ZnS nanoparticles is discussed. By X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), ultraviolet–visible (UV–vis)more » spectroscopy and fluorescence (FL) spectrometer, their phases, crystalline lattice structure, morphologies, chemical and optical properties are characterized. The results show that ZnS has polycrystalline spherical structure with the mean diameter of 130 nm. Sample without starch reveals irregular aggregates with particle size distribution of 0.5–2 μm. The band gap value of ZnS is 3.97 eV. The chemical interaction exists between starch molecules and ZnS nanoparticles by hydrogen bonds. The stronger FL emission peaks of ZnS synthesized with starch, indicate a larger content of sulfur vacancies or defects than ZnS synthesized without starch.« less

Giant Spherical Cluster with I-C140 Fullerene Topology**

PubMed Central

Heinl, Sebastian; Peresypkina, Eugenia; Sutter, Jörg; Scheer, Manfred

2015-01-01

We report on an effective cluster expansion of CuBr-linked aggregates by the increase of the steric bulk of the CpR ligand in the pentatopic molecules [CpRFe(η5-P5)]. Using [CpBIGFe(η5-P5)] (CpBIG=C5(4-nBuC6H4)5), the novel multishell aggregate [{CpBIGFe(η5:2:1:1:1:1:1-P5)}12(CuBr)92] is obtained. It shows topological analogy to the theoretically predicted I-C140 fullerene molecule. The spherical cluster was comprehensively characterized by various methods in solution and in the solid state. PMID:26411255

Interactions between citrate-capped gold nanoparticles and polymersomes

NASA Astrophysics Data System (ADS)

Zhang, Xiaohan; Lopez, Anand; Liu, Yibo; Wang, Feng; Liu, Juewen

2018-06-01

Polymersomes are vesicles formed by self-assembled amphiphilic block copolymers. Polymersomes generally have better stability than liposomes and they have been widely used in making drug delivery vehicles. In this work, the interaction between two types of polymersomes and citrate-capped gold nanoparticles (AuNPs) was studied. The following two polymers: poly(2-methyloxazoline-b-dimethylsiloxane-b-2-methyloxazoline) (called P1) and poly(butadiene-b-ethylene oxide) (called P2) were respectively used to form polymersomes. While P1 only formed spherical vesicle structures, worm-like structures were also observed with P2 as indicated by cryo-TEM. Both polymersomes adsorbed AuNPs leading to their subsequent aggregation. A lower polymersome concentration produced more obvious aggregation of AuNPs as judged from the color change. Capping AuNPs with glutathione inhibited adsorption of AuNPs. Considering the surface property of the polymers, the interaction with AuNPs was likely due to van der Waals forces. P1 polymersomes encapsulated calcein stably and AuNPs did not induce leakage. The P1/AuNP complex was more efficiently internalized by HeLa cells compared to free P1 polymersomes, further indicating a stable adsorption under cell culture conditions. In summary, this work indicates citrate-capped AuNPs form stable adsorption complexes with these polymersomes and their interactions have been explored.

Tunable porosities and shapes of fullerene-like spheres.

PubMed

Dielmann, Fabian; Fleischmann, Matthias; Heindl, Claudia; Peresypkina, Eugenia V; Virovets, Alexander V; Gschwind, Ruth M; Scheer, Manfred

2015-04-13

The formation of reversible switchable nanostructures monitored by solution and solid-state methods is still a challenge in supramolecular chemistry. By a comprehensive solid state and solution study we demonstrate the potential of the fivefold symmetrical building block of pentaphosphaferrocene in combination with Cu(I) halides to switch between spheres of different porosity and shape. With increasing amount of CuX, the structures of the formed supramolecules change from incomplete to complete spherically shaped fullerene-like assemblies possessing an Ih -C80 topology at one side and to a tetrahedral-structured aggregate at the other. In the solid state, the formed nano-sized aggregates reach an outer diameter of 3.14 and 3.56 nm, respectively. This feature is used to reversibly encapsulate and release guest molecules in solution. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.

Giant Spherical Cluster with I-C140 Fullerene Topology.

PubMed

Heinl, Sebastian; Peresypkina, Eugenia; Sutter, Jörg; Scheer, Manfred

2015-11-02

We report on an effective cluster expansion of CuBr-linked aggregates by the increase of the steric bulk of the Cp(R) ligand in the pentatopic molecules [Cp(R)Fe(η(5)-P5)]. Using [Cp(BIG)Fe(η(5)-P5)] (Cp(BIG)=C5(4-nBuC6H4)5), the novel multishell aggregate [{Cp(BIG)Fe(η(5:2:1:1:1:1:1)-P5)}12(CuBr)92] is obtained. It shows topological analogy to the theoretically predicted I-C140 fullerene molecule. The spherical cluster was comprehensively characterized by various methods in solution and in the solid state. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Aggregation of asbestos fibers in water: role of solution chemistry

NASA Astrophysics Data System (ADS)

Wu, L.; Ortiz, C. P.; Jerolmack, D. J.

2016-12-01

Aggregation kinetics and stability of colloidal particles have been extensively studied using bulk techniques such as dynamic light scattering; these techniques involve large ensembles of particles and interpretation of results is difficult when particles are non-spherical and poorly characterized, as is always the case with non-ideal natural hazardous materials such as asbestos fibers. These difficulties hinder greatly progress on fundamental understanding of whether the classic colloidal aggregation theories can be applied to natural materials and how the heterogeneity of particles (e.g., shape) affects the colloidal aggregation kinetics and structure. By using in-situ microscopy and particle tracking techniques, we were able to observe the particle-by-particle growth of aggregated formed by elongated particles (synthetic glass rods and natural asbestos fibers) and demonstrated the rod-shaped geometry induced novel structures and growth dynamics that challenge existing theory. In this study, we continue to use asbestos as model system of elongated colloidal contaminant, and investigate the effects of changing solution chemistry (e.g., ionic strength, pH, and natural organic matter (NOM)), on growth dynamics and aggregates structure. The results show that aggregate growth curves are self-similar with a characteristic timescale that increases with increasing pH. By varying ionic strength for fixed pH values, we determine that the ccc is sensitive to pH. Fractal dimension decreases slightly with increasing pH and decreasing ionic strength, indicating that stronger inter-particle repulsion create sparser aggregates; however, the magnitude of the solution chemistry effects is much smaller than that of colloid shape. In monovalent solutions, regardless of their concentration, HA drastically reduces the aggregation kinetics of asbestos fiber. This work may lead to enhanced prediction of the colloidal contaminants' mobility in the environment, bioavailability, and toxicity to organisms.

Physicochemical perspectives (aggregation, structure and dynamics) of interaction between pluronic (L31) and surfactant (SDS).

PubMed

Prameela, G K S; Phani Kumar, B V N; Pan, A; Aswal, V K; Subramanian, J; Mandal, A B; Moulik, S P

2015-11-11

The influence of the water soluble non-ionic tri-block copolymer PEO-PPO-PEO [poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)] i.e., E2P16E2 (L31) on the microstructure and self-aggregation dynamics of the anionic surfactant sodium dodecylsulfate (SDS) in aqueous solution was investigated using cloud point (CP), isothermal titration calorimetry (ITC), high resolution nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR), and small-angle neutron scattering (SANS) measurements. CP provided the thermodynamic information on the Gibbs free energy, enthalpy, entropy and heat capacity changes pertaining to the phase separation of the system at elevated temperature. The ITC and NMR self-diffusion measurements helped to understand the nature of the binding isotherms of SDS in the presence of L31 in terms of the formation of mixed aggregates and free SDS micelles in solution. EPR analysis provided the micro-viscosity of the spin probe 5-DSA in terms of rotational correlation time. The SANS study indicated the presence of prolate ellipsoidal mixed aggregates, whose size increased with the increasing addition of L31. At a large [L31], SANS also revealed the progressive decreasing size of the ellipsoidal mixed aggregates of SDS-L31 into nearly globular forms with the increasing SDS addition. Wrapping of the spherical SDS micelles by L31 was also corroborated from (13)C NMR and SANS measurements.

Taking the Silver Bullet Colloidal Silver Particles for the Topical Treatment of Biofilm-Related Infections.

PubMed

Richter, Katharina; Facal, Paula; Thomas, Nicky; Vandecandelaere, Ilse; Ramezanpour, Mahnaz; Cooksley, Clare; Prestidge, Clive A; Coenye, Tom; Wormald, Peter-John; Vreugde, Sarah

2017-07-05

Biofilms are aggregates of bacteria residing in a self-assembled matrix, which protects these sessile cells against external stress, including antibiotic therapies. In light of emerging multidrug-resistant bacteria, alternative strategies to antibiotics are emerging. The present study evaluated the activity of colloidal silver nanoparticles (AgNPs) of different shapes against biofilms formed by Staphylococcus aureus (SA), methicillin-resistant SA (MRSA), and Pseudomonas aeruginosa (PA). Colloidal quasi-spherical, cubic, and star-shaped AgNPs were synthesized, and their cytotoxicity on macrophages (THP-1) and bronchial epithelial cells (Nuli-1) was analyzed by the lactate dehydrogenase assay. The antibiofilm activity was assessed in vitro by the resazurin assay and in an in vivo infection model in Caenorhabditis elegans. Cubic and star-shaped AgNPs induced cytotoxicity, while quasi-spherical AgNPs were not toxic. Quasi-spherical AgNPs showed substantial antibiofilm activity in vitro with 96% (±2%), 97% (±1%), and 98% (±1%) biofilm killing of SA, MRSA, and PA, respectively, while significantly reducing mortality of infected nematodes. The in vivo antibiofilm activity was linked to the accumulation of AgNPs in the intestinal tract of C. elegans as observed by 3D X-ray tomography. Quasi-spherical AgNPs were physically stable in suspension for over 6 months with no observed loss in antibiofilm activity. While toxicity and stability limited the utilization of cubic and star-shaped AgNPs, quasi-spherical AgNPs could be rapidly synthesized, were stable and nontoxic, and showed substantial in vitro and in vivo activity against clinically relevant biofilms. Quasi-spherical AgNPs hold potential as pharmacotherapy, for example, as topical treatment for biofilm-related infections.

The Physics of Protoplanetesimal Dust Agglomerates. IX. Mechanical Properties of Dust Aggregates Probed by a Solid-projectile Impact

NASA Astrophysics Data System (ADS)

Katsuragi, Hiroaki; Blum, Jürgen

2017-12-01

Dynamic characterization of mechanical properties of dust aggregates has been one of the most important problems to quantitatively discuss the dust growth in protoplanetary disks. We experimentally investigate the dynamic properties of dust aggregates by low-speed (≤slant 3.2 m s-1) impacts of solid projectiles. Spherical impactors made of glass, steel, or lead are dropped onto a dust aggregate with a packing fraction of ϕ = 0.35 under vacuum conditions. The impact results in cratering or fragmentation of the dust aggregate, depending on the impact energy. The crater shape can be approximated by a spherical segment and no ejecta are observed. To understand the underlying physics of impacts into dust aggregates, the motion of the solid projectile is acquired by a high-speed camera. Using the obtained position data of the impactor, we analyze the drag-force law and dynamic pressure induced by the impact. We find that there are two characteristic strengths. One is defined by the ratio between impact energy and crater volume and is ≃120 kPa. The other strength indicates the fragmentation threshold of dynamic pressure and is ≃10 kPa. The former characterizes the apparent plastic deformation and is consistent with the drag force responsible for impactor deceleration. The latter corresponds to the dynamic tensile strength to create cracks. Using these results, a simple model for the compaction and fragmentation threshold of dust aggregates is proposed. In addition, the comparison of drag-force laws for dust aggregates and loose granular matter reveals the similarities and differences between the two materials.

A nanotectonics approach to produce hierarchically organized bioactive glass nanoparticles-based macrospheres

NASA Astrophysics Data System (ADS)

Luz, Gisela M.; Mano, João F.

2012-09-01

Bioactive particles have been widely used in a series of biomedical applications due to their ability to promote bone-bonding and elicit favorable biological responses in therapies associated with the replacement and regeneration of mineralized tissues. In this work hierarchical architectures are prepared by an innovative methodology using SiO2-CaO sol-gel based nanoparticles. Inspired by colloidal crystals, spherical aggregates were formed on biomimetic superhydrophobic surfaces using bioactive glass nanoparticles (BG-NPs) able to promote bone regeneration. A highly ordered organization, a common feature of mineralized structures in Nature, was achieved at both nano- and microlevels, being the crystallization degree of the structures controlled by the evaporation rates taking place at room temperature (RT) or at 4 °C. The crystallization degree of the structures influenced the Ca/P ratio of the apatitic film formed at their surface, after 7 days of immersion in SBF. This allows the regulation of bioactive properties and the ability to release potential additives that could be also incorporated in such particles with a high efficiency. Such a versatile method to produce bioactive particles with controlled size and internal structure could open new possibilities in designing new spherical devices for orthopaedic applications, including tissue engineering.

Controlled assembly of nanoparticle structures: spherical and toroidal superlattices and nanoparticle-coated polymeric beads.

PubMed

Isojima, Tatsushi; Suh, Su Kyung; Vander Sande, John B; Hatton, T Alan

2009-07-21

The emulsion droplet solvent evaporation method has been used to prepare nanoclusters of monodisperse magnetite nanoparticles of varying morphologies depending on the temperature and rate of solvent evaporation and on the composition (solvent, presence of polymer, nanoparticle concentration, etc.) of the emulsion droplets. In the absence of a polymer, and with increasing solvent evaporation temperatures, the nanoparticles formed single- or multidomain crystalline superlattices, amorphous spherical aggregates, or toroidal clusters, as determined by the energetics and dynamics of the solvent evaporation process. When polymers that are incompatible with the nanoparticle coatings were included in the emulsion formulation, monolayer- and multilayer-coated polymer beads and partially coated Janus beads were prepared; the nanoparticles were expelled by the polymer as its concentration increased on evaporation of the solvent and accumulated on the surfaces of the beads in a well-ordered structure. The precise number of nanoparticle layers depended on the polymer/magnetic nanoparticle ratio in the oil droplet phase parent emulsion. The magnetic nanoparticle superstructures responded to the application of a modest magnetic field by forming regular chains with alignment of nonuniform structures (e.g., toroids and Janus beads) that are in accord with theoretical predictions and with observations in other systems.

Distinct C9orf72-Associated Dipeptide Repeat Structures Correlate with Neuronal Toxicity

PubMed Central

Krans, Amy; Sawaya, Michael R.; Paulson, Henry L.; Todd, Peter K.; Barmada, Sami J.; Ivanova, Magdalena I.

2016-01-01

Hexanucleotide repeat expansions in C9orf72 are the most common inherited cause of amyotrophic lateral sclerosis (ALS) and frontotemporal dementia (FTD). The expansions elicit toxicity in part through repeat-associated non-AUG (RAN) translation of the intronic (GGGGCC)n sequence into dipeptide repeat-containing proteins (DPRs). Little is known, however, about the structural characteristics and aggregation propensities of the dipeptide units comprising DPRs. To address this question, we synthesized dipeptide units corresponding to the three sense-strand RAN translation products, analyzed their structures by circular dichroism, electron microscopy and dye binding assays, and assessed their relative toxicity when applied to primary cortical neurons. Short, glycine-arginine (GR)3 dipeptides formed spherical aggregates and selectively reduced neuronal survival compared to glycine-alanine (GA)3 and glycine-proline (GP)3 dipeptides. Doubling peptide length had little effect on the structure of GR or GP peptides, but (GA)6 peptides formed β-sheet rich aggregates that bound thioflavin T and Congo red yet lacked the typical fibrillar morphology of amyloids. Aging of (GA)6 dipeptides increased their β-sheet content and enhanced their toxicity when applied to neurons. We also observed that the relative toxicity of each tested dipeptide was proportional to peptide internalization. Our results demonstrate that different C9orf72-related dipeptides exhibit distinct structural properties that correlate with their relative toxicity. PMID:27776165

Dynamics of proteins aggregation. II. Dynamic scaling in confined media

NASA Astrophysics Data System (ADS)

Zheng, Size; Shing, Katherine S.; Sahimi, Muhammad

2018-03-01

In this paper, the second in a series devoted to molecular modeling of protein aggregation, a mesoscale model of proteins together with extensive discontinuous molecular dynamics simulation is used to study the phenomenon in a confined medium. The medium, as a model of a crowded cellular environment, is represented by a spherical cavity, as well as cylindrical tubes with two aspect ratios. The aggregation process leads to the formation of β sheets and eventually fibrils, whose deposition on biological tissues is believed to be a major factor contributing to many neuro-degenerative diseases, such as Alzheimer's, Parkinson's, and amyotrophic lateral sclerosis diseases. Several important properties of the aggregation process, including dynamic evolution of the total number of the aggregates, the mean aggregate size, and the number of peptides that contribute to the formation of the β sheets, have been computed. We show, similar to the unconfined media studied in Paper I [S. Zheng et al., J. Chem. Phys. 145, 134306 (2016)], that the computed properties follow dynamic scaling, characterized by power laws. The existence of such dynamic scaling in unconfined media was recently confirmed by experiments. The exponents that characterize the power-law dependence on time of the properties of the aggregation process in spherical cavities are shown to agree with those in unbounded fluids at the same protein density, while the exponents for aggregation in the cylindrical tubes exhibit sensitivity to the geometry of the system. The effects of the number of amino acids in the protein, as well as the size of the confined media, have also been studied. Similarities and differences between aggregation in confined and unconfined media are described, including the possibility of no fibril formation, if confinement is severe.

Small angle X-ray scattering analysis of the effect of cold compaction of Al/MoO3 thermite composites.

PubMed

Hammons, Joshua A; Wang, Wei; Ilavsky, Jan; Pantoya, Michelle L; Weeks, Brandon L; Vaughn, Mark W

2008-01-07

Nanothermites composed of aluminum and molybdenum trioxide (MoO(3)) have a high energy density and are attractive energetic materials. To enhance the surface contact between the spherical Al nanoparticles and the sheet-like MoO(3) particles, the mixture can be cold-pressed into a pelleted composite. However, it was found that the burn rate of the pellets decreased as the density of the pellets increased, contrary to expectation. Ultra-small angle X-ray scattering (USAXS) data and scanning electron microscopy (SEM) were used to elucidate the internal structure of the Al nanoparticles, and nanoparticle aggregate in the composite. Results from both SEM imaging and USAXS analysis indicate that as the density of the pellet increased, a fraction of the Al nanoparticles are compressed into sintered aggregates. The sintered Al nanoparticles lost contrast after forming the larger aggregates and no longer scattered X-rays as individual particles. The sintered aggregates hinder the burn rate, since the Al nanoparticles that make them up can no longer diffuse freely as individual particles during combustion. Results suggest a qualitative relationship for the probability that nanoparticles will sinter, based on the particle sizes and the initial structure of their respective agglomerates, as characterized by the mass fractal dimension.

Cosmic dust synthesis by accretion and coagulation

NASA Technical Reports Server (NTRS)

Praburam, G.; Goree, J.

1995-01-01

The morphology of grains grown by accretion and coagulation is revaled by a new laboratory method of synthesizing cosmic dust analogs. Submicron carbon particles, grown by accretion of carbon atoms from a gas, have a spherical shape with a cauliflower-like surface and an internal micro-structure of radial columns. This shape is probably common for grains grown by accretion at a temperature well below the melting point. Coagulated grains, consisting of spheres that collided to form irregular strings, were also synthesized. Another shape we produced had a bumpy non- spherical morphology, like an interplanetary particle collected in the terrestrial stratosphere. Besides these isolated grains, large spongy aggregates of nanometer-size particles were also found for various experimental conditions. Grains were synthesized using ions to sputter a solid target, producing an atomic vapor at a low temperature. The ions were provided by a plasma, which also provided electrostatic levitation of the grains during their growth. The temporal development of grain growth was studied by extinguishing the plasma after various intervals.

PHOTOPHORESIS IN A DILUTE, OPTICALLY THICK MEDIUM AND DUST MOTION IN PROTOPLANETARY DISKS

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

McNally, Colin P.; Hubbard, Alexander, E-mail: cmcnally@nbi.dk, E-mail: ahubbard@amnh.org

2015-11-20

We derive expressions for the photophoretic force on opaque spherical particles in a dilute gas in the optically thick regime where the radiation field is in local thermal equilibrium. Under those conditions, the radiation field has a simple form, leading to well defined analytical approximations for the photophoretic force that also consider both the internal thermal conduction within the particle, and the effects of heat conduction and radiation to the surrounding gas. We derive these results for homogeneous spherical particles; and for the double layered spheres appropriate for modeling solid grains with porous aggregate mantles. Then, as a specific astrophysicalmore » application of these general physical results, we explore the parameter space relevant to the photophoresis driven drift of dust in protoplanetary disks. We show that highly porous silicate grains have sufficiently low thermal conductivities that photophoretic effects, such as significant relative velocities between particles with differing porosity or levitation above the midplane, are expected to occur.« less

Cell and Particle Interactions and Aggregation During Electrophoretic Motion

NASA Technical Reports Server (NTRS)

Wang, Hua; Zeng, Shulin; Loewenberg, Michael; Todd, Paul; Davis, Robert H.

1996-01-01

The stability and pairwise aggregation rates of small spherical particles under the collective effects of buoyancy-driven motion and electrophoretic migration are analyzed. The particles are assumed to be non-Brownian, with thin double-layers and different zeta potentials. The particle aggregation rates may be enhanced or reduced, respectively, by parallel and antiparallel alignments of the buoyancy-driven and electrophoretic velocities. For antiparallel alignments, with the buoyancy-driven relative velocity exceeding the electrophoretic relative velocity between two widely-separated particles, there is a 'collision-forbidden region' in parameter space due to hydrodynamic interactions; thus, the suspension becomes stable against aggregation.

Metagenomic and metaproteomic analyses of Accumulibacter phosphatis-enriched floccular and granular biofilm.

PubMed

Barr, Jeremy J; Dutilh, Bas E; Skennerton, Connor T; Fukushima, Toshikazu; Hastie, Marcus L; Gorman, Jeffrey J; Tyson, Gene W; Bond, Philip L

2016-01-01

Biofilms are ubiquitous in nature, forming diverse adherent microbial communities that perform a plethora of functions. Here we operated two laboratory-scale sequencing batch reactors enriched with Candidatus Accumulibacter phosphatis (Accumulibacter) performing enhanced biological phosphorus removal. Reactors formed two distinct biofilms, one floccular biofilm, consisting of small, loose, microbial aggregates, and one granular biofilm, forming larger, dense, spherical aggregates. Using metagenomic and metaproteomic methods, we investigated the proteomic differences between these two biofilm communities, identifying a total of 2022 unique proteins. To understand biofilm differences, we compared protein abundances that were statistically enriched in both biofilm states. Floccular biofilms were enriched with pathogenic secretion systems suggesting a highly competitive microbial community. Comparatively, granular biofilms revealed a high-stress environment with evidence of nutrient starvation, phage predation pressure, and increased extracellular polymeric substance and cell lysis. Granular biofilms were enriched in outer membrane transport proteins to scavenge the extracellular milieu for amino acids and other metabolites, likely released through cell lysis, to supplement metabolic pathways. This study provides the first detailed proteomic comparison between Accumulibacter-enriched floccular and granular biofilm communities, proposes a conceptual model for the granule biofilm, and offers novel insights into granule biofilm formation and stability. © 2015 Society for Applied Microbiology and John Wiley & Sons Ltd.

A numerical model for aggregations formation and magnetic driving of spherical particles based on OpenFOAM®.

PubMed

Karvelas, E G; Lampropoulos, N K; Sarris, I E

2017-04-01

This work presents a numerical model for the formation of particle aggregations under the influence of a permanent constant magnetic field and their driving process under a gradient magnetic field, suitably created by a Magnetic Resonance Imaging (MRI) device. The model is developed in the OpenFOAM platform and it is successfully compared to the existing experimental and numerical results in terms of aggregates size and their motion in water solutions. Furthermore, several series of simulations are performed for two common types of particles of different diameter in order to verify their aggregation and flow behaviour, under various constant and gradient magnetic fields in the usual MRI working range. Moreover, the numerical model is used to measure the mean length of aggregations, the total time needed to form and their mean velocity under different permanent and gradient magnetic fields. The present model is found to predict successfully the size, velocity and distribution of aggregates. In addition, our simulations showed that the mean length of aggregations is proportional to the permanent magnetic field magnitude and particle diameter according to the relation : l¯ a =7.5B 0 d i 3/2 . The mean velocity of the aggregations is proportional to the magnetic gradient, according to : u¯ a =6.63G˜B 0 and seems to reach a steady condition after a certain period of time. The mean time needed for particles to aggregate is proportional to permanent magnetic field magnitude, scaled by the relationship : t¯ a ∝7B 0 . A numerical model to predict the motion of magnetic particles for medical application is developed. This model is found suitable to predict the formation of aggregations and their motion under the influence of permanent and gradient magnetic fields, respectively, that are produced by an MRI device. The magnitude of the external constant magnetic field is the most important parameter for the aggregations formation and their driving. Copyright © 2017 Elsevier B.V. All rights reserved.

A Delay-Aware and Reliable Data Aggregation for Cyber-Physical Sensing

PubMed Central

Zhang, Jinhuan; Long, Jun; Zhang, Chengyuan; Zhao, Guihu

2017-01-01

Physical information sensed by various sensors in a cyber-physical system should be collected for further operation. In many applications, data aggregation should take reliability and delay into consideration. To address these problems, a novel Tiered Structure Routing-based Delay-Aware and Reliable Data Aggregation scheme named TSR-DARDA for spherical physical objects is proposed. By dividing the spherical network constructed by dispersed sensor nodes into circular tiers with specifically designed widths and cells, TSTR-DARDA tries to enable as many nodes as possible to transmit data simultaneously. In order to ensure transmission reliability, lost packets are retransmitted. Moreover, to minimize the latency while maintaining reliability for data collection, in-network aggregation and broadcast techniques are adopted to deal with the transmission between data collecting nodes in the outer layer and their parent data collecting nodes in the inner layer. Thus, the optimization problem is transformed to minimize the delay under reliability constraints by controlling the system parameters. To demonstrate the effectiveness of the proposed scheme, we have conducted extensive theoretical analysis and comparisons to evaluate the performance of TSR-DARDA. The analysis and simulations show that TSR-DARDA leads to lower delay with reliability satisfaction. PMID:28218668

Impact of cationic surfactant on the self-assembly of sodium caseinate.

PubMed

Vinceković, Marko; Curlin, Marija; Jurašin, Darija

2014-08-27

The impact of a cationic surfactant, dodecylammonium chloride (DDACl), on the self-assembly of sodium caseinate (SC) has been investigated by light scattering, zeta potential, and rheological measurements as well as by microscopy (transmission electron and confocal laser scanning microscopy). In SC dilute solutions concentration-dependent self-assembly proceeds through the formation of spherical associates and their aggregation into elongated structures composed of connected spheres. DDACl interacts with SC via its hydrophilic and hydrophobic groups, inducing changes in SC self-assembled structures. These changes strongly depend on the surfactant aggregation states (monomeric or micellar) as well as concentration ratio of both components, leading to the formation of soluble and insoluble complexes of nano- to microdimensions. DDACl monomers interact with SC self-assembled entities in a different way compared to their micelles. Surfactant monomers form soluble complexes (similar to surfactant mixed micelles) at lower SC concentration but insoluble gelatinous complexes at higher SC concentration. At surfactant micellar concentration soluble complexes with casein chains wrapped around surfactant micelles are formed. This study suggests that the use of proper cationic surfactant concentration will allow modification and control of structural changes of SC self-assembled entities.

Experimental volcanic ash aggregation: Internal structuring of accretionary lapilli and the role of liquid bonding

NASA Astrophysics Data System (ADS)

Mueller, Sebastian B.; Kueppers, Ulrich; Ayris, Paul M.; Jacob, Michael; Dingwell, Donald B.

2016-01-01

Explosive volcanic eruptions can release vast quantities of pyroclastic material into Earth's atmosphere, including volcanic ash, particles with diameters less than two millimeters. Ash particles can cluster together to form aggregates, in some cases reaching up to several centimeters in size. Aggregation alters ash transport and settling behavior compared to un-aggregated particles, influencing ash distribution and deposit stratigraphy. Accretionary lapilli, the most commonly preserved type of aggregates within the geologic record, can exhibit complex internal stratigraphy. The processes involved in the formation and preservation of these aggregates remain poorly constrained quantitatively. In this study, we simulate the variable gas-particle flow conditions which may be encountered within eruption plumes and pyroclastic density currents via laboratory experiments using the ProCell Lab System® of Glatt Ingenieurtechnik GmbH. In this apparatus, solid particles are set into motion in a fluidized bed over a range of well-controlled boundary conditions (particle concentration, air flow rate, gas temperature, humidity, liquid composition). Experiments were conducted with soda-lime glass beads and natural volcanic ash particles under a range of experimental conditions. Both glass beads and volcanic ash exhibited the capacity for aggregation, but stable aggregates could only be produced when materials were coated with high but volcanically-relevant concentrations of NaCl. The growth and structure of aggregates was dependent on the initial granulometry, while the rate of aggregate formation increased exponentially with increasing relative humidity (12-45% RH), before overwetting promoted mud droplet formation. Notably, by use of a broad granulometry, we generated spherical, internally structured aggregates similar to some accretionary pellets found in volcanic deposits. Adaptation of a powder-technology model offers an explanation for the origin of natural accretionary pellets, suggesting them to be the result of a particular granulometry and fast-acting selective aggregation processes. For such aggregates to survive deposition and be preserved in the deposits of eruption plumes and pyroclastic density currents likely requires a significant pre-existing salt load on ash surfaces, and rapid aggregate drying prior to deposition or interaction with a more energetic environment. Our results carry clear benefits for future efforts to parameterize models of ash transport and deposition in the field.

Iron Oxide Nanospheres and Nanocubes for Magnetic Hyperthermia Therapy: A Comparative Study

NASA Astrophysics Data System (ADS)

Nemati, Z.; Das, R.; Alonso, J.; Clements, E.; Phan, M. H.; Srikanth, H.

2017-06-01

Improving the heating capacity of magnetic nanoparticles (MNPs) for hyperthermia therapy is an important but challenging task. Through a comparative study of the inductive heating properties of spherical and cubic Fe3O4 MNPs with two distinct average volumes (˜7000 nm3 and 80,000 nm3), we demonstrate that, for small size (˜7000 nm3), the cubic MNPs heat better compared with the spherical MNPs. However, the opposite trend is observed for larger size (˜80,000 nm3). The improvement in heating efficiency in cubic small-sized MNPs (˜7000 nm3) can be attributed to enhanced anisotropy and the formation of chain-like aggregates, whereas the decrease of the heating efficiency in cubic large-sized MNPs (˜80,000 nm3) has been attributed to stronger aggregation of particles. Physical motion is shown to contribute more to the heating efficiency in case of spherical than cubic MNPs, when dispersed in water. These findings are of crucial importance in understanding the role of shape anisotropy and optimizing the heating response of magnetic nano-structures for advanced hyperthermia.

Self-assembly formation of palm-based esters nano-emulsion: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Abdul Rahman, Mohd. Basyaruddin; Huan, Qiu-Yi; Tejo, Bimo A.; Basri, Mahiran; Salleh, Abu Bakar; Rahman, Raja Noor Zaliha Abdul

2009-10-01

Palm-oil esters (POEs) are unsaturated and non-ionic esters that can be prepared by enzymatic synthesis from palm oil. Their nano-emulsion properties possess great potential to act as drug carrier for transdermal drug delivery system. A ratio of 75:5:20 (water/POEs/Span20) was chosen from homogenous region in the phase diagram of our previous experimental work to undergo molecular dynamics simulation. A 15 ns molecular dynamics simulation of nano-emulsion system (water/POEs/Span20) was carried out using OPLS-AA force field. The aggregations of the oil and surfactant molecules are observed throughout the simulation. After 8 ns of simulation, the molecules start to aggregate to form one spherical micelle where the POEs molecules are surrounded by the non-ionic surfactant (Span20) molecules with an average size of 4.2 ± 0.05 nm. The size of the micelle and the ability of palm-based nano-emulsion to self-assemble suggest that this nano-emulsion can potentially use in transdermal drug delivery system.

Physical confinement signals regulate the organization of stem cells in three dimensions

PubMed Central

Sean, David; Ignacio, Maxime; Godin, Michel; Slater, Gary W.; Pelling, Andrew E.

2016-01-01

During embryogenesis, the spherical inner cell mass (ICM) proliferates in the confined environment of a blastocyst. Embryonic stem cells (ESCs) are derived from the ICM, and mimicking embryogenesis in vitro, mouse ESCs (mESCs) are often cultured in hanging droplets. This promotes the formation of a spheroid as the cells sediment and aggregate owing to increased physical confinement and cell–cell interactions. In contrast, mESCs form two-dimensional monolayers on flat substrates and it remains unclear if the difference in organization is owing to a lack of physical confinement or increased cell–substrate versus cell–cell interactions. Employing microfabricated substrates, we demonstrate that a single geometric degree of physical confinement on a surface can also initiate spherogenesis. Experiment and computation reveal that a balance between cell–cell and cell–substrate interactions finely controls the morphology and organization of mESC aggregates. Physical confinement is thus an important regulatory cue in the three-dimensional organization and morphogenesis of developing cells. PMID:27798278

Retrieval of microphysical characteristics of particles in atmospheres of distant comets from ground-based polarimetry

NASA Astrophysics Data System (ADS)

Dlugach, Janna M.; Ivanova, Oleksandra V.; Mishchenko, Michael I.; Afanasiev, Viktor L.

2018-01-01

We summarize unique aperture data on the degree of linear polarization observed for distant comets C/2010 S1, C/2010 R1, C/2011 KP36, C/2012 J1, C/2013 V4, and C/2014 A4 with heliocentric distances exceeding 3 AU. Observations have been carried out at the 6-m telescope of the Special Astrophysical Observatory of the Russian Academy of Sciences (Nizhnij Arkhyz, Russia) during the period from 2011 to 2016. The measured negative polarization proves to be significantly larger in absolute value than what is typically observed for comets close to the Sun. We compare the new observational data with the results of numerical modeling performed with the T-matrix and superposition T-matrix methods. In our computer simulations, we assume the cometary coma to be an optically thin cloud containing particles in the form of spheroids, fractal aggregates composed of spherical monomers, and mixtures of spheroids and aggregate particles. We obtain a good semi-quantitative agreement between all polarimetric data for the observed distant comets and the results of numerical modeling for the following models of the cometary dust: (i) a mixture of submicrometer water-ice oblate spheroids with aggregates composed of submicrometer silicate monomers; and (ii) a mixture of submicrometer water-ice oblate spheroids and aggregates consisting of both silicate and organic monomers. The microphysical parameters of these models are presented and discussed.

Copper Nanoparticles: Synthesis and Biological Activity

NASA Astrophysics Data System (ADS)

Satyvaldiev, A. S.; Zhasnakunov, Z. K.; Omurzak, E.; Doolotkeldieva, T. D.; Bobusheva, S. T.; Orozmatova, G. T.; Kelgenbaeva, Z.

2018-01-01

By means of XRD and FESEM analysis, it is established that copper nanoparticles with sizes less than 10 nm are formed during the chemical reduction, which form aggregates mainly with spherical shape. Presence of gelatin during the chemical reduction of copper induced formation of smaller size distribution nanoparticles than that of nanoparticles synthesized without gelatin and it can be related to formation of protective layer. Synthesized Cu nano-powders have sufficiently high activity against the Erwinia amylovora bacterium, and the bacterial growth inhibition depends on the Cu nanoparticles concentration. At a concentration of 5 mg / ml of Cu nanoparticles, the exciter growth inhibition zone reaches a maximum value within 72 hours and the lysis zone is 20 mm, and at a concentration of 1 mg / ml this value is 16 mm, which also indicates the significant antibacterial activity of this sample.

Morphology of clusters of attractive dry and wet self-propelled spherical particle suspensions.

PubMed

Alarcón, Francisco; Valeriani, Chantal; Pagonabarraga, Ignacio

2017-01-25

In order to assess the effect of hydrodynamics in the assembly of active attractive spheres, we simulate a semi-dilute suspension of attractive self-propelled spherical particles in a quasi-two dimensional geometry comparing the case with and without hydrodynamics interactions. To start with, independent of the presence of hydrodynamics, we observe that depending on the ratio between attraction and propulsion, particles either coarsen or aggregate forming finite-size clusters. Focusing on the clustering regime, we characterize two different cluster parameters, i.e. their morphology and orientational order, and compare the case when active particles behave either as pushers or pullers (always in the regime where inter-particle attractions compete with self-propulsion). Studying cluster phases for squirmers with respect to those obtained for active Brownian disks (indicated as ABPs), we have shown that hydrodynamics alone can sustain a cluster phase of active swimmers (pullers), while ABPs form cluster phases due to the competition between attraction and self-propulsion. The structural properties of the cluster phases of squirmers and ABPs are similar, although squirmers show sensitivity to active stresses. Active Brownian disks resemble weakly pusher squirmer suspensions in terms of cluster size distribution, structure of the radius of gyration on the cluster size and degree of cluster polarity.

Hydrogels in endovascular embolization. I. Spherical particles of poly(2-hydroxyethyl methacrylate) and their medico-biological properties.

PubMed

Horák, D; Svec, F; Kálal, J; Gumargalieva, K; Adamyan, A; Skuba, N; Titova, M; Trostenyuk, N

1986-05-01

Spherical macroporous particles based on poly(2-hydroxyethyl methacrylate) with defined porosity, swelling and morphology have been developed, and are suitable for endovascular occlusion of various organs. Unlike cylindrical particles, spherical particles are specifically suited for transcatheteral introduction. The method chosen for the preparation of such particles was suspension radical polymerization, where the monomers were dissolved in a mixture of higher-boiling alcohols, and the solution dispersed in water. Physicochemical and medico-biological properties of spherical particles were examined. The residual amounts of monomers and other low-molecular compounds were checked; haematological analyses showed that the value 10(-5) g/g of the polymer was not toxic and contributed to an irreversible aggregation of thrombocytes. The occlusion effect in the vascular lumen was stable. The histomorphological results fully demonstrated the perfect biocompatibility of artificial spherical emboli. The latter met the requirements of application to clinical practice.

Electronic scattering, focusing, and resonance by a spherical barrier in Weyl semimetals

NASA Astrophysics Data System (ADS)

Lu, Ming; Zhang, Xiao-Xiao

2018-05-01

We solve the Weyl electron scattered by a spherical step potential barrier. Tuning the incident energy and the potential radius, one can enter both quasiclassical and quantum regimes. Transport features related to far-field currents and integrated cross sections are studied to reveal the preferred forward scattering. In the quasiclassical regime, a strong focusing effect along the incident spherical axis is found in addition to optical caustic patterns. In the quantum regime, at energies of successive angular momentum resonances, a polar aggregation of electron density is found inside the potential. The findings will be useful in transport studies and electronic lens applications in Weyl systems.

Three-photon-excited luminescence from unsymmetrical cyanostilbene aggregates: morphology tuning and targeted bioimaging.

PubMed

Mandal, Amal Kumar; Sreejith, Sivaramapanicker; He, Tingchao; Maji, Swarup Kumar; Wang, Xiao-Jun; Ong, Shi Li; Joseph, James; Sun, Handong; Zhao, Yanli

2015-05-26

We report an experimental observation of aggregation-induced enhanced luminescence upon three-photon excitation in aggregates formed from a class of unsymmetrical cyanostilbene derivatives. Changing side chains (-CH3, -C6H13, -C7H15O3, and folic acid) attached to the cyanostilbene core leads to instantaneous formation of aggregates with sizes ranging from micrometer to nanometer scale in aqueous conditions. The crystal structure of a derivative with a methyl side chain reveals the planarization in the unsymmetrical cyanostilbene core, causing luminescence from corresponding aggregates upon three-photon excitation. Furthermore, folic acid attached cyanostilbene forms well-dispersed spherical nanoaggregates that show a high three-photon cross-section of 6.0 × 10(-80) cm(6) s(2) photon(-2) and high luminescence quantum yield in water. In order to demonstrate the targeted bioimaging capability of the nanoaggregates, three cell lines (HEK293 healthy cell line, MCF7 cancerous cell line, and HeLa cancerous cell line) were employed for the investigations on the basis of their different folate receptor expression level. Two kinds of nanoaggregates with and without the folic acid targeting ligand were chosen for three-photon bioimaging studies. The cell viability of three types of cells incubated with high concentration of nanoaggregates still remained above 70% after 24 h. It was observed that the nanoaggregates without the folic acid unit could not undergo the endocytosis by both healthy and cancerous cell lines. No obvious endocytosis of folic acid attached nanoaggregates was observed from the HEK293 and MCF7 cell lines having a low expression of the folate receptor. Interestingly, a significant amount of endocytosis and internalization of folic acid attached nanoaggregates was observed from HeLa cells with a high expression of the folate receptor under three-photon excitation, indicating targeted bioimaging of folic acid attached nanoaggregates to the cancer cell line. This study presents a paradigm of using organic nanoaggregates for targeted three-photon bioimaging.

Empirical Relationships Between Optical Properties and Equivalent Diameters of Fractal Soot Aggregates at 550 Nm Wavelength.

NASA Technical Reports Server (NTRS)

Pandey, Apoorva; Chakrabarty, Rajan K.; Liu, Li; Mishchenko, Michael I.

2015-01-01

Soot aggregates (SAs)-fractal clusters of small, spherical carbonaceous monomers-modulate the incoming visible solar radiation and contribute significantly to climate forcing. Experimentalists and climate modelers typically assume a spherical morphology for SAs when computing their optical properties, causing significant errors. Here, we calculate the optical properties of freshly-generated (fractal dimension Df = 1.8) and aged (Df = 2.6) SAs at 550 nm wavelength using the numericallyexact superposition T-Matrix method. These properties were expressed as functions of equivalent aerosol diameters as measured by contemporary aerosol instruments. This work improves upon previous efforts wherein SA optical properties were computed as a function of monomer number, rendering them unusable in practical applications. Future research will address the sensitivity of variation in refractive index, fractal prefactor, and monomer overlap of SAs on the reported empirical relationships.

[A study of the aggregation of human red blood cells induced by picric acid].

PubMed

Sheremet'ev, Iu A; Sheremet'eva, A V; Lednev, A V

2005-01-01

The effect of picric acid on the aggregation of human erythrocytes was studied. It was shown that the addition of picric acid to a suspension of washed erythrocytes leads to a decrease in pH of medium to 1.5-2 and the formation of echinocytes. Stirring the suspension of echinocytes at low pH values results in a strong aggregation of cells. Increasing the pH value to 7.4 leads to a desaggregation of echinocytes. It was found that picric acid does not induce the aggregation of cells fixed by glutaraldehyde. A substantial decrease in the aggegation of spheric erythrocytes obtained after heating the cells at 50 degrees C was observed.

Spatial Modeling of Iron Transformations Within Artificial Soil Aggregates

NASA Astrophysics Data System (ADS)

Kausch, M.; Meile, C.; Pallud, C.

2008-12-01

Structured soils exhibit significant variations in transport characteristics at the aggregate scale. Preferential flow occurs through macropores while predominantly diffusive exchange takes place in intra-aggregate micropores. Such environments characterized by mass transfer limitations are conducive to the formation of small-scale chemical gradients and promote strong spatial variation in processes controlling the fate of redox-sensitive elements such as Fe. In this study, we present a reactive transport model used to spatially resolve iron bioreductive processes occurring within a spherical aggregate at the interface between advective and diffusive domains. The model is derived from current conceptual models of iron(hydr)oxide (HFO) transformations and constrained by literature and experimental data. Data were obtained from flow-through experiments on artificial soil aggregates inoculated with Shewanella putrefaciens strain CN32, and include the temporal evolution of the bulk solution composition, as well as spatial information on the final solid phase distribution within aggregates. With all iron initially in the form of ferrihydrite, spatially heterogeneous formation of goethite/lepidocrocite, magnetite and siderite was observed during the course of the experiments. These transformations were reproduced by the model, which ascribes a central role to divalent iron as a driver of HFO transformations and master variable in the rate laws of the considered reaction network. The predicted dissolved iron breakthrough curves also match the experimental ones closely. Thus, the computed chemical concentration fields help identify factors governing the observed trends in the solid phase distribution patterns inside the aggregate. Building on a mechanistic description of transformation reactions, fluid flow and solute transport, the model was able to describe the observations and hence illustrates the importance of small-scale gradients and dynamics of bioreductive processes for assessing bulk iron cycling. As HFOs are ubiquitous in soils, such process-level understanding of aggregate-scale iron dynamics has broad implications for the prediction of the subsurface fate of nutrients and contaminants that interact strongly with HFO surfaces.

Charging of Aggregate Grains in Astrophysical Environments

NASA Astrophysics Data System (ADS)

Ma, Qianyu; Matthews, Lorin S.; Land, Victor; Hyde, Truell W.

2013-02-01

The charging of dust grains in astrophysical environments has been investigated with the assumption that these grains are homogeneous spheres. However, there is evidence which suggests that many grains in astrophysical environments are irregularly shaped aggregates. Recent studies have shown that aggregates acquire higher charge-to-mass ratios due to their complex structures, which in turn may alter their subsequent dynamics and evolution. In this paper, the charging of aggregates is examined including secondary electron emission and photoemission in addition to primary plasma currents. The results show that the equilibrium charge on aggregates can differ markedly from spherical grains with the same mass, but that the charge can be estimated for a given environment based on structural characteristics of the grain. The "small particle effect" due to secondary electron emission is also important for de terming the charge of micron-sized aggregates consisting of nano-sized particles.

Novel platelet substitutes: disk-shaped biodegradable nanosheets and their enhanced effects on platelet aggregation.

PubMed

Okamura, Yosuke; Fukui, Yoshihito; Kabata, Koki; Suzuki, Hidenori; Handa, Makoto; Ikeda, Yasuo; Takeoka, Shinji

2009-10-21

We have studied biocompatible spherical carriers carrying a dodecapeptide, HHLGGAKQAGDV (H12), on their surface as platelet substitutes. This peptide is a fibrinogen γ-chain carboxy-terminal sequence (γ400-411) and specifically recognizes the active form of glycoprotein IIb/IIIa on activated platelets. Our purpose is to assess the possibility of making a novel platelet substitute consisting of disk-shaped nanosheets having a large contact area for the targeting site, rather than conventional small contact area spherical carriers. The H12 peptide was conjugated to the surface of the free-standing nanosheets made of biodegradable poly(d,l-lactide-co-glycolide) (PLGA). These H12-PLGA nanosheets were fabricated onto 3 μm disk-shaped patterned hydrophobic octadecyl regions on a SiO(2) substrate. By way of comparison, spherical H12-PLGA microparticles with the same surface area and conjugation number of H12 were also prepared. The resulting H12-PLGA nanosheets specifically interacted with the activated platelets adhered on the collagen surface at twice the rate of the H12-PLGA microparticles under flow conditions, and showed platelet thrombus formation in a two-dimensional spreading manner. Thus, H12-PLGA nanosheets might be a suitable candidate novel platelet alternative substitute for infused human platelet concentrates for the treatment of bleeding in patients with severe thrombocytopenia.

Formation of aggregated nanoparticle spheres through femtosecond laser surface processing

NASA Astrophysics Data System (ADS)

Tsubaki, Alfred T.; Koten, Mark A.; Lucis, Michael J.; Zuhlke, Craig; Ianno, Natale; Shield, Jeffrey E.; Alexander, Dennis R.

2017-10-01

A detailed structural and chemical analysis of a class of self-organized surface structures, termed aggregated nanoparticle spheres (AN-spheres), created using femtosecond laser surface processing (FLSP) on silicon, silicon carbide, and aluminum is reported in this paper. AN-spheres are spherical microstructures that are 20-100 μm in diameter and are composed entirely of nanoparticles produced during femtosecond laser ablation of material. AN-spheres have an onion-like layered morphology resulting from the build-up of nanoparticle layers over multiple passes of the laser beam. The material properties and chemical composition of the AN-spheres are presented in this paper based on scanning electron microscopy (SEM), focused ion beam (FIB) milling, transmission electron microscopy (TEM), and energy dispersive x-ray spectroscopy (EDX) analysis. There is a distinct difference in the density of nanoparticles between concentric rings of the onion-like morphology of the AN-sphere. Layers of high-density form when the laser sinters nanoparticles together and low-density layers form when nanoparticles redeposit while the laser ablates areas surrounding the AN-sphere. The dynamic nature of femtosecond laser ablation creates a variety of nanoparticles that make-up the AN-spheres including Si/C core-shell, nanoparticles that directly fragmented from the base material, nanoparticles with carbon shells that retarded oxidation, and amorphous, fully oxidized nanoparticles.

Root-Knot Nematodes Exhibit Strain-Specific Clumping Behavior That Is Inherited as a Simple Genetic Trait

PubMed Central

Wang, Congli; Lower, Steven; Thomas, Varghese P.; Williamson, Valerie M.

2010-01-01

Root-knot nematodes are obligate parasites of a wide range of plant species and can feed only on the cytoplasm of living plant cells. In the absence of a suitable plant host, infective juveniles of strain VW9 of the Northern root-knot nematode, Meloidogyne hapla, when dispersed in Pluronic F-127 gel, aggregate into tight, spherical clumps containing thousands of worms. Aggregation or clumping behavior has been observed in diverse genera in the phylum Nematoda spanning free-living species such as Caenorhabditis elegans as well as both plant and animal parasites. Clumping behavior differs between strains of M. hapla and occurs with other species within this genus where strain-specific differences in clumping ability are also apparent. Exposure of M. hapla juveniles to a gradient formed using low levels of cyanide promotes formation of clumps at a preferred cyanide level. Analysis of F2 lines from a cross of M. hapla strains that differ in clump-forming behavior reveals that the behavior segregates as a single, major locus that can be positioned on the genetic map of this nematode. Clumping behavior may be a survival strategy whose importance and function depend on the niche of the nematode strain or species. PMID:21151553

Modelling and shadowgraph imaging of cocrystal dissolution and assessment of in vitro antimicrobial activity for sulfadimidine/4-aminosalicylic acid cocrystals.

PubMed

Serrano, Dolores R; Persoons, Tim; D'Arcy, Deirdre M; Galiana, Carolina; Dea-Ayuela, Maria Auxiliadora; Healy, Anne Marie

2016-06-30

The aim of this work was to evaluate the influence of crystal habit on the dissolution and in vitro antibacterial and anitiprotozoal activity of sulfadimidine:4-aminosalicylic acid cocrystals. Cocrystals were produced via milling or solvent mediated processes. In vitro dissolution was carried out in the flow-through apparatus, with shadowgraph imaging and mechanistic mathematical models used to observe and simulate particle dissolution. In vitro activity was tested using agar diffusion assays. Cocrystallisation via milling produced small polyhedral crystals with antimicrobial activity significantly higher than sulfadimidine alone, consistent with a fast dissolution rate which was matched only by cocrystals which were milled following solvent evaporation. Cocrystallisation by solvent evaporation (ethanol, acetone) or spray drying produced flattened, plate-like or quasi-spherical cocrystals, respectively, with more hydrophobic surfaces and greater tendency to form aggregates in aqueous media, limiting both the dissolution rate and in vitro activity. Deviation from predicted dissolution profiles was attributable to aggregation behaviour, supported by observations from shadowgraph imaging. Aggregation behaviour during dissolution of cocrystals with different habits affected the dissolution rate, consistent with in vitro activity. Combining mechanistic models with shadowgraph imaging is a valuable approach for dissolution process analysis. Copyright © 2016 Elsevier B.V. All rights reserved.

Effects of Complementary DNA and Salt on the Thermoresponsiveness of Poly(N-isopropylacrylamide)-b-DNA.

PubMed

Fujita, Masahiro; Hiramine, Hayato; Pan, Pengju; Hikima, Takaaki; Maeda, Mizuo

2016-02-02

The thermoresponsive structural transition of poly(N-isopropylacrylamide) (PNIPAAm)-b-DNA copolymers was explored. Molecular assembly of the block copolymers was facilitated by adding salt, and this assembly was not nucleated by the association between DNA strands but by the coil-globule transition of PNIPAAm blocks. Below the lower critical solution temperature (LCST) of PNIPAAm, the copolymer solution remained transparent even at high salt concentrations, regardless of whether DNA was hybridized with its complementary partner to form a double-strand (or single-strand) structure. At the LCST, the hybridized copolymer assembled in spherical nanoparticles, surrounded by double-stranded DNA; subsequently, the non-cross-linking aggregation occurred, while the nanoparticles were dispersed if the salt concentration was low or DNA blocks were unhybridized. When the DNA duplex was denatured to a single-stranded state by heating, the aggregated nanoparticles redispersed owing to the recovery of the steric repulsion of the DNA strands. The changes in the steric and electrostatic effects by hybridization and the addition of salt did not result in any specific attraction between DNA strands but merely decreased the repulsive interactions. The van der Waals attraction between the nanoparticles overcame such repulsive interactions so that the non-cross-linking aggregation of the micellar particles was mediated.

A new attraction-disseverance model for explaining landsliding in clay-rich tephras

NASA Astrophysics Data System (ADS)

Kluger, M. O.; Moon, V.; Kreiter, S.; Lowe, D.; Churchman, J.; Hepp, D. A.; Seibel, D.; Jorat, E.; Mörz, T.

2016-12-01

Altered tephras are highly susceptible to landsliding and account for fatalities and property damage every year. The clay mineral halloysite is often associated with landslide-prone layers within weathered tephra successions, especially in deposits with high sensitivity, which describes the post-failure strength loss. However, the precise role of halloysite on the development of sensitivity and thus sudden and unpredictable landsliding is unknown. Here we show that an abundance of halloysite, dominated by a distinctive ovate mushroom-cap-shaped (MCS) spherical morphology, governs the development of sensitivity, and hence proneness to landsliding, in weathered rhyolitic tephras in eastern North Island, New Zealand. We found that a highly sensitive layer, which was involved in a retrogressive landslide, has an extraordinarily high content of aggregated MCS spheres with imperfectly-closed exterior surfaces, i.e., the MCS spheres have substantial openings on one side. We suggest that short-range electrostatic and van der Waals' interactions enabled the MCS spheres to form interconnected aggregates by attraction between numerous paired silanol and aluminol layers with a weakly positive, or neutral, charge exposed in the openings and the negatively-charged convex silanol faces on the curved exterior surfaces of the spheres. However, if these weak attractions are overcome during slope failure, the prevailing repulsion between two exterior surfaces result in a low remolded shear strength, i.e., a high sensitivity, and thus a high propensity for flow-like landsliding. Our results indicate that this novel electrostatic attraction-disseverance model explains the high sensitivity and therefore contributes to a general understanding of the mechanisms of landsliding in sensitive altered tephras rich in spherical halloysite.

A novel embeddable spherical smart aggregate for structural health monitoring: part I. Fabrication and electrical characterization

NASA Astrophysics Data System (ADS)

Kong, Qingzhao; Fan, Shuli; Bai, Xiaolong; Mo, Y. L.; Song, Gangbing

2017-09-01

Recently developed piezoceramic-based transducers, known as smart aggregates (SAs), have shown their applicability and versatility in various applications of structural health monitoring (SHM). The lead zirconate titanate (PZT) patches embedded inside SAs have different modes that are more suitable for generating or receiving different types of stress waves (e.g. P and S waves, each of which has a unique role in SHM). However, due to the geometry of the 2D PZT patch, the embedded SA can only generate or receive the stress wave in a single direction and thus greatly limits its applications. This paper is the first of a series of two companion papers that introduces the authors’ latest work in developing a novel, embeddable spherical smart aggregate (SSA) for the health monitoring of concrete structures. In addition to the 1D guided wave produced by SA, the SSA embedded in concrete structures can generate or receive omni-directional stress waves that can significantly improve the detection aperture and provide additional functionalities in SHM. In the first paper (Part I), the detailed fabrication procedures with the help of 3D printing technology and electrical characterization of the proposed SSA is presented. The natural frequencies of the SSA were experimentally obtained and further compared with the numerical results. In addition, the influence of the components’ thickness (spherical piezoceramic shell and epoxy) and outer radius (spherical piezoceramic shell and protection concrete) on the natural frequencies of the SSA were analytically studied. The results will help elucidate the key parameters that determine the natural frequencies of the SSA. The natural frequencies of the SSA can thus be designed for suitability in the damage detection of concrete structures. In the second paper (Part II), further numerical and experimental verifications on the performance of the proposed SSA in concrete structures will be discussed.

Predictive modeling of multicellular structure formation by using Cellular Particle Dynamics simulations

NASA Astrophysics Data System (ADS)

McCune, Matthew; Shafiee, Ashkan; Forgacs, Gabor; Kosztin, Ioan

2014-03-01

Cellular Particle Dynamics (CPD) is an effective computational method for describing and predicting the time evolution of biomechanical relaxation processes of multicellular systems. A typical example is the fusion of spheroidal bioink particles during post bioprinting structure formation. In CPD cells are modeled as an ensemble of cellular particles (CPs) that interact via short-range contact interactions, characterized by an attractive (adhesive interaction) and a repulsive (excluded volume interaction) component. The time evolution of the spatial conformation of the multicellular system is determined by following the trajectories of all CPs through integration of their equations of motion. CPD was successfully applied to describe and predict the fusion of 3D tissue construct involving identical spherical aggregates. Here, we demonstrate that CPD can also predict tissue formation involving uneven spherical aggregates whose volumes decrease during the fusion process. Work supported by NSF [PHY-0957914]. Computer time provided by the University of Missouri Bioinformatics Consortium.

Casein Aggregates Built Step-by-Step on Charged Polyelectrolyte Film Surfaces Are Calcium Phosphate-cemented*

PubMed Central

Nagy, Krisztina; Pilbat, Ana-Maria; Groma, Géza; Szalontai, Balázs; Cuisinier, Frédéric J. G.

2010-01-01

The possible mechanism of casein aggregation and micelle buildup was studied in a new approach by letting α-casein adsorb from low concentration (0.1 mg·ml−1) solutions onto the charged surfaces of polyelectrolyte films. It was found that α-casein could adsorb onto both positively and negatively charged surfaces. However, only when its negative phosphoseryl clusters remained free, i.e. when it adsorbed onto a negative surface, could calcium phosphate (CaP) nanoclusters bind to the casein molecules. Once the CaP clusters were in place, step-by-step building of multilayered casein architectures became possible. The presence of CaP was essential; neither Ca2+ nor phosphate could alone facilitate casein aggregation. Thus, it seems that CaP is the organizing motive in the casein micelle formation. Atomic force microscopy revealed that even a single adsorbed casein layer was composed of very small (in the range of tens of nanometers) spherical forms. The stiffness of the adsorbed casein layer largely increased in the presence of CaP. On this basis, we can imagine that casein micelles emerge according to the following scheme. The amphipathic casein monomers aggregate into oligomers via hydrophobic interactions even in the absence of CaP. Full scale, CaP-carrying micelles could materialize by interlocking these casein oligomers with CaP nanoclusters. Such a mechanism would not contradict former experimental results and could offer a synthesis between the submicelle and the block copolymer models of casein micelles. PMID:20921229

Cellular Particle Dynamics simulation of biomechanical relaxation processes of multi-cellular systems

NASA Astrophysics Data System (ADS)

McCune, Matthew; Kosztin, Ioan

2013-03-01

Cellular Particle Dynamics (CPD) is a theoretical-computational-experimental framework for describing and predicting the time evolution of biomechanical relaxation processes of multi-cellular systems, such as fusion, sorting and compression. In CPD, cells are modeled as an ensemble of cellular particles (CPs) that interact via short range contact interactions, characterized by an attractive (adhesive interaction) and a repulsive (excluded volume interaction) component. The time evolution of the spatial conformation of the multicellular system is determined by following the trajectories of all CPs through numerical integration of their equations of motion. Here we present CPD simulation results for the fusion of both spherical and cylindrical multi-cellular aggregates. First, we calibrate the relevant CPD model parameters for a given cell type by comparing the CPD simulation results for the fusion of two spherical aggregates to the corresponding experimental results. Next, CPD simulations are used to predict the time evolution of the fusion of cylindrical aggregates. The latter is relevant for the formation of tubular multi-cellular structures (i.e., primitive blood vessels) created by the novel bioprinting technology. Work supported by NSF [PHY-0957914]. Computer time provided by the University of Missouri Bioinformatics Consortium.

A novel approach to a fine particle coating using porous spherical silica as core particles.

PubMed

Ishida, Makoto; Uchiyama, Jumpei; Isaji, Keiko; Suzuki, Yuta; Ikematsu, Yasuyuki; Aoki, Shigeru

2014-08-01

Abstract The applicability of porous spherical silica (PSS) was evaluated as core particles for pharmaceutical products by comparing it with commercial core particles such as mannitol (NP-108), sucrose and microcrystalline cellulose spheres. We investigated the physical properties of core particles, such as particle size distribution, flow properties, crushing strength, plastic limit, drying rate, hygroscopic property and aggregation degree. It was found that PSS was a core particle of small particle size, low friability, high water adsorption capacity, rapid drying rate and lower occurrence of particle aggregation, although wettability is a factor to be carefully considered. The aggregation and taste-masking ability using PSS and NP-108 as core particles were evaluated at a fluidized-bed coating process. The functional coating under the excess spray rate shows different aggregation trends and dissolution profiles between PSS and NP-108; thereby, exhibiting the formation of uniform coating under the excess spray rate in the case of PSS. This expands the range of the acceptable spray feed rates to coat fine particles, and indicates the possibility of decreasing the coating time. The results obtained in this study suggested that the core particle, which has a property like that of PSS, was useful in overcoming such disadvantages as large particle size, which feels gritty in oral cavity; particle aggregation; and the long coating time of the particle coating process. These results will enable the practical fine particle coating method by increasing the range of optimum coating conditions and decreasing the coating time in fluidized bed technology.

Numerical investigation on the Ångström exponent of black carbon aerosol

NASA Astrophysics Data System (ADS)

Li, Ji; Liu, Chao; Yin, Yan; Kumar, K. Raghavendra

2016-04-01

Black carbon (BC) plays an important role on the global and regional climate, whereas there are significant uncertainties on its optical properties. Among various optical properties, the Ångström exponent (AE) indicates the spectral variation of the particle-optic interaction and is widely used to understand the aerosol properties. We consider the influence of BC geometry on its optical properties and assess the sensitivity of the AE to particle geometry and size distribution. The fractal aggregates with different fractal dimensions are used to represent realistic BC particles, and popular equivalent volume spherical and spheroidal models are also considered for comparison. Even if the fractal aggregates become highly compact and spherical, their optical properties are still significantly different from those of equivalent volume spheres or spheroids. Meanwhile, the Rayleigh-Debye-Gans approximation can hardly provide accurate results for all optical quantities of aggregates with different dimensions. The extinction Ångström exponent (EAE) and absorption Ångström exponent (AAE) are sensitive to both particle geometry and size distribution. With BC becoming more compact (from fractal aggregate to spheroid and to sphere), the AE becomes more sensitive to particle size distribution. The EAE and AAE of aggregates with different size distributions vary between 1.10-1.63 and 0.87-1.50, respectively, whereas those of the spheres or spheroids have wider ranges. Furthermore, the AE at smaller wavelengths (between 0.35 µm and 0.55 µm) is more sensitive to geometry and size distribution than that given by optical properties at larger wavelengths (between 0.55 µm and 0.88 µm).

Chromatic patchy particles: Effects of specific interactions on liquid structure

DOE PAGES

Vasilyev, Oleg A.; Tkachenko, Alexei V.; Klumov, Boris A.

2015-07-13

We study the structural and thermodynamic properties of patchy particle liquids, with a special focus on the role of “color,” i.e., specific interactions between individual patches. A possible experimental realization of such “chromatic” interactions is by decorating the particle patches with single-stranded DNA linkers. The complementarity of the linkers can promote selective bond formation between predetermined pairs of patches. By using MD simulations, we compare the local connectivity, the bond orientation order, and other structural properties of the aggregates formed by the “colored” and “colorless” systems. The analysis is done for spherical particles with two different patch arrangements (tetrahedral andmore » cubic). It is found that the aggregated (liquid) phase of the “colorless” patchy particles is better connected, denser and typically has stronger local order than the corresponding “colored” one. This, in turn, makes the colored liquid less stable thermodynamically. Specifically, we predict that in a typical case the chromatic interactions should increase the relative stability of the crystalline phase with respect to the disordered liquid, thus expanding its region in the phase diagram.« less

Spontaneously Assembled Nano-aggregates in Clear Green Tea Infusions from Camellia ptilophylla and Camellia sinensis.

PubMed

Lin, Xiaorong; Gao, Xiong; Chen, Zhongzheng; Zhang, Yuanyuan; Luo, Wei; Li, Xiaofei; Li, Bin

2017-05-10

Tea nano-aggregates spontaneously assembled in clear tea infusions are considered as the precursors of tea cream, although their molecular basis remains obscure. Here, we characterized nano-aggregates in green tea infusions from Camellia ptilophylla, a peculiar tea variety with 6.0% of theobromine, and Camellia sinensis as the control for comparative purpose. Numerous negatively charged spherical colloidal particles of 50-100 nm in diameter were primarily found in both green tea infusions. Catechins, proteins, and carbohydrates were confirmed as the dominant components in green tea nano-aggregates. In addition, iron, copper, nickel, proteins, and gallated catechins exhibited higher aggregating affinity than other components, whereas methylxanthines and calcium contributed to the transformation of nano-aggregates into tea cream. Green tea nano-aggregates were partly destroyed by simulated gastrointestinal digestion, and removing theses peculiar particles dramatically attenuated the bioaccessibility of methylxanthines, theanine, and some catechin monomers in green tea infusions. This study enhanced our knowledge of molecular interactions in the formation of green tea cream and provided insight into physicochemical profiles, phytochemical nature, and functional effects of green tea nano-aggregates.

Single-wall nanohorn structure and distribution of incorporated materials

NASA Astrophysics Data System (ADS)

Maigne, Alan; Gloter, Alexandre; Ajima, Kumiko; Colliex, Christian; Iijima, Sumio

2005-03-01

Single-wall carbon nanohorns (SWNHs) are unique spherical-aggregates of single-wall carbon quasi-nanotubes. So far, the observable area has been limited to the aggregate surfaces. We studied core-region structure with TEM using thickness measurement method, EELS, and EDS, and found that carbon density was uniform over the whole aggregate. This result allows to modelize the core-region and to clarify previous models of SWNHs. We used same tools to investigate the incorporation of materials such as fullerenes or platinium compounds. We found that particles can even be incorporated in the core-region and that their distribution in the aggregate depends on their concentration. The information available with these models should be useful in the study of SWNH applications to, for example, drug delivery system.

High-molecular weight Aβ oligomers and protofibrils are the predominant Aβ species in the native soluble protein fraction of the AD brain.

PubMed

Upadhaya, Ajeet Rijal; Lungrin, Irina; Yamaguchi, Haruyasu; Fändrich, Marcus; Thal, Dietmar Rudolf

2012-02-01

Alzheimer's disease (AD) is characterized by the aggregation and deposition of amyloid β protein (Aβ) in the brain. Soluble Aβ oligomers are thought to be toxic. To investigate the predominant species of Aβ protein that may play a role in AD pathogenesis, we performed biochemical analysis of AD and control brains. Sucrose buffer-soluble brain lysates were characterized in native form using blue native (BN)-PAGE and also in denatured form using SDS-PAGE followed by Western blot analysis. BN-PAGE analysis revealed a high-molecular weight smear (>1000 kD) of Aβ(42) -positive material in the AD brain, whereas low-molecular weight and monomeric Aβ species were not detected. SDS-PAGE analysis, on the other hand, allowed the detection of prominent Aβ monomer and dimer bands in AD cases but not in controls. Immunoelectron microscopy of immunoprecipitated oligomers and protofibrils/fibrils showed spherical and protofibrillar Aβ-positive material, thereby confirming the presence of high-molecular weight Aβ (hiMWAβ) aggregates in the AD brain. In vitro analysis of synthetic Aβ(40) - and Aβ(42) preparations revealed Aβ fibrils, protofibrils, and hiMWAβ oligomers that were detectable at the electron microscopic level and after BN-PAGE. Further, BN-PAGE analysis exhibited a monomer band and less prominent low-molecular weight Aβ (loMWAβ) oligomers. In contrast, SDS-PAGE showed large amounts of loMWAβ but no hiMWAβ(40) and strikingly reduced levels of hiMWAβ(42) . These results indicate that hiMWAβ aggregates, particularly Aβ(42) species, are most prevalent in the soluble fraction of the AD brain. Thus, soluble hiMWAβ aggregates may play an important role in the pathogenesis of AD either independently or as a reservoir for release of loMWAβ oligomers. © 2011 The Authors Journal of Cellular and Molecular Medicine © 2011 Foundation for Cellular and Molecular Medicine/Blackwell Publishing Ltd.

High-molecular weight Aβ oligomers and protofibrils are the predominant Aβ species in the native soluble protein fraction of the AD brain

PubMed Central

Upadhaya, Ajeet Rijal; Lungrin, Irina; Yamaguchi, Haruyasu; Fändrich, Marcus; Thal, Dietmar Rudolf

2012-01-01

Abstract Alzheimer’s disease (AD) is characterized by the aggregation and deposition of amyloid β protein (Aβ) in the brain. Soluble Aβ oligomers are thought to be toxic. To investigate the predominant species of Aβ protein that may play a role in AD pathogenesis, we performed biochemical analysis of AD and control brains. Sucrose buffer-soluble brain lysates were characterized in native form using blue native (BN)-PAGE and also in denatured form using SDS-PAGE followed by Western blot analysis. BN-PAGE analysis revealed a high-molecular weight smear (>1000 kD) of Aβ42-positive material in the AD brain, whereas low-molecular weight and monomeric Aβ species were not detected. SDS-PAGE analysis, on the other hand, allowed the detection of prominent Aβ monomer and dimer bands in AD cases but not in controls. Immunoelectron microscopy of immunoprecipitated oligomers and protofibrils/fibrils showed spherical and protofibrillar Aβ-positive material, thereby confirming the presence of high-molecular weight Aβ (hiMWAβ) aggregates in the AD brain. In vitro analysis of synthetic Aβ40- and Aβ42 preparations revealed Aβ fibrils, protofibrils, and hiMWAβ oligomers that were detectable at the electron microscopic level and after BN-PAGE. Further, BN-PAGE analysis exhibited a monomer band and less prominent low-molecular weight Aβ (loMWAβ) oligomers. In contrast, SDS-PAGE showed large amounts of loMWAβ but no hiMWAβ40 and strikingly reduced levels of hiMWAβ42. These results indicate that hiMWAβ aggregates, particularly Aβ42 species, are most prevalent in the soluble fraction of the AD brain. Thus, soluble hiMWAβ aggregates may play an important role in the pathogenesis of AD either independently or as a reservoir for release of loMWAβ oligomers. PMID:21418518

Meso-oblate spheroids of thermal-stabile linker-free aggregates with size-tunable subunits for reversible lithium storage.

PubMed

Deng, Da; Lee, Jim Yang

2014-01-22

The organization of nanoscale materials as building units into extended structures with specific geometry and functional properties is a challenging endeavor. Hereby, an environmentally benign, simple, and scalable method for preparation of stable, linker-free, self-supported, high-order 3D meso-oblate spheroids of CuO nanoparticle aggregates with size-tunable building nanounits for reversible lithium-ion storage is reported. In contrast to traditional spherical nanoparticle aggregation, a unique oblate spheroid morphology is achieved. The formation mechanism of the unusual oblate spheroid of aggregated nanoparticles is proposed. When tested for reversible lithium ion storage, the unique 3D meso-oblate spheroids of CuO nanoparticle aggregate demonstrated highly improved electrochemical performance (around ∼600 mAh/g over 20 cycles), which could be ascribed to the nanoporous aggregated mesostructure with abundant crystalline imperfection. Furthermore, the size of building units can be controlled (12 and 21 nm were tested) to further improve their electrochemical performance.

Looking into the evolution of granular asteroids in the Solar System

NASA Astrophysics Data System (ADS)

Sánchez, Paul; Scheeres, Daniel; Hirabayashi, Masatoshi; Tardivel, Simon

2017-06-01

By now it has been accepted that most of the small asteroids in the Solar System are granular aggregates kept together by gravitational and possibly, cohesive forces. These aggregates can form, deform and disrupt over millennia subjected to different internal and external factors that would ultimately determine how they evolve over time. Parameters such as porosity, cohesive and tensile strength, angles of friction, particle size distributions, stress states, heterogeneity and yield criteria among others, determine how these granular systems will react when subjected to different, changing, external factors. These external factors include solar photon momentum, gravitational tides, micro- and macro-impacts and are believed to have produced and shaped the current asteroid population. In our research we use a combination of Soil Mechanics theory, Soft-Sphere Discrete Element Method (SSDEM) Simulations and Orbital Mechanics in order to understand how simulated, homogeneous and heterogeneous, ellipsoidal and spherical gravitational aggregates, a crude but useful representation of an asteroid, evolve when rotated to the point of disruption. Then, we compare our results to the shapes of observed asteroids as well as to the disruption patterns of a few active asteroids. Our results lead us to believe that the different shapes of observed asteroids as well as their unique disruption patterns could give us clues about their internal structure, strength and geophysical properties in general.

Structural Characterization of IgG1 mAb Aggregates and Particles Generated under Various Stress Conditions

PubMed Central

Telikepalli, Srivalli N.; Kumru, Ozan S.; Kalonia, Cavan; Esfandiary, Reza; Joshi, Sangeeta B.; Middaugh, C. Russell; Volkin, David B.

2014-01-01

IgG1 mAb solutions were prepared with and without sodium chloride and subjected to different environmental stresses. Formation of aggregates and particles of varying size was monitored by a combination of size exclusion chromatography (SEC), Nanosight Tracking Analysis (NTA), Micro-flow Imaging (MFI), turbidity, and visual assessments. Stirring and heating induced the highest concentration of particles. In general, the presence of NaCl enhanced this effect. The morphology of the particles formed from mAb samples exposed to different stresses was analyzed from TEM and MFI images. Shaking samples without NaCl generated the most fibrillar particles, while stirring created largely spherical particles. The composition of the particles was evaluated for covalent cross-linking by SDS-PAGE, overall secondary structure by FTIR microscopy, and surface apolarity by extrinsic fluorescence spectroscopy. Freeze-thaw and shaking led to particles containing protein with native-like secondary structure. Heating and stirring produced IgG1 containing aggregates and particles with some non-native disulfide crosslinks, varying levels of intermolecular beta sheet content, and increased surface hydrophobicity. These results highlight the importance of evaluating protein particle morphology and composition, in addition to particle number and size distributions, to better understand the effect of solution conditions and environmental stresses on the formation of protein particles in mAb solutions. PMID:24452866

Structural characterization of IgG1 mAb aggregates and particles generated under various stress conditions.

PubMed

Telikepalli, Srivalli N; Kumru, Ozan S; Kalonia, Cavan; Esfandiary, Reza; Joshi, Sangeeta B; Middaugh, C Russell; Volkin, David B

2014-03-01

IgG1 mAb solutions were prepared with and without sodium chloride and subjected to different environmental stresses. Formation of aggregates and particles of varying size was monitored by a combination of size-exclusion chromatography, Nanoparticle Tracking Analysis, Micro-flow Imaging (MFI), turbidity, and visual assessments. Stirring and heating induced the highest concentration of particles. In general, the presence of NaCl enhanced this effect. The morphology of the particles formed from mAb samples exposed to different stresses was analyzed from transmission electron microscopy and MFI images. Shaking samples without NaCl generated the most fibrillar particles, whereas stirring created largely spherical particles. The composition of the particles was evaluated for covalent cross-linking by SDS-PAGE, overall secondary structure by FTIR microscopy, and surface apolarity by extrinsic fluorescence spectroscopy. Freeze-thaw and shaking led to particles containing protein with native-like secondary structure. Heating and stirring produced IgG1-containing aggregates and particles with some non-native disulfide cross-links, varying levels of intermolecular beta sheet content, and increased surface hydrophobicity. These results highlight the importance of evaluating protein particle morphology and composition, in addition to particle number and size distributions, to better understand the effect of solution conditions and environmental stresses on the formation of protein particles in mAb solutions. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

Measurement of rheologic property of blood by a falling-ball blood viscometer.

PubMed

Eguchi, Yoko; Karino, Takeshi

2008-04-01

The viscosity of blood obtained by using a rotational viscometer decreases with the time elapsed from the beginning of measurement until it reaches a constant value determined by the magnitude of shear rate. It is not possible to obtain an initial value of viscosity at time t = 0 that is considered to exhibit an intrinsic property of the fluid by this method. Therefore, we devised a new method by which one can obtain the viscosity of various fluids that are not affected by both the time elapsed from the beginning of measurement and the magnitude of shear rate by considering the balance of the forces acting on a solid spherical particle freely falling in a quiescent viscous fluid. By using the new method, we studied the rheologic behavior of corn syrups, carboxy-methyl cellulose, and human blood; and compared the results with those obtained with a cone-and-plate viscometer. It was found that in the case of corn syrups and washed red cell suspensions in which no red cell aggregate (rouleau) was formed, the viscosity obtained with the two different methods were almost the same. In contrast to this, in the case of the whole blood in which massive aggregates were formed, the viscosity obtained with a falling-ball viscometer was much larger than that obtained with a cone-plate viscometer.

Decorating graphene oxide with CuO nanoparticles in a water-isopropanol system.

PubMed

Zhu, Junwu; Zeng, Guiyu; Nie, Fude; Xu, Xiaoming; Chen, Sheng; Han, Qiaofeng; Wang, Xin

2010-06-01

A facile chemical procedure capable of aligning CuO nanoparticles on graphene oxide (GO) in a water-isopropanol system has been described. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations indicate that the exfoliated GO sheets are decorated randomly by spindly or spherical CuO nanoparticle aggregates, forming well-ordered CuO:GO nanocomposites. A formation mechanism of these interesting nanocomposites is proposed as intercalation and adsorption of Cu2+ ions onto the GO sheets, followed by the nucleation and growth of the CuO crystallites, which in return resulted in the exfoliation of GO sheets. Moreover, the obtained nanocomposites exhibit a high catalytic activity for the thermal decomposition of ammonium perchlorate (AP), due to the concerted effect of CuO and GO.

ULTRASTRUCTURAL CHANGES IN THE MITOTIC APPARATUS AT THE METAPHASE-TO-ANAPHASE TRANSITION

PubMed Central

Robbins, Elliott; Jentzsch, Gisela

1969-01-01

As the metaphase HeLa cell approaches anaphase, pericentriolar spindle tubules fragment and become encapsulated by a unit membrane. By early anaphase, the encapsulated forms appear to have expanded, giving rise to polar spherical aggregates. Some of these elements show ribosomes on their bounding membrane, and some of them localize on the condensed chromatin during reformation of the nuclear membrane. It thus is suggested that these elements are newly derived cisternae of the endoplasmic reticulum (ER). Similar transformations are seen in later anaphase in the interzonal region, and it may be that the ER serves as a storage depot for some fraction of depolymerized microtubules. The time and location of the pericentriolar transitions are consistent with their being intimately involved in the mechanics of chromosome separation. PMID:5765760

Constraints on the microphysics of Pluto's photochemical haze from New Horizons observations

NASA Astrophysics Data System (ADS)

Gao, Peter; Fan, Siteng; Wong, Michael L.; Liang, Mao-Chang; Shia, Run-Lie; Kammer, Joshua A.; Yung, Yuk L.; Summers, Michael E.; Gladstone, G. Randall; Young, Leslie A.; Olkin, Catherine B.; Ennico, Kimberly; Weaver, Harold A.; Stern, S. Alan; New Horizons Science Team

2017-05-01

The New Horizons flyby of Pluto confirmed the existence of hazes in its atmosphere. Observations of a large high- to low- phase brightness ratio, combined with the blue color of the haze (indicative of Rayleigh scattering), suggest that the haze particles are fractal aggregates, perhaps analogous to the photochemical hazes on Titan. Therefore, studying the Pluto hazes can shed light on the similarities and differences between the Pluto and Titan atmospheres. We model the haze distribution using the Community Aerosol and Radiation Model for Atmospheres assuming that the distribution is shaped by downward transport and coagulation of particles originating from photochemistry. Hazes composed of both purely spherical and purely fractal aggregate particles are considered. General agreement between model results and solar occultation observations is obtained with aggregate particles when the downward mass flux of photochemical products is equal to the column-integrated methane destruction rate ∼1.2 × 10-14 g cm-2 s-1, while for spherical particles the mass flux must be 2-3 times greater. This flux is nearly identical to the haze production flux of Titan previously obtained by comparing microphysical model results to Cassini observations. The aggregate particle radius is sensitive to particle charging effects, and a particle charge to radius ratio of 30 e-/μm is necessary to produce ∼0.1-0.2 μm aggregates near Pluto's surface, in accordance with forward scattering measurements. Such a particle charge to radius ratio is 2-4 times higher than those previously obtained for Titan. Hazes composed of spheres with the same particle charge to radius ratio have particles that are 4 times smaller at Pluto's surface. These results further suggest that the haze particles are fractal aggregates. We also consider the effect of condensation of HCN, C2H2, C2H4, and C2H6 on the haze particles, which may play an important role in shaping their altitude and size distributions.

Laboratory Experiments to Study Spherical, Iron Oxide Concretion Growth Without Solid Nuclei: Implications for Understanding Meridiani "Blueberries"

NASA Astrophysics Data System (ADS)

Ormö, J.; Souza-Egipsy, V.; Chan, M. A.; Park, A. J.; Stich, M.; Komatsu, G.

2006-03-01

Spherical hematite concretions can form without a nucleus. Self-organized zones of super-saturated solution cause spherical precipitates of amorphous iron-hydroxide. Diffusion of Fe ions towards the outer perimeter of the amorphous sphere forms a rind, which then grows inwards.

Small angle neutron scattering study of sodium dodecyl sulfate micellar growth driven by addition of a hydrotropic salt.

PubMed

Hassan, P A; Fritz, Gerhard; Kaler, Eric W

2003-01-01

The structures of aggregates formed in aqueous solutions of an anionic surfactant, sodium dodecyl sulfate (SDS), with the addition of a cationic hydrotropic salt, p-toluidine hydrochloride (PTHC), have been investigated by small angle neutron scattering (SANS). The SANS spectra exhibit a pronounced peak at low salt concentration, indicating the presence of repulsive intermicellar interactions. Model-independent real space information about the structure is obtained from a generalized indirect Fourier transformation (GIFT) technique in combination with a suitable model for the interparticle structure factor. The interparticle interaction is captured using the rescaled mean spherical approximation (RMSA) closure relation and a Yukawa form of the interaction potential. Further quantification of the geometrical parameters of the micelles was achieved by a complete fit of the SANS data using a prolate ellipsoidal form factor and the RMSA structure factor. The present study shows that PTHC induces a decrease in the fractional charge of the micelles due to adsorption at the micellar surface and consequent growth of the SDS micelles from nearly globular to rodlike as the concentration of PTHC increases.

A probabilistic mechanical model for prediction of aggregates’ size distribution effect on concrete compressive strength

NASA Astrophysics Data System (ADS)

Miled, Karim; Limam, Oualid; Sab, Karam

2012-06-01

To predict aggregates' size distribution effect on the concrete compressive strength, a probabilistic mechanical model is proposed. Within this model, a Voronoi tessellation of a set of non-overlapping and rigid spherical aggregates is used to describe the concrete microstructure. Moreover, aggregates' diameters are defined as statistical variables and their size distribution function is identified to the experimental sieve curve. Then, an inter-aggregate failure criterion is proposed to describe the compressive-shear crushing of the hardened cement paste when concrete is subjected to uniaxial compression. Using a homogenization approach based on statistical homogenization and on geometrical simplifications, an analytical formula predicting the concrete compressive strength is obtained. This formula highlights the effects of cement paste strength and aggregates' size distribution and volume fraction on the concrete compressive strength. According to the proposed model, increasing the concrete strength for the same cement paste and the same aggregates' volume fraction is obtained by decreasing both aggregates' maximum size and the percentage of coarse aggregates. Finally, the validity of the model has been discussed through a comparison with experimental results (15 concrete compressive strengths ranging between 46 and 106 MPa) taken from literature and showing a good agreement with the model predictions.

Re-evaluation of ``;The Propagation of Radiation in the Spherical Wave Form''

NASA Astrophysics Data System (ADS)

Joshi, Narahari V.

2012-03-01

It is well accepted that radiation propagates in the free space (without obstacles) in a spherical wave form as well as in a plane wave form. Almost all observed phenomena such as interference, diffraction etc are explained satisfactorily on the basis of spherical wave propagation with a slight alteration in the mathematical treatment. However, one of the fundamental aspects, namely the intensity of the radiation as a function of the distance still remains an unsolved problem as the intensity varies with 1/(distance)2 when one represents the propagation in terms of spherical waves while it is independent of the distance if it is considered as a plane wave. In order to understand this puzzle, the propagation by a spherical wave form is reexamined. It is found that conversion of fields into particle (vice versa), via the field quantization process, explains several dilemma related with the radiation propagation.

Effect of Particle Shape on Mechanical Behaviors of Rocks: A Numerical Study Using Clumped Particle Model

PubMed Central

Rong, Guan; Liu, Guang; Zhou, Chuang-bing

2013-01-01

Since rocks are aggregates of mineral particles, the effect of mineral microstructure on macroscopic mechanical behaviors of rocks is inneglectable. Rock samples of four different particle shapes are established in this study based on clumped particle model, and a sphericity index is used to quantify particle shape. Model parameters for simulation in PFC are obtained by triaxial compression test of quartz sandstone, and simulation of triaxial compression test is then conducted on four rock samples with different particle shapes. It is seen from the results that stress thresholds of rock samples such as crack initiation stress, crack damage stress, and peak stress decrease with the increasing of the sphericity index. The increase of sphericity leads to a drop of elastic modulus and a rise in Poisson ratio, while the decreasing sphericity usually results in the increase of cohesion and internal friction angle. Based on volume change of rock samples during simulation of triaxial compression test, variation of dilation angle with plastic strain is also studied. PMID:23997677

Effect of particle shape on mechanical behaviors of rocks: a numerical study using clumped particle model.

PubMed

Rong, Guan; Liu, Guang; Hou, Di; Zhou, Chuang-Bing

2013-01-01

Since rocks are aggregates of mineral particles, the effect of mineral microstructure on macroscopic mechanical behaviors of rocks is inneglectable. Rock samples of four different particle shapes are established in this study based on clumped particle model, and a sphericity index is used to quantify particle shape. Model parameters for simulation in PFC are obtained by triaxial compression test of quartz sandstone, and simulation of triaxial compression test is then conducted on four rock samples with different particle shapes. It is seen from the results that stress thresholds of rock samples such as crack initiation stress, crack damage stress, and peak stress decrease with the increasing of the sphericity index. The increase of sphericity leads to a drop of elastic modulus and a rise in Poisson ratio, while the decreasing sphericity usually results in the increase of cohesion and internal friction angle. Based on volume change of rock samples during simulation of triaxial compression test, variation of dilation angle with plastic strain is also studied.

Fractal scaling laws of black carbon aerosol and their influence on spectral radiative properties

NASA Astrophysics Data System (ADS)

Tiwari, S.; Chakrabarty, R. K.; Heinson, W.

2016-12-01

Current estimates of the direct radiative forcing for Black Carbon (BC) aerosol span over a poorly constrained range between 0.2 and 1 W.m-2. To improve this large uncertainty, tighter constraints need to be placed on BC's key wavelength-dependent optical properties, namely, the absorption (MAC) and scattering (MSC) cross sections per unit mass and hemispherical upscatter fraction (β; a dimensionless scattering directionality parameter). These parameters are very sensitive to changes in particle morphology and complex refractive index nindex. Their interplay determines the magnitude of net positive or negative radiative forcing efficiencies. The current approach among climate modelers for estimating MAC and MSC values of BC is from their optical cross-sections calculated assuming spherical particle morphology with homogeneous, constant-valued refractive index in the visible solar spectrum. The β values are typically assumed to be a constant across this spectrum. This approach, while being computationally inexpensive and convenient, ignores the inherent fractal morphology of BC and its scaling behaviors, and resulting optical properties. In this talk, I will present recent results from my laboratory on determination of the fractal scaling laws of BC aggregate packing density and its complex refractive index for size spanning across three orders of magnitude, and their effects on spectral (Visible-infrared wavelength) scaling of MAC, MSC, and β values. Our experiments synergistically combined novel BC generation techniques, aggregation models, contact-free multi-wavelength optical measurements, and electron microscopy analysis. The scale dependence of nindex on aggregate size followed power-law exponents of -1.4 and -0.5 for sub- and super-micron size aggregates, respectively. The spherical Rayleigh-optics approximation limits, used by climate models for spectral extrapolation of BC optical cross-sections and deconvolution of multi-species mixing ratios, are redefined using the concept of phase shift parameter. I will highlight the importance of size-dependent β values and its role in offsetting the strong light absorbing nature of BC. Finally, the errors introduced in forcing efficiency calculations of BC by assuming spherical homogeneous morphology will be evaluated.

Optimal conditions for particle-bubble attachment in flotation: an experimental study

NASA Astrophysics Data System (ADS)

Sanchez Yanez, Aaron; Hernandez Sanchez, Jose Federico; Thoroddsen, Sigurdur T.

2017-11-01

Mineral flotation is a process used in the mining industry for separating solid particles of different sizes and densities. The separation is done by injecting bubbles into a slurry where the particles attach to them, forming floating aggregates. The attachment depends mainly on the bubbles and particles sizes as well as the hydrophobicity and roughness of the particles. We simplified the collective behavior in the industrial process to a single free particle-bubble collision, in contrast with previous studies where one of the two was kept fixed. We experimentally investigated the collision of spherical solid particles of a fixed diameter with bubbles of different sizes. By controlling the initial relative offset of the bubble and the particle, we conducted experiments observing their interaction. Recording with two synchronized high-speed cameras, perpendicular to each other, we can reconstruct the tridimensional trajectories of the bubble, the solid particle, and the aggregate. We describe the conditions for which the attachment happens in terms of dimensionless parameters such as the Ohnesorge number, the relative particle-bubble offset and the hydrophobicity of the particle surface. We furthermore investigate the role of the surface roughness in the attachment.

Structure evolution of gelatin particles induced by pH and ionic strength.

PubMed

Xu, Jing; Li, Tianduo; Tao, Furong; Cui, Yuezhi; Xia, Yongmei

2013-03-01

Microstructure of gelatin particles played a key role in determining the physicochemical properties of gelatin. Ionic strength and pH as systematic manners were considered to affect gelatin particles structure on the micrometer scale. Scanning electron microscopy was used for depicting the morphologies of gelatin particles. Increasing pH to 10.0 or decreasing pH to 4.0, spherical, spindle, and irregular aggregates of gelatin particles at 2, 6, 10, and 14% solution (w/w) were all transformed to spindle aggregates. When NaCl was added to the system, the molecular chains of gelatin possibly rearranged themselves in a stretched state, and the ribbon aggregates was observed. The structural transitions of gelatin aggregates were strongly depended on the electrostatic repulsion. In the gelatin-sodium dodecyl sulfate (SDS) case, the micrometer scale of aggregates was larger and the different degrees of cross-links were induced through hydrophobic interaction and electrostatic repulsion. Copyright © 2012 Wiley Periodicals, Inc.

Aeolian comminution experiments revealing surprising sandball mineral aggregates

NASA Astrophysics Data System (ADS)

Nørnberg, P.; Bak, E.; Finster, K.; Gunnlaugsson, H. P.; Iversen, J. J.; Jensen, S. Knak; Merrison, J. P.

2014-06-01

We have undertaken a set of wind erosion experiments on a simple and well defined mineral, quartz. In these experiments wind action is simulated by end over end tumbling of quartz grains in a sealed quartz flask. The tumbling induces collisions among the quartz grains and the walls of the flask. This process simulates wind action impact speed of ∼1.2 m/s. After several months of tumbling we observed the formation of a large number of spherical sand aggregates, which resemble small snowballs under optical microscopy. Upon mechanical load the aggregates are seen to be more elastic than quartz and their mechanical strength is comparable, though slightly lower than that of sintered silica aerogels. Aggregates of this kind have not been reported from field sites or from closed circulation systems. However, sparse occurrence might explain this, or in nature the concentration of the aggregate building particles is so low that they never meet and just appear as the most fine grained tail of the sediment particle size distribution.

Synthesis and characterization of hollow spherical copper phosphide (Cu 3P) nanopowders

NASA Astrophysics Data System (ADS)

Liu, Shuling; Qian, Yitai; Xu, Liqiang

2009-03-01

In this paper, hollow spherical Cu 3P nanopowders were synthesized by using copper sulfate pentahydrate (CuSO 4ṡ5H 2O) and yellow phosphorus in a mixed solvent of glycol, ethanol and water at 140-180 ∘C for 12 h. X-ray powder diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), electron diffraction pattern (ED) and transmission electronic microscopy (TEM) studies show that the as-synthesized nanocrystal is pure hexagonal phase Cu 3P with a hollow spherical morphology. Based on the TEM observations, a possible aggregation growth mechanism was proposed for the formation of Cu 3P hollow structures. Meanwhile, the effects of some key factors such as solvents, reaction temperature and reaction time on the final formation of the Cu 3P hollow structure were also discussed.

Role of clay minerals in the formation of atmospheric aggregates of Saharan dust

NASA Astrophysics Data System (ADS)

Cuadros, Javier; Diaz-Hernandez, José L.; Sanchez-Navas, Antonio; Garcia-Casco, Antonio

2015-11-01

Saharan dust can travel long distances in different directions across the Atlantic and Europe, sometimes in episodes of high dust concentration. In recent years it has been discovered that Saharan dust aerosols can aggregate into large, approximately spherical particles of up to 100 μm generated within raindrops that then evaporate, so that the aggregate deposition takes place most times in dry conditions. These aerosol aggregates are an interesting phenomenon resulting from the interaction of mineral aerosols and atmospheric conditions. They have been termed "iberulites" due to their discovery and description from aerosol deposits in the Iberian Peninsula. Here, these aggregates are further investigated, in particular the role of the clay minerals in the aggregation process of aerosol particles. Iberulites, and common aerosol particles for reference, were studied from the following periods or single dust events and locations: June 1998 in Tenerife, Canary Islands; June 2001 to August 2002, Granada, Spain; 13-20 August 2012, Granada; and 1-6 June 2014, Granada. Their mineralogy, chemistry and texture were analysed using X-ray diffraction, electron microprobe analysis, SEM and TEM. The mineral composition and structure of the iberulites consists of quartz, carbonate and feldspar grains surrounded by a matrix of clay minerals (illite, smectite and kaolinite) that also surrounds the entire aggregate. Minor phases, also distributed homogenously within the iberulites, are sulfates and Fe oxides. Clays are apparently more abundant in the iberulites than in the total aerosol deposit, suggesting that iberulite formation concentrates clays. Details of the structure and composition of iberulites differ from descriptions of previous samples, which indicates dependence on dust sources and atmospheric conditions, possibly including anthropic activity. Iberulites are formed by coalescence of aerosol mineral particles captured by precursor water droplets. The concentration of clays in the iberulites is suggested to be the result of higher efficiency for clay capture than for the capture of larger mineral grains. The high hygroscopicity of clay minerals probably causes retention of water in the evaporation stage and some secondary minerals (mainly gypsum) are associated with clays.

Spherical boron nitride particles and method for preparing them

DOEpatents

Phillips, Jonathan; Gleiman, Seth S.; Chen, Chun-Ku

2003-11-25

Spherical and polyhedral particles of boron nitride and method of preparing them. Spherical and polyhedral particles of boron nitride are produced from precursor particles of hexagonal phase boron nitride suspended in an aerosol gas. The aerosol is directed to a microwave plasma torch. The torch generates plasma at atmospheric pressure that includes nitrogen atoms. The presence of nitrogen atoms is critical in allowing boron nitride to melt at atmospheric pressure while avoiding or at least minimizing decomposition. The plasma includes a plasma hot zone, which is a portion of the plasma that has a temperature sufficiently high to melt hexagonal phase boron nitride. In the hot zone, the precursor particles melt to form molten particles that acquire spherical and polyhedral shapes. These molten particles exit the hot zone, cool, and solidify to form solid particles of boron nitride with spherical and polyhedral shapes. The molten particles can also collide and join to form larger molten particles that lead to larger spherical and polyhedral particles.

Aggregation in particle rich environments: a textural study of examples from volcanic eruptions, meteorite impacts, and fluidized bed processing

NASA Astrophysics Data System (ADS)

Mueller, Sebastian B.; Kueppers, Ulrich; Huber, Matthew S.; Hess, Kai-Uwe; Poesges, Gisela; Ruthensteiner, Bernhard; Dingwell, Donald B.

2018-04-01

Aggregation is a common process occurring in many diverse particulate gas mixtures (e.g. those derived from explosive volcanic eruptions, meteorite impact events, and fluid bed processing). It results from the collision and sticking of particles suspended in turbulent gas/air. To date, there is no generalized model of the underlying physical processes. Here, we investigate aggregates from 18 natural deposits (16 volcanic deposits and two meteorite impact deposits) as well as aggregates produced experimentally via fluidized bed techniques. All aggregates were analyzed for their size, internal structuring, and constituent particle size distribution. Commonalities and differences between the aggregate types are then used to infer salient features of the aggregation process. Average core to rim ratios of internally structured aggregates (accretionary lapilli) is found to be similar for artificial and volcanic aggregates but up to an order of magnitude different than impact-related aggregates. Rim structures of artificial and volcanic aggregates appear to be physically similar (single, sub-spherical, regularly-shaped rims) whereas impact-related aggregates more often show multiple or irregularly shaped rims. The particle size distributions (PSDs) of all three aggregate types are similar (< 200 μm). This proves that in all three environments, aggregation occurs under broadly similar conditions despite the significant differences in source conditions (particle volume fraction, particle size distribution, particle composition, temperature), residence times, plume conditions (e.g., humidity and temperature), and dynamics of fallout and deposition. Impact-generated and volcanic aggregates share many similarities, and in some cases may be indistinguishable without their stratigraphic context.

Aggregation in particle rich environments: a textural study of examples from volcanic eruptions, meteorite impacts, and fluidized bed processing.

PubMed

Mueller, Sebastian B; Kueppers, Ulrich; Huber, Matthew S; Hess, Kai-Uwe; Poesges, Gisela; Ruthensteiner, Bernhard; Dingwell, Donald B

2018-01-01

Aggregation is a common process occurring in many diverse particulate gas mixtures (e.g. those derived from explosive volcanic eruptions, meteorite impact events, and fluid bed processing). It results from the collision and sticking of particles suspended in turbulent gas/air. To date, there is no generalized model of the underlying physical processes. Here, we investigate aggregates from 18 natural deposits (16 volcanic deposits and two meteorite impact deposits) as well as aggregates produced experimentally via fluidized bed techniques. All aggregates were analyzed for their size, internal structuring, and constituent particle size distribution. Commonalities and differences between the aggregate types are then used to infer salient features of the aggregation process. Average core to rim ratios of internally structured aggregates (accretionary lapilli) is found to be similar for artificial and volcanic aggregates but up to an order of magnitude different than impact-related aggregates. Rim structures of artificial and volcanic aggregates appear to be physically similar (single, sub-spherical, regularly-shaped rims) whereas impact-related aggregates more often show multiple or irregularly shaped rims. The particle size distributions (PSDs) of all three aggregate types are similar (< 200 μm). This proves that in all three environments, aggregation occurs under broadly similar conditions despite the significant differences in source conditions (particle volume fraction, particle size distribution, particle composition, temperature), residence times, plume conditions (e.g., humidity and temperature), and dynamics of fallout and deposition. Impact-generated and volcanic aggregates share many similarities, and in some cases may be indistinguishable without their stratigraphic context.

Self-assembly behavior of pH- and thermosensitive amphiphilic triblock copolymers in solution: experimental studies and self-consistent field theory simulations.

PubMed

Cai, Chunhua; Zhang, Liangshun; Lin, Jiaping; Wang, Liquan

2008-10-09

We investigated, both experimentally and theoretically, the self-assembly behaviors of pH- and thermosensitive poly(L-glutamic acid)- b-poly(propylene oxide)-b-poly(L-glutamic acid) (PLGA-b-PPO-b-PLGA) triblock copolymers in aqueous solution by means of transmission electron microscopy (TEM), scanning electron microscopy (SEM), dynamic light scattering (DLS), circular dichroism (CD), and self-consistent field theory (SCFT) simulations. Vesicles were observed when the hydrophilic PLGA block length is shorter or the pH value of solution is lower. The vesicles were found to transform to spherical micelles when the PLGA block length increases or its conformation changes from helix to coil with increasing the pH value. In addition, increasing temperature gives rise to a decrease in the size of aggregates, which is related to the dehydration of the PPO segments at higher temperatures. The SCFT simulation results show that the vesicles transform to the spherical micelles with increasing the fraction or statistical length of A block in model ABA triblock copolymer, which corresponds to the increase in the PLGA length or its conformation change from helix to coil in experiments, respectively. The SCFT calculations also provide chain distribution information in the aggregates. On the basis of both experimental and SCFT results, the mechanism of the structure change of the PLGA- b-PPO- b-PLGA aggregates was proposed.

Easy synthesis of hierarchical carbon spheres with superior capacitive performance in supercapacitors.

PubMed

Huang, Xinhua; Kim, Seok; Heo, Min Seon; Kim, Ji Eun; Suh, Hongsuk; Kim, Il

2013-10-01

An easy template-free approach to the fabrication of pure carbon microspheres has been achieved via direct pyrolysis of as-prepared polyaromatic hydrocarbons including polynaphthalene and polypyrene. The polyaromatics were synthesized from aromatic hydrocarbons (AHCs) using anhydrous zinc chloride as the Friedel-Crafts catalyst and chloromethyl methyl ether as a cross-linker. The experimental results show that the methylene bridges between phenyl rings generate a hierarchical porous polyaromatic precursor to form three-dimensionally (3D) interconnected micro-, meso-, and macroporous networks during carbonization. These hierarchical porous carbon aggregates of spherical carbon spheres exhibit faster ion transport/diffusion behavior and increased surface area usage in electric double-layer capacitors. Furthermore, micropores are present in the 3D interconnected network inside the cross-linked AHC-based carbon microspheres, thus imparting an exceptionally large, electrochemically accessible surface area for charge accumulation.

Enhanced magnetostriction derived from magnetic single domain structures in cluster-assembled SmCo films

NASA Astrophysics Data System (ADS)

Bai, Yulong; Yang, Bo; Guo, Fei; Lu, Qingshan; Zhao, Shifeng

2017-11-01

Cluster-assembled SmCo alloy films were prepared by low energy cluster beam deposition. The structure, magnetic domain, magnetization, and magnetostriction of the films were characterized. It is shown that the as-prepared films are assembled in compact and uniformly distributed spherical cluster nanoparticles, most of which, after vacuum in situ annealing at 700 K, aggregated to form cluster islands. These cluster islands result in transformations from superparamagnetic states to magnetic single domain (MSD) states in the films. Such MSD structures contribute to the enhanced magnetostrictive behaviors with a saturation magnetostrictive coefficient of 160 × 10-6 in comparison to 105 × 10-6 for the as-prepared films. This work demonstrates candidate materials that could be applied in nano-electro-mechanical systems, low power information storage, and weak magnetic detecting devices.

Biochemical separations by continuous-bed chromatography.

PubMed

Tisch, T L; Frost, R; Liao, J L; Lam, W K; Remy, A; Scheinpflug, E; Siebert, C; Song, H; Stapleton, A

1998-08-07

Innovations in column-packing media for biomolecule purification have progressed from large spherical, porous polysaccharide beads to advanced polymeric supports. Continuous-bed technology is a radical new technology for chromatography based on the polymerization of advanced monomers and ionomers directly in the chromatographic column. The polymer chains form aggregates which coalesce into a dense, homogeneous network of interconnected nodules consisting of microparticles with an average diameter of 3000 A. The voids or channels between the nodules are large enough to permit a high hydrodynamic flow. Due to the high cross-linking of the polymer matrix, the surface of each nodule is nonporous yet the polymeric microparticles provide a very large surface area for high binding capacity. This paper will demonstrate the properties and advantages of using a continuous bed support for high resolution biomolecule separations at high flow-rates without sacrificing capacity.

The Stability of Silver Nanoparticles in a Model of Pulmonary Surfactant

PubMed Central

Fen, Leo Bey; Chen, Shu; Kyo, Yoshihiko; Herpoldt, Karla-Luise; Terrill, Nicholas J.; Dunlop, Iain E.; McPhail, David S.; Shaffer, Milo S.; Schwander, Stephan; Gow, Andrew; Zhang, Junfeng (Jim); Chung, Kian Fan; Tetley, Teresa D.; Porter, Alexandra E.; Ryan, Mary P.

2013-01-01

The growing use of silver nanoparticles (AgNPs) in consumer products has raised concerns about their potential impact on the environment and human health. Whether AgNPs dissolve and release Ag+ ions, or coarsen to form large aggregates, is critical in determining their potential toxicity. In this work, the stability of AgNPs in dipalmitoylphosphatidylcholine (DPPC), the major component of pulmonary surfactant, was investigated as a function of pH. Spherical, citrate-capped AgNPs with average diameters of 14 ± 1.6 nm (n=200) were prepared by a chemical bath reduction. The kinetics of Ag+ ion release was strongly pH-dependent. After 14 days of incubation in sodium perchlorate (NaClO4) or perchloric acid (HClO4) solutions, the total fraction of AgNPs dissolved varied from ~10 % at pH 3, to ~2 % at pH 5, with negligible dissolution at pH 7. A decrease in pH from 7 to 3 also promoted particle aggregation and coarsening. DPPC (100 mg.L−1) delayed the release of Ag+ ions, but did not significantly alter the total amount of Ag+ released after two weeks. In addition, DPPC improved the dispersion of the AgNPs and inhibited aggregation and coarsening. TEM images revealed that the AgNPs were coated with a DPPC layer serving as a semi-permeable layer. Hence, lung lining fluid, particularly DPPC, can modify the aggregation state and kinetics of Ag+ ion release of inhaled AgNPs in the lung. These observations have important implications for predicting the potential reactivity of AgNPs in the lung and the environment. PMID:23988335

Method to produce large, uniform hollow spherical shells

DOEpatents

Hendricks, C.D.

1983-09-26

The invention is a method to produce large uniform hollow spherical shells by (1) forming uniform size drops of heat decomposable or vaporizable material, (2) evaporating the drops to form dried particles, (3) coating the dried particles with a layer of shell forming material and (4) heating the composite particles to melt the outer layer and to decompose or vaporize the inner particle to form an expanding inner gas bubble. The expanding gas bubble forms the molten outer layer into a shell of relatively large diameter. By cycling the temperature and pressure on the molten shell, nonuniformities in wall thickness can be reduced. The method of the invention is utilized to produce large uniform spherical shells, in the millimeter to centimeter diameter size range, from a variety of materials and of high quality, including sphericity, concentricity and surface smoothness, for use as laser fusion or other inertial confinement fusion targets as well as other applications.

Kinetics of Thermal Denaturation and Aggregation of Bovine Serum Albumin

PubMed Central

Borzova, Vera A.; Markossian, Kira A.; Chebotareva, Natalia A.; Kleymenov, Sergey Yu.; Poliansky, Nikolay B.; Muranov, Konstantin O.; Stein-Margolina, Vita A.; Shubin, Vladimir V.; Markov, Denis I.; Kurganov, Boris I.

2016-01-01

Thermal aggregation of bovine serum albumin (BSA) has been studied using dynamic light scattering, asymmetric flow field-flow fractionation and analytical ultracentrifugation. The studies were carried out at fixed temperatures (60°C, 65°C, 70°C and 80°C) in 0.1 M phosphate buffer, pH 7.0, at BSA concentration of 1 mg/ml. Thermal denaturation of the protein was studied by differential scanning calorimetry. Analysis of the experimental data shows that at 65°C the stage of protein unfolding and individual stages of protein aggregation are markedly separated in time. This circumstance allowed us to propose the following mechanism of thermal aggregation of BSA. Protein unfolding results in the formation of two forms of the non-native protein with different propensity to aggregation. One of the forms (highly reactive unfolded form, Uhr) is characterized by a high rate of aggregation. Aggregation of Uhr leads to the formation of primary aggregates with the hydrodynamic radius (Rh,1) of 10.3 nm. The second form (low reactive unfolded form, Ulr) participates in the aggregation process by its attachment to the primary aggregates produced by the Uhr form and possesses ability for self-aggregation with formation of stable small-sized aggregates (Ast). At complete exhaustion of Ulr, secondary aggregates with the hydrodynamic radius (Rh,2) of 12.8 nm are formed. At 60°C the rates of unfolding and aggregation are commensurate, at 70°C the rates of formation of the primary and secondary aggregates are commensurate, at 80°C the registration of the initial stages of aggregation is complicated by formation of large-sized aggregates. PMID:27101281

Curvature-induced capillary interaction of spherical particles at a liquid interface.

PubMed

Würger, Alois

2006-10-01

We consider a liquid interface with different principal curvatures +/-c and find that the mere presence of a spherical particle leads to a deformation field of quadrupolar symmetry; the corresponding "capillary quadrupole moment" is given by the ratio of the particle size and the curvature radius. The resulting pair interaction of nearby particles is anisotropic and favors the formation of aggregates of cubic symmetry. Since the single-particle trapping energy depends quadratically on curvature with a negative prefactor, a curvature gradient induces a lateral force that pushes the particles towards strongly curved regions of the interface. As an illustration we discuss the effects occurring on a catenoid.

Solvothermal Synthesis of a Hollow Micro-Sphere LiFePO4/C Composite with a Porous Interior Structure as a Cathode Material for Lithium Ion Batteries

PubMed Central

Liu, Yang; Zhang, Jieyu; Li, Ying; Hu, Yemin; Li, Wenxian; Zhu, Mingyuan; Hu, Pengfei; Chou, Shulei; Wang, Guoxiu

2017-01-01

To overcome the low lithium ion diffusion and slow electron transfer, a hollow micro sphere LiFePO4/C cathode material with a porous interior structure was synthesized via a solvothermal method by using ethylene glycol (EG) as the solvent medium and cetyltrimethylammonium bromide (CTAB) as the surfactant. In this strategy, the EG solvent inhibits the growth of the crystals and the CTAB surfactant boots the self-assembly of the primary nanoparticles to form hollow spheres. The resultant carbon-coat LiFePO4/C hollow micro-spheres have a ~300 nm thick shell/wall consisting of aggregated nanoparticles and a porous interior. When used as materials for lithium-ion batteries, the hollow micro spherical LiFePO4/C composite exhibits superior discharge capacity (163 mAh g−1 at 0.1 C), good high-rate discharge capacity (118 mAh g−1 at 10 C), and fine cycling stability (99.2% after 200 cycles at 0.1 C). The good electrochemical performances are attributed to a high rate of ionic/electronic conduction and the high structural stability arising from the nanosized primary particles and the micro-sized hollow spherical structure. PMID:29099814

Adjustable bridge blocks make huge difference to the self-assembly of multiblock copolymers

NASA Astrophysics Data System (ADS)

Li, Weihua

We present theoretical studies on two types of multiblock copolymers, whose self-assemblies lead to a lot of novel ordered nanostructures. The first example is BABCB multiblock terpolymer, where A- and C-blocks separately aggregate into isolated domains and the three B-blocks with adjustable lengths form the matrix. As a result, the middle B-block forms a natural bridge connecting A- and C-domains. In contrast to ABC, the BABCB can form many binary spherical and cylindrical phases with tunable coordination numbers. In addition, the ABCB solution can form a lot of planet-satellite micellar superstructures with tunable number of satellites that varies from 3 to 20. The another system is AB-type multiblock copolymers. In contrast to the above system, there is no natural bridge. Accordingly, we introduce multiple arms into the architecture which tend to partition themselves into different domains to maximize their configurational entropy, thus forming effective bridges. Furthermore, each arm is devised as BAB triblock to enable adjustable length of bridges. With this copolymer, we predict a few non-classical ordered phases, including a square array cylinder. Our study opens the possibilities of fabricating desired nanostructures using designed block copolymers. National Natural Science Foundation of China (No. 21322407, 21574026).

Poly(styrene-co-butadiene) random copolymer thin films and nanostructures on a mica surface: morphology and contact angles of nanodroplets.

PubMed

McClements, Jake; Buffone, Cosimo; Shaver, Michael P; Sefiane, Khellil; Koutsos, Vasileios

2017-09-20

The self-assembly of poly(styrene-co-butadiene) random copolymers on mica surfaces was studied by varying solution concentrations and polymer molecular weights. Toluene solutions of the poly(styrene-co-butadiene) samples were spin coated onto a mica surface and the resulting polymer morphology was investigated by atomic force microscopy. At higher concentrations, thin films formed with varying thicknesses; some dewetting was observed which depended on the molecular weight. Total dewetting did not occur despite the polymer's low glass transition temperature. Instead, partial dewetting was observed suggesting that the polymer was in a metastable equilibrium state. At lower concentrations, spherical cap shaped nanodroplets formed with varying sizes from single polymer chains to aggregates containing millions of chains. As the molecular weight was increased, fewer aggregates were observed on the surface, albeit with larger sizes resulting from increased solution viscosities and more chain entanglements at higher molecular weights. The contact angles of the nanodroplets were shown to be size dependent. A minimum contact angle occurs for droplets with radii of 100-250 nm at each molecular weight. Droplets smaller than 100 nm showed a sharp increase in contact angle; attributed to an increase in the elastic modulus of the droplets, in addition, to a positive line tension value. Droplets larger than 250 nm also showed an increased contact angle due to surface heterogeneities which cannot be avoided for larger droplets. This increase in contact angle plateaus as the droplet size reaches the macroscopic scale.

Experimental Study of Unsupported Nonane fuel Droplet Combustion in Microgravity

NASA Technical Reports Server (NTRS)

Callahan, B. J.; Avedisian, C. T.; Hertzog, D. E.; Berkery, J. W.

1999-01-01

Soot formation in droplet flames is the basic component of the particulate emission process that occurs in spray combustion. The complexity of soot formation motivates a one-dimensional transport condition which has obvious advantages in modeling. Recent models of spherically symmetric droplet combustion have made this assumption when incorporating such aspects as detailed chemistry and radiation. Interestingly, spherical symmetry does not necessarily restrict the results because it has been observed that the properties of carbon formed in flames are not strongly affected by the nature of the fuel or flaming configuration. What is affected, however, are the forces acting on the soot aggregates and where they are trapped by a balance of drag and thermophoretic forces. The distribution of these forces depends on the transport conditions of the flame. Prior studies of spherical droplet flames have examined the droplet burning history of alkanes, alcohols and aromatics. Data are typically the evolution of droplet, flame, extinction, and soot shell diameters. These data are only now just beginning to find their way into comprehensive numerical models of droplet combustion to test proposed oxidation schemes for fuels such as methanol and heptane. In the present study, we report new measurements on the burning history of unsupported nonane droplets in a convection-free environment to promote spherical symmetry. The far-field gas is atmospheric pressure air at room temperature. The evolution of droplet diameter was measured using high speed cine photography of a spark-ignited, droplet within a confined volume in a drop tower. The initial droplet diameters varied between 0.5 mm and 0.6 mm. The challenge of unsupported droplets is to form, deploy and ignite them with minimal disturbance, and then to keep them in the camera field of view. Because of the difficulty of this undertaking, more sophisticated diagnostics for studying soot than photographic were not used. Supporting the test droplet by a fiber fixes the droplet position but the fiber can perturb the burning process especially for a sooting fuel. Prior studies on heptane showed little evidence for soot formation due to g-droplets of similar size the relationship between sooting and droplet diameter. For nonane droplets we expect increased sooting due to the greater number of carbon atoms. As a sooting droplet burns and its diameter decreases, proportionally less soot should form. This reduced soot, as well as the influence of soot formed earlier in the burning process which collects in a 'shell', on heat transport to the flame offers the potential for a time-varying burning rate. Such an effect was investigated and revealed in results reported here. Speculation is offered for the cause of this effect and its possible relation to soot formation.

Cryogenic target formation using cold gas jets

DOEpatents

Hendricks, Charles D.

1981-01-01

A method and apparatus using cold gas jets for producing a substantially uniform layer of cryogenic materials on the inner surface of hollow spherical members having one or more layers, such as inertially imploded targets. By vaporizing and quickly refreezing cryogenic materials contained within a hollow spherical member, a uniform layer of the materials is formed on an inner surface of the spherical member. Basically the method involves directing cold gas jets onto a spherical member having one or more layers or shells and containing the cryogenic material, such as a deuterium-tritium (DT) mixture, to freeze the contained material, momentarily heating the spherical member so as to vaporize the contained material, and quickly refreezing the thus vaporized material forming a uniform layer of cryogenic material on an inner surface of the spherical member.

Cryogenic target formation using cold gas jets

DOEpatents

Hendricks, Charles D. [Livermore, CA

1980-02-26

A method and apparatus using cold gas jets for producing a substantially uniform layer of cryogenic materials on the inner surface of hollow spherical members having one or more layers, such as inertially imploded targets. By vaporizing and quickly refreezing cryogenic materials contained within a hollow spherical member, a uniform layer of the materials is formed on an inner surface of the spherical member. Basically the method involves directing cold gas jets onto a spherical member having one or more layers or shells and containing the cryogenic material, such as a deuterium-tritium (DT) mixture, to freeze the contained material, momentarily heating the spherical member so as to vaporize the contained material, and quickly refreezing the thus vaporized material forming a uniform layer of cryogenic material on an inner surface of the spherical member.

Macrostructure-dependent photocatalytic property of high-surface-area porous titania films

NASA Astrophysics Data System (ADS)

Kimura, T.

2014-11-01

Porous titania films with different macrostructures were prepared with precise control of condensation degree and density of the oxide frameworks in the presence of spherical aggregates of polystyrene-block-poly(oxyethylene) (PS-b-PEO) diblock copolymer. Following detailed explanation of the formation mechanisms of three (reticular, spherical, and large spherical) macrostructures by the colloidal PS-b-PEO templating, structural variation of the titania frameworks during calcination were investigated by X-ray diffraction and X-ray photoelectron spectroscopy. Then, photocatalytic performance of the macroporous titania films was evaluated through simple degradation experiments of methylene blue under an UV irradiation. Consequently, absolute surface area of the film and crystallinity of the titania frameworks were important for understanding the photocatalytic performance, but the catalytic performance can be improved further by the macrostructural design that controls diffusivity of the targeted molecules inside the film and their accessibility to active sites.

Theoretical study of nanoparticle formation in thermal plasma processing: Nucleation, coagulation and aggregation

NASA Astrophysics Data System (ADS)

Mendoza Gonzalez, Norma Yadira

This work presents a mathematical modeling study of the synthesis of nanoparticles in radio frequency (RF) inductively coupled plasma (ICP) reactors. The purpose is to further investigate the influence of process parameters on the final size and morphology of produced particles. The proposed model involves the calculation of flow and temperature fields of the plasma gas. Evaporation of raw particles is also accounted with the particle trajectory and temperature history calculated with a Lagrangian approach. The nanoparticle formation is considered by homogeneous nucleation and the growth is caused by condensation and Brownian coagulation. The growth of fractal aggregates is considered by introducing a power law exponent Df. Transport of nanoparticles occurs by convection, thermophoresis and Brownian diffusion. The method of moments is used to solve the particle dynamics equation. The model is validated using experimental results from plasma reactors at laboratory scale. The results are presented in the following manner. First, use is made of the computational fluid dynamics software (CFD), Fluent 6.1 with a commercial companion package specifically developped for aerosols named: Fine Particle Model (FPM). This package is used to study the relationship between the operating parameters effect and the properties of the end products at the laboratory scale. Secondly, a coupled hybrid model for the synthesis of spherical particles and fractal aggregates is developped in place of the FPM package. Results obtained from this model will allow to identify the importance of each parameter in defining the morphology of spherical primary particles and fractal aggregates of nanoparticles. The solution of the model was made using the geometries and operating conditions of existing reactors at the Centre de Recherche en Energie, Plasma et Electrochimie (CREPE) of the Universite de Sherbrooke, for which experimental results were obtained experimentally. Additionally, this study demonstrates the importance of the flow and temperature fields on the growth of fractal particles; namely the aggregates.

Cryogenic target formation using cold gas jets

DOEpatents

Hendricks, C.D.

1980-02-26

A method and apparatus using cold gas jets for producing a substantially uniform layer of cryogenic materials on the inner surface of hollow spherical members having one or more layers, such as inertially imploded targets are disclosed. By vaporizing and quickly refreezing cryogenic materials contained within a hollow spherical member, a uniform layer of the materials is formed on an inner surface of the spherical member. Basically the method involves directing cold gas jets onto a spherical member having one or more layers or shells and containing the cryogenic material, such as a deuterium-tritium (DT) mixture, to freeze the contained material, momentarily heating the spherical member so as to vaporize the contained material, and quickly refreezing the thus vaporized material forming a uniform layer of cryogenic material on an inner surface of the spherical member. 4 figs.

Tetanus toxoid-loaded cationic non-aggregated nanostructured lipid particles triggered strong humoral and cellular immune responses.

PubMed

Kaur, Amandeep; Jyoti, Kiran; Rai, Shweta; Sidhu, Rupinder; Pandey, Ravi Shankar; Jain, Upendra Kumar; Katyal, Anju; Madan, Jitender

2016-05-01

In the present investigation, non-aggregated cationic and unmodified nanoparticles (TT-C-NLPs4 and TT-NLPs1) were prepared of about 49.2 ± 6.8-nm and 40.8 ± 8.3-nm, respectively. In addition, spherical shape, crystalline architecture and cationic charge were also noticed. Furthermore, integrity and conformational stability of TT were maintained in both TT-C-NLPs4 and TT-NLPs1, as evidenced by symmetrical position of bands and superimposed spectra, respectively in SDS-PAGE and circular dichroism. Cellular uptake in RAW264.7 cells indicating the concentration-dependent internalisation of nanoparticles. Qualitatively, CLSM exhibited enhanced cellular uptake of non-aggregated TT-C-NLPs4 owing to interaction with negatively charged plasma membrane and clevaloe mediated/independent endocytosis. In last, in vivo immunisation with non-aggregated TT-C-NLPs4 elicited strong humoral (anti-TT IgG) and cellular (IFN-γ) immune responses at day 42, as compared to non-aggregated TT-NLPs1 and TT-Alum following booster immunisation at day 14 and 28. Thus, non-aggregated cationic lipid nanoparticles may be a potent immune-adjuvant for parenteral delivery of weak antigens.

Absorption and scattering by fractal aggregates and by their equivalent coated spheres

NASA Astrophysics Data System (ADS)

Kandilian, Razmig; Heng, Ri-Liang; Pilon, Laurent

2015-01-01

This paper demonstrates that the absorption and scattering cross-sections and the asymmetry factor of randomly oriented fractal aggregates of spherical monomers can be rapidly estimated as those of coated spheres with equivalent volume and average projected area. This was established for fractal aggregates with fractal dimension ranging from 2.0 to 3.0 and composed of up to 1000 monodisperse or polydisperse monomers with a wide range of size parameter and relative complex index of refraction. This equivalent coated sphere approximation was able to capture the effects of both multiple scattering and shading among constituent monomers on the integral radiation characteristics of the aggregates. It was shown to be superior to the Rayleigh-Debye-Gans approximation and to the equivalent coated sphere approximation proposed by Latimer. However, the scattering matrix element ratios of equivalent coated spheres featured large angular oscillations caused by internal reflection in the coating which were not observed in those of the corresponding fractal aggregates. Finally, the scattering phase function and the scattering matrix elements of aggregates with large monomer size parameter were found to have unique features that could be used in remote sensing applications.

Design and Synthesis of Spherical Multicomponent Aggregates Composed of Core-Shell, Yolk-Shell, and Hollow Nanospheres and Their Lithium-Ion Storage Performances.

PubMed

Park, Gi Dae; Kang, Yun Chan

2018-03-01

Micrometer-sized spherical aggregates of Sn and Co components containing core-shell, yolk-shell, hollow nanospheres are synthesized by applying nanoscale Kirkendall diffusion in the large-scale spray drying process. The Sn 2 Co 3 -Co 3 SnC 0.7 -C composite microspheres uniformly dispersed with Sn 2 Co 3 -Co 3 SnC 0.7 mixed nanocrystals are formed by the first-step reduction of spray-dried precursor powders at 900 °C. The second-step oxidation process transforms the Sn 2 Co 3 -Co 3 SnC 0.7 -C composite into the porous microsphere composed of Sn-Sn 2 Co 3 @CoSnO 3 -Co 3 O 4 core-shell, Sn-Sn 2 Co 3 @CoSnO 3 -Co 3 O 4 yolk-shell, and CoSnO 3 -Co 3 O 4 hollow nanospheres at 300, 400, and 500 °C, respectively. The discharge capacity of the microspheres with Sn-Sn 2 Co 3 @CoSnO 3 -Co 3 O 4 core-shell, Sn-Sn 2 Co 3 @CoSnO 3 -Co 3 O 4 yolk-shell, and CoSnO 3 -Co 3 O 4 hollow nanospheres for the 200 th cycle at a current density of 1 A g -1 is 1265, 987, and 569 mA h g -1 , respectively. The ultrafine primary nanoparticles with a core-shell structure improve the structural stability of the porous-structured microspheres during repeated lithium insertion and desertion processes. The porous Sn-Sn 2 Co 3 @CoSnO 3 -Co 3 O 4 microspheres with core-shell primary nanoparticles show excellent cycling and rate performances as anode materials for lithium-ion batteries. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanocrystalline Chalcopyrite Materials (CuInS2 and CuInSe2) via Low-Temperature Pyrolysis of Molecular Single-Source Precursors

NASA Technical Reports Server (NTRS)

Castro, Stephanie L.; Bailey, Sheila G.; Raffaelle, Ryne P.; Banger, Kulbinder K.; Hepp, Aloysius F.

2003-01-01

Nanometer sized particles of the chalcopyrite compounds CuInS2 and CuInSe2 were synthesized by thermal decomposition of molecular single-source precursors (PPh3)2CuIn(SEt)4 and (PPh3)2CuIn(SePh)4, respectively, in the non-coordinating solvent dioctyl phthalate at temperatures between 200 and 300 C. The nanoparticles range in size from 3 - 30 nm and are aggregated to form roughly spherical clusters of about 500 nm in diameter. X-ray diffraction of the nanoparticle powders shows greatly broadened lines indicative of very small particle sizes, which is confirmed by TEM. Peaks present in the XRD can be indexed to reference patterns for the respective chalcopyrite compounds. Optical spectroscopy and elemental analysis by energy dispersive spectroscopy support the identification of the nanoparticles as chalcopyrites.

The study of the structural properties of very low viscosity sodium alginate by small-angle neutron scattering

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

Badita, C. R., E-mail: ramona@tandem.nipne.ro; University of Bucharest, Faculty of Physics, Atomiştilor 405, CP MG - 11, RO – 077125, Bucharest-Magurele; Aranghel, D., E-mail: daranghe@nipne.ro

2016-03-25

Sodium alginate is a linear polymer extract from brown algae and it is used in the biomedical, food, cosmetics and pharmaceutical industries as solution property modifiers and gelling agents. But despite the extensive studies of the alginate gelation process, still some fundamental questions remain unresolved. The fractal behavior of very low viscosity sodium alginate solutions and their influence on the critical gelation of alginate induced by Ca{sup 2+} ions were investigated using Small-Angle Neutron Scattering (SANS) measurements. SANS data are interpreted using both standard linear plots and the Beaucage model. The scattering intensity is dependent by alginate concentration and Ca{supmore » 2+} concentration. From a critical concentration of 1.0 % w/w our polymer swelled forming spherical structures with rough surfaces. Also the addition of the salt induces the collapse and the appearance of the aggregation and clusters formation.« less

Statistical cyclicity of the supercontinent cycle

NASA Astrophysics Data System (ADS)

Rolf, T.; Coltice, N.; Tackley, P. J.

2014-04-01

Supercontinents like Pangea impose a first-order control on Earth's evolution as they modulate global heat loss, sea level, climate, and biodiversity. In a traditional view, supercontinents form and break up in a regular, perhaps periodic, manner in a cycle lasting several 100 Myr as reflected in the assembly times of Earth's major continental aggregations: Columbia, Rodinia, and Pangea. However, modern views of the supercontinent cycle propose a more irregular evolution on the basis of an improved understanding of the Precambrian geologic record. Here we use fully dynamic spherical mantle convection models featuring plate-like behavior and continental drift to investigate supercontinent formation and breakup. We further dismiss the concept of regularity but suggest a statistical cyclicity in which the supercontinent cycle may have a characteristic period imposed by mantle and lithosphere properties, but this is hidden in immense fluctuations between different cycles that arise from the chaotic nature of mantle flow.

The coordination chemistry of group 15 element ligand complexes--a developing area.

PubMed

Scheer, Manfred

2008-09-07

A survey of the contemporary challenges of the field of unsubstituted group 15 element ligand complexes (excluding N) is given. The focus of the article is on the coordination chemistry behaviour of such E(n) ligand complexes. This field is subdivided into two areas of reactivity: E(n) ligand complexes with (i) noncoordinated Lewis-acidic cations and (ii) Lewis-acidic coordination compounds containing at least one permanently coordinating ligand. In the latter case, insoluble 1D and 2D polymers respectively are obtained; however, under special conditions soluble, spherical, fullerene-like giant molecules are formed. These nano-sized molecules are up to 2.4 nm in diameter and are able to encapsulate small molecules in their holes. In contrast, the first-mentioned field uses weakly coordinating anions to obtain readily soluble di- and polycationic products. These show depolymerisation tendencies in solution under the formation of oligomer-monomer equilibria and thus reveal dynamic supramolecular aggregation processes.

The study of the structural properties of very low viscosity sodium alginate by small-angle neutron scattering

NASA Astrophysics Data System (ADS)

Badita, C. R.; Aranghel, D.; Radulescu, A.; Anitas, E. M.

2016-03-01

Sodium alginate is a linear polymer extract from brown algae and it is used in the biomedical, food, cosmetics and pharmaceutical industries as solution property modifiers and gelling agents. But despite the extensive studies of the alginate gelation process, still some fundamental questions remain unresolved. The fractal behavior of very low viscosity sodium alginate solutions and their influence on the critical gelation of alginate induced by Ca2+ ions were investigated using Small-Angle Neutron Scattering (SANS) measurements. SANS data are interpreted using both standard linear plots and the Beaucage model. The scattering intensity is dependent by alginate concentration and Ca2+ concentration. From a critical concentration of 1.0 % w/w our polymer swelled forming spherical structures with rough surfaces. Also the addition of the salt induces the collapse and the appearance of the aggregation and clusters formation.

Formation of Polymeric Nanocubes by Self-Assembly and Crystallization of Dithiolane-Containing Triblock Copolymers

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

Margulis, Katherine; Zhang, Xiangyi; Joubert, Lydia -Marie

Template–free fabrication of non–spherical polymeric nanoparticles is desirable for various applications, but has had limited success owing to thermodynamic favorability of sphere formation. Herein we present a simple way to prepare cubic nanoparticles of block copolymers by self–assembly from aqueous solutions at room temperature. Nanocubes with edges of 40–200 nm are formed spontaneously on different surfaces upon water evaporation from micellar solutions of triblock copolymers containing a central poly(ethylene oxide) block and terminal trimethylene carbonate/dithiolane blocks. These polymers self–assemble into 28±5 nm micelles in water. Upon drying, micelle aggregation and a kinetically controlled crystallization of central blocks evidently induce solidmore » cubic particle formation. An approach for preserving the structures of these cubes in water by thiol– or photo–induced crosslinking was developed. In conclusion, the ability to solubilize a model hydrophobic drug, curcumin, was also explored.« less

Formation of Polymeric Nanocubes by Self-Assembly and Crystallization of Dithiolane-Containing Triblock Copolymers

DOE PAGES

Margulis, Katherine; Zhang, Xiangyi; Joubert, Lydia -Marie; ...

2017-10-27

Template–free fabrication of non–spherical polymeric nanoparticles is desirable for various applications, but has had limited success owing to thermodynamic favorability of sphere formation. Herein we present a simple way to prepare cubic nanoparticles of block copolymers by self–assembly from aqueous solutions at room temperature. Nanocubes with edges of 40–200 nm are formed spontaneously on different surfaces upon water evaporation from micellar solutions of triblock copolymers containing a central poly(ethylene oxide) block and terminal trimethylene carbonate/dithiolane blocks. These polymers self–assemble into 28±5 nm micelles in water. Upon drying, micelle aggregation and a kinetically controlled crystallization of central blocks evidently induce solidmore » cubic particle formation. An approach for preserving the structures of these cubes in water by thiol– or photo–induced crosslinking was developed. In conclusion, the ability to solubilize a model hydrophobic drug, curcumin, was also explored.« less

Laser ablated copper plasmas in liquid and gas ambient

NASA Astrophysics Data System (ADS)

Kumar, Bhupesh; Thareja, Raj K.

2013-05-01

The dynamics of copper ablated plasma plumes generated using laser ablation of copper targets in both liquid (de-ionized water) and gas (air) ambients is reported. Using time and space resolved visible emission spectroscopy (450-650 nm), the plasma plumes parameters are investigated. The electron density (ne) determined using Stark broadening of the Cu I (3d104d1 2D3/2-3d104p1 2P3/2 at 521.8 nm) line is estimated and compared for both plasma plumes. The electron temperature (Te) was estimated using the relative line emission intensities of the neutral copper transitions. Field emission scanning electron microscopy and energy dispersive x-ray spectral analysis of the ablated copper surface indicated abundance of spherical nanoparticles in liquid while those in air are amalgamates of irregular shapes. The nanoparticles suspended in the confining liquid form aggregates and exhibit a surface plasmon resonance at ˜590 nm.

Research on flux of dry atmospheric falling dust and its characterization in a subtropical city, Guangzhou, South China.

PubMed

Zhao, Jinping; Peng, Ping'an; Song, Jianzhong; Ma, Shexia; Sheng, Guoying; Fu, Jiamo

2010-09-01

Guangzhou is the central city in the Pearl River Delta (PRD), China, and is one of the most polluted cities in the world. To characterize the ambient falling dust pollution, two typical sampling sites: urban (Wushan) and suburban (University Town) areas in Guangzhou city were chosen for falling dust collection over 1 year at time intervals of 1 or 2 months. The flux of dry deposition was calculated. In addition, mineral composition and morphology of atmospheric falling dust were studied by X-ray diffraction, scanning electron microscopy, and microscopic observation. The results revealed that the dust flux in Guangzhou city was 3.34-3.78 g/(m(2) month) during the study period. The main minerals in the dust were quartz, illite, calcite, kaolinite, gypsum, plagioclase, dolomite, and amorphous matter. The morphological types included grained and flaky individual minerals, chain-like aggregates, spherical flying beads, and irregular aggregates, with the chain-like and spherical aggregates indicators of industrial ash. The major dusts were derived from industrial and construction activities. The gypsum present in the dust collected in winter season was not only derived from cement dust but may also have originated from the reaction of calcic material with sulfuric acids resulting from photooxidation of SO(x) and NO(x), which confirmed serious air pollution due to SO(x) and NO(x) in Guangzhou. The abatement of fossil fuel combustion emissions and construction dust will have a significant beneficial effect on dust reduction.

Wormlike micelle formation by acylglutamic acid with alkylamines.

PubMed

Sakai, Kenichi; Nomura, Kazuyuki; Shrestha, Rekha Goswami; Endo, Takeshi; Sakamoto, Kazutami; Sakai, Hideki; Abe, Masahiko

2012-12-21

Rheological properties of alkyl dicarboxylic acid-alkylamine complex systems have been characterized. The complex materials employed in this study consist of an amino acid-based surfactant (dodecanoylglutamic acid, C12Glu) and a tertiary alkylamine (dodecyldimethylamine, C12DMA) or a secondary alkylamine (dodecylmethylamine, C12MA). (1)H NMR and mass spectroscopic data have suggested that C12Glu forms a stoichiometric 1:1 complex with C12DMA and C12MA. Rheological measurements have suggested that the complex systems yield viscoelastic wormlike micellar solutions and the rheological behavior is strongly dependent on the aqueous solution pH. This pH-dependent behavior results from the structural transformation of the wormlike micelles to occur in the narrow pH range 5.5-6.2 (in the case of C12Glu-C12DMA system); i.e., positive curved aggregates such as spherical or rodlike micelles tend to be formed at high pH values. Our current study offers a unique way to obtain viscoelastic wormlike micellar solutions by means of alkyl dicarboxylic acid-alkylamine complex as gemini-like amphiphiles.

Microphysical Characteristics of Tropical Updrafts in Clean Conditions.

NASA Astrophysics Data System (ADS)

Stith, Jeffrey L.; Haggerty, Julie A.; Heymsfield, Andrew; Grainger, Cedric A.

2004-05-01

The distributions of ice particles, precipitation embryos, and supercooled water are examined within updrafts in convective clouds in the Amazon and at Kwajalein, Marshall Islands, based on in situ measurements during two Tropical Rainfall Measuring Mission field campaigns. Composite vertical profiles of liquid water, small particle concentration, and updraft/downdraft magnitudes exhibit similar peak values for the two tropical regions. Updrafts were found to be favored locations for precipitation embryos in the form of liquid or frozen drizzle-sized droplets. Most updrafts glaciated rapidly, removing most of the liquid water between -5° and -17°C. However, occasional encounters with liquid water occurred in much colder updraft regions. The updraft magnitudes where liquid water was observed at cold (e.g., -16° to -19°C) temperatures do not appear to be stronger than updrafts without liquid water at similar temperatures, however. The concentrations of small spherical frozen particles in glaciated regions without liquid water are approximately one-half of the concentrations in regions containing liquid cloud droplets, suggesting that a substantial portion of the cloud droplets may be freezing at relatively warm temperatures. Further evidence for a possible new type of aggregate ice particle, a chain aggregate found at cloud midlevels, is given.

Aggregation of heteropolyanions in aqueous solutions exhibiting short-range attractions and long-range repulsions

DOE PAGES

Bera, Mrinal K.; Qiao, Baofu; Seifert, Soenke; ...

2015-12-15

Charged colloids and proteins in aqueous solutions interact via short-range attractions and long-range repulsions (SALR) and exhibit complex structural phases. These include homogeneously dispersed monomers, percolated monomers, clusters, and percolated clusters. We report the structural architectures of simple charged systems in the form of spherical, Keggin-type heteropolyanions (HPAs) by small-angle X-ray scattering (SAXS) and molecular dynamics (MD) simulations. Structure factors obtained from the SAXS measurements show that the HPAs interact via SALR. Concentration and temperature dependences of the structure factors for HPAs with –3e (e is the charge of an electron) charge are consistent with a mixture of nonassociated monomersmore » and associated randomly percolated monomers, whereas those for HPAs with –4e and –5e charges exhibit only nonassociated monomers in aqueous solutions. Our experiments show that the increase in magnitude of the charge of the HPAs increases their repulsive interactions and inhibits their aggregation in aqueous solutions. MD simulations were done to reveal the atomistic scale origins of SALR between HPAs. As a result, the short-range attractions result from water or proton-mediated hydrogen bonds between neighboring HPAs, whereas the long-range repulsions are due to the distributions of ions surrounding the HPAs.« less

Viral Aggregation: Impact on Virus Behavior in the Environment.

PubMed

Gerba, Charles P; Betancourt, Walter Q

2017-07-05

Aggregates of viruses can have a significant impact on quantification and behavior of viruses in the environment. Viral aggregates may be formed in numerous ways. Viruses may form crystal like structures and aggregates in the host cell during replication or may form due to changes in environmental conditions after virus particles are released from the host cells. Aggregates tend to form near the isoelectric point of the virus, under the influence of certain salts and salt concentrations in solution, cationic polymers, and suspended organic matter. The given conditions under which aggregates form in the environment are highly dependent on the type of virus, type of salts in solution (cation, anion. monovalent, divalent) and pH. However, virus type greatly influences the conditions when aggregation/disaggregation will occur, making predictions difficult under any given set of water quality conditions. Most studies have shown that viral aggregates increase the survival of viruses in the environment and resistance to disinfectants, especially with more reactive disinfectants. The presence of viral aggregates may also result in overestimation of removal by filtration processes. Virus aggregation-disaggregation is a complex process and predicting the behavior of any individual virus is difficult under a given set of environmental circumstances without actual experimental data.

The sagitta and lens thickness: the exact solution and a matrix approximation for lenses with toric, spherical, and cylindrical surfaces.

PubMed

Harris, W F

1989-03-01

The exact equation for sagitta of spherical surfaces is generalized to toric surfaces which include spherical and cylindrical surfaces as special cases. Lens thickness, therefore, can be calculated accurately anywhere on a lens even in cases of extreme spherical and cylindrical powers and large diameters. The sagittae of tire- and barrel-form toric surfaces differ off the principal meridians, as is shown by a numerical example. The same holds for pulley- and capstan-form toric surfaces. A general expression is given for thickness at an arbitrary point on a toric lens. Approximate expressions are derived and re-expressed in terms of matrices. The matrix provides an elegant means of generalizing equations for spherical surfaces and lenses to toric surfaces and lenses.

Photoisomerisation and light-induced morphological switching of a polyoxometalate-azobenzene hybrid.

PubMed

Markiewicz, Grzegorz; Pakulski, Dawid; Galanti, Agostino; Patroniak, Violetta; Ciesielski, Artur; Stefankiewicz, Artur R; Samorì, Paolo

2017-06-29

The functionalization of a spherical Keplerate-type polyoxometalate {Mo 72 V 30 } with a cationic azobenzene surfactant has been achieved through ionic self-assembly. The photoisomerisation reaction of this complex, which emerges in a light-triggered aggregation-disaggregation process, has been followed by 1 H NMR spectroscopy, dynamic light scattering, absorption spectroscopy and scanning electron microscopy analyses.

An insight into the influence of crystallite size on the performances of microsized spherical Li(Ni0.5Co0.2Mn0.3)O2 cathode material composed of aggregated nanosized particles

NASA Astrophysics Data System (ADS)

Fan, Guangxin; Wen, Yin; Liu, Baozhong; Yang, Wenpeng

2018-02-01

Relationships between the performance and the crystallite size of the microsized spherical Li(Ni0.5Co0.2Mn0.3)O2 cathode material composed of aggregated nanosized primary particles have been comprehensively studied. The cathode material was synthesized by a high-temperature solid-state method. The results obtained by XRD, Rietveld refinement, SEM, HR-TEM, DSC, and galvanostatic test show that the crystallite size (XS) of Li(Ni0.5Co0.2Mn0.3)O2 is greatly affected by the temperature in the range of 750 to 820 °C. Most of all, the crystallite size plays a unique role in the performance of the material. That is, the electrochemical characteristics of Li(Ni0.5Co0.2Mn0.3)O2, such as discharge capacity, rate performance, and thermal stability, are closely related to the crystallite size. Furthermore, the retention of discharge capacity is determined by that of crystallite size in Li(Ni0.5Co0.2Mn0.3)O2 after 100 cycles.

Heating of Porous Icy Dust Aggregates

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

Sirono, Sin-iti

At the beginning of planetary formation, highly porous dust aggregates are formed through coagulation of dust grains. Outside the snowline, the main component of an aggregate is H{sub 2}O ice. Because H{sub 2}O ice is formed in amorphous form, its thermal conductivity is extremely small. Therefore, the thermal conductivity of an icy dust aggregate is low. There is a possibility of heating inside an aggregate owing to the decay of radionuclides. It is shown that the temperature increases substantially inside an aggregate, leading to crystallization of amorphous ice. During the crystallization, the temperature further increases sufficiently to continue sintering. Themore » mechanical properties of icy dust aggregates change, and the collisional evolution of dust aggregates is affected by the sintering.« less

A study of sedimentation and aggregation of volcanic particles based on experiments carried out with a vertical wind tunnel

NASA Astrophysics Data System (ADS)

Bagheri, G.; Bonadonna, C.; Manzella, I.; Pontelandolfo, P.; Haas, P.

2012-12-01

A complete understanding and parameterization of both particle sedimentation and particle aggregation require systematic and detailed laboratory investigations performed in controlled conditions. For this purpose, a dedicated 4-meter-high vertical wind tunnel has been designed and constructed at the University of Geneva in collaboration with the Groupe de compétence en mécanique des fluides et procédés énergétiques (CMEFE). Final design is a result of Computational Fluid Dynamics simulations combined with laboratory tests. With its diverging test section, the tunnel is designed to suspend particles of different shapes and sizes in order to study the aero-dynamical behavior of volcanic particles and their collision and aggregation. In current set-up, velocities between 5.0 to 27 ms-1 can be obtained, which correspond to typical volcanic particles with diameters between 10 to 40 mm. A combination of Particle Tracking Velocimetry (PTV) and statistical methods is used to derive particle terminal velocity. The method is validated using smooth spherical particles with known drag coefficient. More than 120 particles of different shapes (i.e. spherical, regular and volcanic) and compositions are 3D-scanned and almost 1 million images of their suspension in the test section of wind tunnel are recorded by a high speed camera and analyzed by a PTV code specially developed for the wind tunnel. Measured values of terminal velocity for tested particles are between 3.6 and 24.9 ms-1 which corresponds to Reynolds numbers between 8×103 and 1×105. In addition to the vertical wind tunnel, an apparatus with height varying between 0.5 and 3.5 m has been built to measure terminal velocity of micrometric particles in Reynolds number between 4 and 100. In these experiments, particles are released individually in the air at top of the apparatus and their terminal velocities are measured at the bottom of apparatus by a combination of high-speed camera imaging and PTV post-analyzing. Effects of shape, porosity and orientation of the particles on their terminal velocity are studied. Various shape factors are measured based on different methods, such as 3D-scanning, 2D-image processing, SEM image analysis, caliper measurements, pycnometer and buoyancy tests. Our preliminary experiments on non-smooth spherical particles and irregular particles reveal some interesting aspects. First, the effect of surface roughness and porosity is more important for spherical particles than for regular non-spherical and irregular particles. Second, results underline how, the aero-dynamical behavior of individual irregular particles is better characterized by a range of values of drag coefficients instead of a single value. Finally, since all the shape factors are calculated precisely for each individual particle, the resulted database can provide important information to benchmark and improve existing terminal-velocity models. Modifications of the wind tunnel, i.e. very low air speed (0.03-5.0 ms-1) for suspension of micrometric particles, and of the PTV code, i.e. multiple particle tracking and collision counting, have also been performed in combination to the installation of a particle charging device, a controlled humidifier and a high-power chiller (to reach values down to -20 °C) in order to investigate both wet and dry aggregation of volcanic particles.

Multiple impacts of dusty projectiles

NASA Astrophysics Data System (ADS)

Kothe, Stefan; Güttler, Carsten; Blum, Jurgen

In the context of early stages of planetesimal formation we performed laboratory and drop tower experiments to study multiple impacts of small dust-aggregate projectiles into solid sintered dust targets. Both collision partners consisted of 1.5 µm monodisperse spherical SiO2 monomers with volume filling factors of 0.15 (projectiles) and 0.35 (targets), respectively. The fragile projectiles were accelerated by a solenoid accelerator with a linear projectile magazine, which enabled us to perform 25 impacts within 4.5 s of microgravity time in the Bremen drop tower. We measured the mass-accretion efficiency for different impact velocities between 3 and 5 m s-1 , using an analytical balance and imaging methods. Furthermore, we observed random collisions among small dust aggregates with sizes around 1 mm and collision velocities of the order of 0.25 m s-1 and used them to improve the dust-aggregate collision model of Güttler et al. (2010). u

Quantitative imaging of aggregated emulsions.

PubMed

Penfold, Robert; Watson, Andrew D; Mackie, Alan R; Hibberd, David J

2006-02-28

Noise reduction, restoration, and segmentation methods are developed for the quantitative structural analysis in three dimensions of aggregated oil-in-water emulsion systems imaged by fluorescence confocal laser scanning microscopy. Mindful of typical industrial formulations, the methods are demonstrated for concentrated (30% volume fraction) and polydisperse emulsions. Following a regularized deconvolution step using an analytic optical transfer function and appropriate binary thresholding, novel application of the Euclidean distance map provides effective discrimination of closely clustered emulsion droplets with size variation over at least 1 order of magnitude. The a priori assumption of spherical nonintersecting objects provides crucial information to combat the ill-posed inverse problem presented by locating individual particles. Position coordinates and size estimates are recovered with sufficient precision to permit quantitative study of static geometrical features. In particular, aggregate morphology is characterized by a novel void distribution measure based on the generalized Apollonius problem. This is also compared with conventional Voronoi/Delauney analysis.

Colorimetric As (V) detection based on S-layer functionalized gold nanoparticles.

PubMed

Lakatos, Mathias; Matys, Sabine; Raff, Johannes; Pompe, Wolfgang

2015-11-01

Herein, we present simple and rapid colorimetric and UV/VIS spectroscopic methods for detecting anionic arsenic (V) complexes in aqueous media. The methods exploit the aggregation of S-layer-functionalized spherical gold nanoparticles of sizes between 20 and 50 nm in the presence of arsenic species. The gold nanoparticles were functionalized with oligomers of the S-layer protein of Lysinibacillus sphaericus JG-A12. The aggregation of the nanoparticles results in a color change from burgundy-red for widely dispersed nanoparticles to blue for aggregated nanoparticles. A detailed signal analysis was achieved by measuring the shift of the particle plasmon resonance signal with UV/VIS spectroscopy. To further improve signal sensitivity, the influence of larger nanoparticles was tested. In the case of 50 nm gold nanoparticles, a concentration of the anionic arsenic (V) complex lower than 24 ppb was detectable. Copyright © 2015 Elsevier B.V. All rights reserved.

Kinetic model for astaxanthin aggregation in water-methanol mixtures

NASA Astrophysics Data System (ADS)

Giovannetti, Rita; Alibabaei, Leila; Pucciarelli, Filippo

2009-07-01

The aggregation of astaxanthin in hydrated methanol was kinetically studied in the temperature range from 10 °C to 50 °C, at different astaxanthin concentrations and solvent composition. A kinetic model for the formation and transformation of astaxanthin aggregated has been proposed. Spectrophotometric studies showed that monomeric astaxanthin decayed to H-aggregates that after-wards formed J-aggregates when water content was 50% and the temperature lower than 20 °C; at higher temperatures, very stable J-aggregates were formed directly. Monomer formed very stable H-aggregates when the water content was greater than 60%; in these conditions H-aggregates decayed into J-aggregates only when the temperature was at least 50 °C. Through these findings it was possible to establish that the aggregation reactions took place through a two steps consecutive reaction with first order kinetic constants and that the values of these depended on the solvent composition and temperature.

Effect of curcumin on amyloid-like aggregates generated from methionine-oxidized apolipoprotein A-I

DOE PAGES

Krishnamoorthy, Aparna; Tavoosi, Narjes; Chan, Gary K. L.; ...

2018-01-10

Curcumin is a polyphenolic phytonutrient that has antineurodegenerative properties. Here, we investigated the anti-amyloidogenic properties of curcumin. Following incubation with curcumin, intrinsic tryptophan fluorescence emission of apolipoprotein (apo) A-I was strongly quenched. At the same time, curcumin fluorescence emission was enhanced. The fluorescence emission spectra of curcumin in the presence of amyloid-like aggregates formed by methionine-oxidized (ox) apoA-I varied, depending on whether curcumin was added before, or after, aggregate formation. The impact of curcumin on the structure of the aggregating material was revealed by the lower amount of β-structure in ox-apoA-I amyloid-like aggregates formed in the presence of curcumin, comparedmore » to aggregates formed without curcumin. However, the kinetics of ox-apoA-I amyloid-like aggregate formation was not altered by the presence of curcumin. Moreover, electron microscopy analysis detected no discernable differences in amyloid morphology when ox-apoA-I amyloid-like aggregates were formed in the presence or absence of curcumin. In conclusion, curcumin interacts with apoA-I and alters the structure of ox-apoA-I amyloid-like aggregates yet does not diminish the propensity of ox-apoA-I to form aggregates.« less

Effect of curcumin on amyloid-like aggregates generated from methionine-oxidized apolipoprotein A-I

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

Krishnamoorthy, Aparna; Tavoosi, Narjes; Chan, Gary K. L.

Curcumin is a polyphenolic phytonutrient that has antineurodegenerative properties. Here, we investigated the anti-amyloidogenic properties of curcumin. Following incubation with curcumin, intrinsic tryptophan fluorescence emission of apolipoprotein (apo) A-I was strongly quenched. At the same time, curcumin fluorescence emission was enhanced. The fluorescence emission spectra of curcumin in the presence of amyloid-like aggregates formed by methionine-oxidized (ox) apoA-I varied, depending on whether curcumin was added before, or after, aggregate formation. The impact of curcumin on the structure of the aggregating material was revealed by the lower amount of β-structure in ox-apoA-I amyloid-like aggregates formed in the presence of curcumin, comparedmore » to aggregates formed without curcumin. However, the kinetics of ox-apoA-I amyloid-like aggregate formation was not altered by the presence of curcumin. Moreover, electron microscopy analysis detected no discernable differences in amyloid morphology when ox-apoA-I amyloid-like aggregates were formed in the presence or absence of curcumin. In conclusion, curcumin interacts with apoA-I and alters the structure of ox-apoA-I amyloid-like aggregates yet does not diminish the propensity of ox-apoA-I to form aggregates.« less

High-beta spherical tokamak startup in TS-4 merging experiment by use of toroidal field ramp-up

NASA Astrophysics Data System (ADS)

Kaminou, Yasuhiro; , Toru, II; Kato, Joji; Inomoto, Michiaki; Ono, Yasushi; TS Group Team; National InstituteFusion Science Collaboration

2014-10-01

We demonstrated the formation method of an ultrahigh-beta spherical tokamak by use of a field-reversed configuration and a spheromak in TS-4 device (R ~ 0.5 m, A ~ 1.5, Ip ~ 30-100 kA, B ~ 100 mT). This method is composed of the following steps: 1. Two spheromaks are merged together and a high-beta spheromak or FRC is formed by reconnection heating. 2. External toroidal magnetic field is added (current rising time ~50 μs), and spherical tokamak-like configuration is formed. In this way, the ultrahigh-beta ST is formed. The ultrahigh-beta ST formed by FRC has a diamagnetic toroidal field, and it presumed to be in a second-stable state for ballooning stability, and the one formed by spheromak has a weak paramagnetic toroidal magnetic field, while a spheormak has a strong paramagnetic toroidal magnetic field. This diamagnetic current derives from inductive electric field by ramping up the external toroidal magnetic field, and the diamagnetic current sustains high thermal pressure of the ultrahigh-beta spherical tokamak. And the beta of the ultrahigh-beta ST formed by FRC reaches about 50%. To sustain the high-beta state, 0.6 MW neutral beam injection and center solenoid coils are installed to the TS-4 device. In the poster, we report the experimental results of ultrahigh-beta spherical tokamak startup and sustainment by NBI and CS current driving experiment.

Considering the formation of hematite spherules on Mars by freezing aqueous hematite nanoparticle suspensions

NASA Astrophysics Data System (ADS)

Sexton, M. R.; Elwood Madden, M. E.; Swindle, A. L.; Hamilton, V. E.; Bickmore, B. R.; Elwood Madden, A. S.

2017-04-01

The enigmatic and unexpected occurrence of coarse crystalline (gray) hematite spherules at Terra Meridiani on Mars in association with deposits of jarosite-rich sediments fueled a variety of hypotheses to explain their origin. In this study, we tested the hypothesis that freezing of aqueous hematite nanoparticle suspensions, possibly produced from low-temperature weathering of jarosite-bearing deposits, could produce coarse-grained hematite aggregate spherules. We synthesized four hematite nanoparticle suspensions with a range of sizes and morphologies and performed freezing experiments. All sizes of hematite nanoparticles rapidly aggregate during freezing. Regardless of the size or shape of the initial starting material, they rapidly collect into aggregates that are then too big to push in front of a stable advancing ice front, leading to incohesive masses of particles, rather than solid spherules. We also explored the effects of "seed" silicates, a matrix of sand grains, various concentrations of NaCl and CaCl2, and varying the freezing temperature on hematite nanoparticle aggregation. However, none of these factors resulted in mm-scale spherical aggregates. By comparing our measured freezing rates with empirical and theoretical values from the literature, we conclude that the spherules on Mars could not have been produced through the freezing of aqueous hematite nanoparticle suspensions; ice crystallization front instability disrupts the aggregation process and prevents the formation of mm-scale continuous aggregates.

Reduction and degradation of amyloid aggregates by a pulsed radio-frequency cold atmospheric plasma jet

NASA Astrophysics Data System (ADS)

Bayliss, D. L.; Walsh, J. L.; Shama, G.; Iza, F.; Kong, M. G.

2009-11-01

Surface-borne amyloid aggregates with mature fibrils are used as a non-infectious prion model to evaluate cold atmospheric plasmas (CAPs) as a prion inactivation strategy. Using a helium-oxygen CAP jet with pulsed radio-frequency (RF) excitation, amyloid aggregates deposited on freshly cleaved mica discs are reduced substantially leaving only a few spherical fragments of sub-micrometer sizes in areas directly treated by the CAP jet. Outside the light-emitting part of the CAP jet, plasma treatment results in a 'skeleton' of much reduced amyloid stacks with clear evidence of fibril fragmentation. Analysis of possible plasma species and the physical configuration of the jet-sample interaction suggests that the skeleton structures observed are unlikely to have arisen as a result of physical forces of detachment, but instead by progressive diffusion of oxidizing plasma species into porous amyloid aggregates. Composition of chemical bonds of this reduced amyloid sample is very different from that of intact amyloid aggregates. These suggest the possibility of on-site degradation by CAP treatment with little possibility of spreading contamination elsewhere , thus offering a new reaction chemistry route to protein infectivity control with desirable implications for the practical implementation of CAP-based sterilization systems.

Physical properties of elongated magnetic particles: magnetization and friction coefficient anisotropies.

PubMed

Vereda, Fernando; de Vicente, Juan; Hidalgo-Alvarez, Roque

2009-06-02

Anisotropy counts: A brief review of the main physical properties of elongated magnetic particles (EMPs) is presented. The most important characteristic of an EMP is the additional contribution of shape anisotropy to the total anisotropy energy of the particle, when compared to spherical magnetic particles. The electron micrograph shows Ni-ferrite microrods fabricated by the authors.We present an overview of the main physical properties of elongated magnetic particles (EMPs), including some of their more relevant properties in suspension. When compared to a spherical magnetic particle, the most important characteristic of an EMP is an additional contribution of shape anisotropy to the total anisotropy energy of the particle. Increasing aspect ratios also lead to an increase in both the critical single-domain size of a magnetic particle and its resistance to thermally activated spontaneous reversal of the magnetization. For single-domain EMPs, magnetization reversal occurs primarily by one of two modes, coherent rotation or curling, the latter being facilitated by larger aspect ratios. When EMPs are used to prepare colloidal suspensions, other physical properties come into play, such as their anisotropic friction coefficient and the consequent enhanced torque they experience in a shear flow, their tendency to align in the direction of an external field, to form less dense sediments and to entangle into more intricate aggregates. From a more practical point of view, EMPs are discussed in connection with two interesting types of magnetic colloids: magnetorheological fluids and suspensions for magnetic hyperthermia. Advances reported in the literature regarding the use of EMPs in these two systems are included. In the final section, we present a summary of the most relevant methods documented in the literature for the fabrication of EMPs, together with a list of the most common ferromagnetic materials that have been synthesized in the form of EMPs.

Spherical nanoindentation stress-strain analysis, Version 1

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

Weaver, Jordan S.; Turner, David; Miller, Calvin

Nanoindentation is a tool that allows the mechanical response of a variety of materials at the nano to micron length scale to be measured. Recent advances in spherical nanoindentation techniques have allowed for a more reliable and meaningful characterization of the mechanical response from nanoindentation experiments in the form on an indentation stress-strain curve. This code base, Spin, is written in MATLAB (The Mathworks, Inc.) and based on the analysis protocols developed by S.R. Kalidindi and S. Pathak [1, 2]. The inputs include the displacement, load, harmonic contact stiffness, harmonic displacement, and harmonic load from spherical nanoindentation tests in themore » form of an Excel (Microsoft) spreadsheet. The outputs include indentation stress-strain curves and indentation properties as well their variance due to the uncertainty of the zero-point correction in the form of MATLAB data (.mat) and figures (.png). [1] S. Pathak, S.R. Kalidindi. Spherical nanoindentation stress–strain curves, Mater. Sci. Eng R-Rep 91 (2015). [2] S.R. Kalidindi, S. Pathak. Determination of the effective zero-point and the extraction of spherical nanoindentation stress-strain curves, Acta Materialia 56 (2008) 3523-3532.« less

Experiment to Form and Characterize a Section of a Spherically Imploding Plasma Liner

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

Hsu, S. C.; Langendorf, S. J.; Yates, K. C.

Here, we describe an experiment to form and characterize a section of a spherically imploding plasma liner by merging six supersonic plasma jets that are launched by newly designed contoured-gap coaxial plasma guns. This experiment is a prelude to forming a fully spherical imploding plasma liner using many dozens of plasma guns, as a standoff driver for plasma-jet-driven magneto-inertial fusion. The objectives of the six-jet experiments are to assess the evolution and scalings of liner Mach number and uniformity, which are important metrics for spherically imploding plasma liners to compress magnetized target plasmas to fusion conditions. Lastly, this article describesmore » the design of the coaxial plasma guns, experimental characterization of the plasma jets, six-jet experimental setup and diagnostics, initial diagnostic data from three- and six-jet experiments, and the high-level objectives of associated numerical modeling.« less

Experiment to Form and Characterize a Section of a Spherically Imploding Plasma Liner

DOE PAGES

Hsu, S. C.; Langendorf, S. J.; Yates, K. C.; ...

2017-12-18

Here, we describe an experiment to form and characterize a section of a spherically imploding plasma liner by merging six supersonic plasma jets that are launched by newly designed contoured-gap coaxial plasma guns. This experiment is a prelude to forming a fully spherical imploding plasma liner using many dozens of plasma guns, as a standoff driver for plasma-jet-driven magneto-inertial fusion. The objectives of the six-jet experiments are to assess the evolution and scalings of liner Mach number and uniformity, which are important metrics for spherically imploding plasma liners to compress magnetized target plasmas to fusion conditions. Lastly, this article describesmore » the design of the coaxial plasma guns, experimental characterization of the plasma jets, six-jet experimental setup and diagnostics, initial diagnostic data from three- and six-jet experiments, and the high-level objectives of associated numerical modeling.« less

Method of Manufacturing a Light Emitting, Photovoltaic or Other Electronic Apparatus and System

NASA Technical Reports Server (NTRS)

Blanchard, Richard A. (Inventor); Fuller, Kirk A. (Inventor); Ray, William Johnstone (Inventor); Shotton, Neil O. (Inventor); Frazier, Donald Odell (Inventor); Lowenthal, Mark D. (Inventor); Lewandowski, Mark Allan (Inventor)

2013-01-01

The present invention provides a method of manufacturing an electronic apparatus, such as a lighting device having light emitting diodes (LEDs) or a power generating device having photovoltaic diodes. The exemplary method includes forming at least one first conductor coupled to a base; coupling a plurality of substantially spherical substrate particles to the at least one first conductor; converting the substrate particles into a plurality of substantially spherical diodes; forming at least one second conductor coupled to the substantially spherical diodes; and depositing or attaching a plurality of substantially spherical lenses suspended in a first polymer. The lenses and the suspending polymer have different indices of refraction. In some embodiments, the lenses and diodes have a ratio of mean diameters or lengths between about 10:1 and 2:1. In various embodiments, the forming, coupling and converting steps are performed by or through a printing process.

OUTWARD MOTION OF POROUS DUST AGGREGATES BY STELLAR RADIATION PRESSURE IN PROTOPLANETARY DISKS

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

Tazaki, Ryo; Nomura, Hideko, E-mail: rtazaki@kusastro.kyoto-u.ac.jp

2015-02-01

We study the dust motion at the surface layer of protoplanetary disks. Dust grains in the surface layer migrate outward owing to angular momentum transport via gas-drag force induced by the stellar radiation pressure. In this study we calculate the mass flux of the outward motion of compact grains and porous dust aggregates by the radiation pressure. The radiation pressure force for porous dust aggregates is calculated using the T-Matrix Method for the Clusters of Spheres. First, we confirm that porous dust aggregates are forced by strong radiation pressure even if they grow to be larger aggregates, in contrast tomore » homogeneous and spherical compact grains, for which radiation pressure efficiency becomes lower when their sizes increase. In addition, we find that the outward mass flux of porous dust aggregates with monomer size of 0.1 μm is larger than that of compact grains by an order of magnitude at the disk radius of 1 AU, when their sizes are several microns. This implies that large compact grains like calcium-aluminum-rich inclusions are hardly transported to the outer region by stellar radiation pressure, whereas porous dust aggregates like chondritic-porous interplanetary dust particles are efficiently transported to the comet formation region. Crystalline silicates are possibly transported in porous dust aggregates by stellar radiation pressure from the inner hot region to the outer cold cometary region in the protosolar nebula.« less

Particle aggregation during receptor-mediated endocytosis

NASA Astrophysics Data System (ADS)

Mao, Sheng; Kosmrlj, Andrej

Receptor-mediated endocytosis of particles is driven by large binding energy between ligands on particles and receptors on a membrane, which compensates for the membrane bending energy and for the cost due to the mixing entropy of receptors. While the receptor-mediated endocytosis of individual particle is well understood, much less is known about the joint entry of multiple particles. Here, we demonstrate that the endocytosis of multiple particles leads to a kinetically driven entropic attraction, which may cause the aggregation of particles observed in experiments. During the endocytosis particles absorb nearby receptors and thus produce regions, which are depleted of receptors. When such depleted regions start overlapping, the corresponding particles experience osmotic-like attractive entropic force. If the attractive force between particles is large enough to overcome the repulsive interaction due to membrane bending, then particles tend to aggregate provided that they are sufficiently close, such that they are not completely engulfed before they come in contact. We discuss the necessary conditions for the aggregation of cylindrical particles during receptor-mediated endocytosis and comment on the generalization to spherical particles.

Glutathione regulation-based dual-functional upconversion sensing-platform for acetylcholinesterase activity and cadmium ions.

PubMed

Fang, Aijin; Chen, Hongyu; Li, Haitao; Liu, Meiling; Zhang, Youyu; Yao, Shouzhuo

2017-01-15

A dual-functional platform for the sensing of acetylcholinesterase (AChE) activity and cadmium ions (Cd 2+ ) was developed based on the fluorescence resonance energy transfer (FRET) between NaYF 4 :Yb,Er upconversion nanoparticles (UCNPs) and gold nanoparticles (AuNPs) via glutathione regulation. The detection mechanism is based on the fact that AuNPs can quench the fluorescence of UCNPs. AChE catalyzes the hydrolysis of acetylthiocholine (ATC) into thiocholine which reacts with AuNPs by S-Au conjunction and results the aggregation of AuNPs and change in fluorescence of UCNPs. Therefore, the AChE activity can be detected through the changes of the color of solution and fluorescence recovery of UCNPs. However, the presence of glutathione (GSH) can protect AuNPs from aggregation and enlarge the inter-particle distance between AuNPs and UCNPs. When Cd 2+ is added into the stable mixture of AuNPs, GSH and AChE/ATC, Cd 2+ could interact with GSH to form a spherical shaped (GSH) 4 Cd complex, which decreases the free GSH on the surface of AuNPs to weaken the stability of AuNPs and lead to the easily aggregation of them in the system. The aggregated-AuNPs are released from the surface of UCNPs, which results in the fluorescence of UCNPs gradually recovered. Under the optimized conditions, the detection limits of AChE activity and Cd 2+ are estimated to be 0.015mU/mL and 0.2µM, respectively. The small molecules regulated dual-functional platform based on UCNPs/AuNPs is a simple, label-free method and can be applied for the turn-on fluorescence detection of AChE activity in human serum and Cd 2+ in real water samples. The present work demonstrates a general strategy for the design of small molecules regulated multifunctional platform and will be expanded for different areas in the future. Copyright © 2016 Elsevier B.V. All rights reserved.

Aggregation of Carbocyanine Dyes in Choline Chloride-Based Deep Eutectic Solvents in the Presence of an Aqueous Base.

PubMed

Pal, Mahi; Yadav, Anita; Pandey, Siddharth

2017-09-26

Deep eutectic solvents (DESs) have shown potential as novel media to support molecular aggregation. The self-aggregation behavior of two common and popular carbocyanine dyes, 5,5',6,6'-tetrachloro-1,1'-diethyl-3,3'-di(4-sulfobutyl)-benzimidazole carbocyanine (TDBC) and 5,5'-dichloro-3,3'-di(3-sulfopropyl)-9-methyl-benzothiacarbo cyanine (DMTC), is investigated within DES-based systems under ambient conditions. Although TDBC is known to form J-aggregates in basic aqueous solution, DMTC forms H-aggregates under similar conditions. The DESs used, glyceline and reline, are composed of salt choline chloride and two vastly different H-bond donors, glycerol and urea, respectively, in 1:2 mol ratios. Both DESs in the presence of base are found to support J-aggregates of TDBC. These fluorescent J-aggregates are characterized by small Stokes' shifts and subnanosecond fluorescence lifetimes. Under similar conditions, DMTC forms fluorescent H-aggregates along with J-aggregates within the two DES-based systems. The addition of cationic surfactant cetyltrimethylammonium bromide (CTAB) below its critical micelle concentration (cmc) to a TDBC solution of aqueous base-added glyceline shows the prominent presence of J-aggregates, and increasing the CTAB concentration to above cmc results in the disruption of J-aggregates and the formation of unprecedented H-aggregates. DMTC exclusively forms H-aggregates within a CTAB solution of aqueous base-added glyceline irrespective of the surfactant concentration. Anionic surfactant, sodium dodecylsulfate (SDS), present below its cmc within aqueous base-added DESs supports J-aggregation by TDBC; for similar SDS addition, DMTC forms H-aggregates within the glyceline-based system whereas both H- and J-aggregates exist within the reline-based system. A comparison of the carbocyanine dye behavior in various aqueous base-added DES systems to that in aqueous basic media reveals contrasting aggregation tendencies and/or efficiencies. Surfactants as additives are demonstrated to control and modulate carbocyanine dye self-aggregation within DES-based media. The unique nature of DESs as alternate media toward affecting cyanine dye aggregation is highlighted.

GENERAL: Kinetic Behaviors of Catalysis-Driven Growth of Three-Species Aggregates on Base of Exchange-Driven Aggregations

NASA Astrophysics Data System (ADS)

Sun, Yun-Fei; Chen, Dan; Lin, Zhen-Quan; Ke, Jian-Hong

2009-06-01

We propose a solvable aggregation model to mimic the evolution of population A, asset B, and the quantifiable resource C in a society. In this system, the population and asset aggregates themselves grow through self-exchanges with the rate kernels K1(k, j) = K1kj and K2(k, j) = K2kj, respectively. The actions of the population and asset aggregations on the aggregation evolution of resource aggregates are described by the population-catalyzed monomer death of resource aggregates and asset-catalyzed monomer birth of resource aggregates with the rate kernels J1(k, j) = J1k and J2(k, j) = J2k, respectively. Meanwhile, the asset and resource aggregates conjunctly catalyze the monomer birth of population aggregates with the rate kernel I1(k, i, j) = I1kiμjη, and population and resource aggregates conjunctly catalyze the monomer birth of asset aggregates with the rate kernel I2(k, i, j) = I2kivjη. The kinetic behaviors of species A, B, and C are investigated by means of the mean-field rate equation approach. The effects of the population-catalyzed death and asset-catalyzed birth on the evolution of resource aggregates based on the self-exchanges of population and asset appear in effective forms. The coefficients of the effective population-catalyzed death and the asset-catalyzed birth are expressed as J1e = J1/K1 and J2e = J2/K2, respectively. The aggregate size distribution of C species is found to be crucially dominated by the competition between the effective death and the effective birth. It satisfies the conventional scaling form, generalized scaling form, and modified scaling form in the cases of J1e < J2e, J1e = J2e, and J1e > J2e, respectively. Meanwhile, we also find the aggregate size distributions of populations and assets both fall into two distinct categories for different parameters μ, ν, and η: (i) When μ = ν = η = 0 and μ = ν = 0, η = 1, the population and asset aggregates obey the generalized scaling forms; and (ii) When μ = ν = 1, η = 0, and μ = ν = η = 1, the population and asset aggregates experience gelation transitions at finite times and the scaling forms break down.

Temperature dependence of aggregated structure of β-carotene by absorption spectral experiment and simulation

NASA Astrophysics Data System (ADS)

Lu, Liping; Wu, Jie; Wei, Liangshu; Wu, Fang

2016-12-01

β-carotene can self-assemble to form J- or H-type aggregate in hydrophilic environments, which is crucial for the proper functioning of biological system. Although several ways controlling the formation of the two types of aggregate in hydrated ethanol have been investigated in recent years, our study provided another way to control whether J- or H- β-carotene was formed and presented a method to investigate the aggregated structure. For this purpose, the aggregates of β-carotene formed at different temperatures were studied by UV-Vis spectra and a computational method based on Frenkel exciton was applied to simulate the absorption spectra to obtain the aggregated structure of the β-carotene. The analysis showed that β-carotene formed weakly coupled H-aggregate at 15 °C in 1:1 ethanol-water solvent, and with the increase of temperature it tended to form J-type of aggregate. The absorption spectral simulation based on one-dimensional Frenkel exciton model revealed that good fit with the experiment was obtained with distance between neighbor molecules r = 0.82 nm, disorder of the system D = 1500 cm- 1 for H-type and r = 1.04 nm, D = 1800 cm- 1 for J-type.

Structure and dynamics in self-organized C60 fullerenes.

PubMed

Patnaik, Archita

2007-01-01

This manuscript on 'structure and dynamics in self-organized C60 fullerenes' has three sections dealing with: (A) pristine C60 aggregate structure and geometry in solvents of varying dielectric constant. Here, using positronium (Ps) as a fundamental probe which maps changes in the local electron density of the microenvironment, the onset concentration for stable C60 aggregate formation and its phase behavior is deduced from the specific interactions of the Ps atom with the surrounding. (B) A novel methanofullerene dyad, based on a hydrophobic (acceptor C60 moiety)-hydrophilic (bridge with benzene and ester functionalities)-hydrophobic (donor didodecyloxybenzene) network is chosen for investigation of characteristic self-assembly it undergoes leading to supramolecular aggregates. The pi-electronic amphiphile, necessitating a critical dielectric constant epsilon > or = 30 in binary THF-water mixtures, dictated the formation of bilayer vesicles as precursors for spherical fractal aggregates upon complete dyad extraction into a more polar water phase. (C) While the molecular orientation is dependent on the packing density, the ordering of the molecular arrangement, indispensable for self-assembly depends on the balance between the structures demanded by inter-molecular and molecule-substrate interactions. The molecular orientation in a monolayer affects the orientation in a multilayer, formed on the monolayer, suggesting the possibility of the latter to act as a template for controlling the structure of the three dimensionally grown self-assembled molecular aggregation. A systematic study on the electronic structure and orientation associated with C60 functionalized aminothiol self-assembled monolayers on Au(111) surface is presented using surface sensitive Ultra-Violet Photoelectron Spectroscopy (UPS) and C-K edge Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy. The results revealed drastic modifications to d-band structure of Au(111) and the electronic structure was found sensitive towards the S-Au interface and the C60 end functional moiety with formation of localized sigma-(S-Au) and sigma(N-C) bonds, respectively. Upon binding C60 to the amine-terminated alkanethiol SAM, a drastically reduced HOMO-LUMO gap of 2.7 eV as compared to a large electronic gap of approximately 8 eV in alkanethiols enables the SAM to be a potential electron transport medium.

Ocean manganese nodules as stromatolite with a fractal like-signature

NASA Astrophysics Data System (ADS)

Akai, Junji; Akiyama, Shigeki; Tsuchiyama, Akira; Akai, Kurumi

Deep-sea manganese (Mn) nodules are problematic in terms of factors such as their characteristic form and genesis. There are many reports of bacterial species from manganese nodules. However, the genesis of these nodules has not been fully confirmed. Samples, mainly from the Clarion Clipperton Fracture zone in the Pacific Ocean, were examined by mineralogical methods and X-ray CT. Thin sections of these samples showed columnar stromatolite structures with rhythmic bands. Mineralized bacteria were observed by SEM and TEM. Surface morphology could be described as having a fractal-like nature. The fractal characteristics of spherical to dome-like forms were fundamentally composed of at least four ranks. The 4th order form corresponds to the stromatolite dome top shapes. Similar granular domain units and porous characteristics in manganese nodules were clearly observed by X-ray CT sections. Mathematical simulation based on fractal models reproduced similar morphological characteristics to the natural samples. So, we arrived at the concluding hypothesis that manganese nodules are aggregated stromatolite with fractal-like characteristics. Furthermore, we discussed the possibility that the nature of the layer manganese oxide minerals as the major component of the nodule and associated Fe-oxyhydroxide minerals may become an absorber/scavenger of strategic heavy metals and also toxic metals in the environments.

Spherical neutron generator

DOEpatents

Leung, Ka-Ngo

2006-11-21

A spherical neutron generator is formed with a small spherical target and a spherical shell RF-driven plasma ion source surrounding the target. A deuterium (or deuterium and tritium) ion plasma is produced by RF excitation in the plasma ion source using an RF antenna. The plasma generation region is a spherical shell between an outer chamber and an inner extraction electrode. A spherical neutron generating target is at the center of the chamber and is biased negatively with respect to the extraction electrode which contains many holes. Ions passing through the holes in the extraction electrode are focused onto the target which produces neutrons by D-D or D-T reactions.

Lysosomal enzyme cathepsin B enhances the aggregate forming activity of exogenous α-synuclein fibrils.

PubMed

Tsujimura, Atsushi; Taguchi, Katsutoshi; Watanabe, Yoshihisa; Tatebe, Harutsugu; Tokuda, Takahiko; Mizuno, Toshiki; Tanaka, Masaki

2015-01-01

The formation of intracellular aggregates containing α-synuclein (α-Syn) is one of the key steps in the progression of Parkinson's disease and dementia with Lewy bodies. Recently, it was reported that pathological α-Syn fibrils can undergo cell-to-cell transmission and form Lewy body-like aggregates. However, little is known about how they form α-Syn aggregates from fibril seeds. Here, we developed an assay to study the process of aggregate formation using fluorescent protein-tagged α-Syn-expressing cells and examined the aggregate forming activity of exogenous α-Syn fibrils. α-Syn fibril-induced formation of intracellular aggregates was suppressed by a cathepsin B specific inhibitor, but not by a cathepsin D inhibitor. α-Syn fibrils pretreated with cathepsin B in vitro enhanced seeding activity in cells. Knockdown of cathepsin B also reduced fibril-induced aggregate formation. Moreover, using LAMP-1 immunocytochemistry and live-cell imaging, we observed that these aggregates initially occurred in the lysosome. They then rapidly grew larger and moved outside the boundary of the lysosome within one day. These results suggest that the lysosomal protease cathepsin B is involved in triggering intracellular aggregate formation by α-Syn fibrils. Copyright © 2015. Published by Elsevier Inc.

Local growth of dust- and ice-mixed aggregates as cometary building blocks in the solar nebula

NASA Astrophysics Data System (ADS)

Lorek, S.; Lacerda, P.; Blum, J.

2018-03-01

Context. Comet formation by gravitational instability requires aggregates that trigger the streaming instability and cluster in pebble-clouds. These aggregates form as mixtures of dust and ice from (sub-)micrometre-sized dust and ice grains via coagulation in the solar nebula. Aim. We investigate the growth of aggregates from (sub-)micrometre-sized dust and ice monomer grains. We are interested in the properties of these aggregates: whether they might trigger the streaming instability, how they compare to pebbles found on comets, and what the implications are for comet formation in collapsing pebble-clouds. Methods: We used Monte Carlo simulations to study the growth of aggregates through coagulation locally in the comet-forming region at 30 au. We used a collision model that can accommodate sticking, bouncing, fragmentation, and porosity of dust- and ice-mixed aggregates. We compared our results to measurements of pebbles on comet 67P/Churyumov-Gerasimenko. Results: We find that aggregate growth becomes limited by radial drift towards the Sun for 1 μm sized monomers and by bouncing collisions for 0.1 μm sized monomers before the aggregates reach a Stokes number that would trigger the streaming instability (Stmin). We argue that in a bouncing-dominated system, aggregates can reach Stmin through compression in bouncing collisions if compression is faster than radial drift. In the comet-forming region ( 30 au), aggregates with Stmin have volume-filling factors of 10-2 and radii of a few millimetres. These sizes are comparable to the sizes of pebbles found on comet 67P/Churyumov-Gerasimenko. The porosity of the aggregates formed in the solar nebula would imply that comets formed in pebble-clouds with masses equivalent to planetesimals of the order of 100 km in diameter.

Effect of aggregation form on bioavailability of zeaxanthin in humans: a randomised cross-over study.

PubMed

Hempel, Judith; Fischer, Anja; Fischer, Monique; Högel, Josef; Bosy-Westphal, Anja; Carle, Reinhold; Schweiggert, Ralf M

2017-11-01

Carotenoid bioavailability from plant and animal food is highly variable depending on numerous factors such as the physical deposition form of carotenoids. As the carotenoid zeaxanthin is believed to play an important role in eye and brain health, we sought to compare the human bioavailability of an H-aggregated with that of a J-aggregated deposition form of zeaxanthin encapsulated into identical formulation matrices. A randomised two-way cross-over study with sixteen participants was designed to compare the post-prandial bioavailability of an H-aggregated zeaxanthin and a J-aggregated zeaxanthin dipalmitate formulation, both delivering 10 mg of free zeaxanthin. Carotenoid levels in TAG-rich lipoprotein fractions were analysed over 9·5 h after test meal consumption. Bioavailability from the J-aggregated formulation (AUC=55·9 nmol h/l) was 23 % higher than from the H-aggregated one (AUC=45·5 nmol h/l), although being only marginally significant (P=0·064). Furthermore, the same formulations were subjected to an internationally recognised in vitro digestion protocol to reveal potential strengths and weaknesses of simulated digestions. In agreement with our human study, liberation of zeaxanthin from the J-aggregated formulation into the simulated duodenal fluids was superior to that from the H-aggregated form. However, micellization rate (bioaccessibility) of the J-aggregated zeaxanthin dipalmitate was lower than that of the H-aggregated zeaxanthin, being contradictory to our in vivo results. An insufficient ester cleavage during simulated digestion was suggested to be the root cause for these observations. In brief, combining our in vitro and in vivo observations, the effect of the different aggregation forms on human bioavailability was lower than expected.

Structural characterization of astaxanthin aggregates as revealed by analysis and simulation of optical spectra

NASA Astrophysics Data System (ADS)

Lu, Liping; Hu, Taoping; Xu, Zhigang

2017-10-01

Carotenoids can self-assemble in hydrated polar solvents to form J- or H-type aggregates, inducing dramatic changes in photophysical properties. Here, we measured absorption and emission spectra of astaxanthin in ethanol-water solution using ultraviolet-visible and fluorescence spectrometers. Two types of aggregates were distinguished in mixed solution at different water contents by absorption spectra. After addition of water, all probed samples immediately formed H-aggregates with maximum blue shift of 31 nm. In addition, J-aggregate was formed in 1:3 ethanol-water solution measured after an hour. Based on Frenkel exciton model, we calculated linear absorption and emission spectra of these aggregates to describe aggregate structures in solution. For astaxanthin, experimental results agreed well with the fitted spectra of H-aggregate models, which consisted of tightly packed stacks of individual molecules, including hexamers, trimers, and dimers. Transition moment of single astaxanthin in ethanol was obtained by Gaussian 09 program package to estimate the distance between molecules in aggregates. Intermolecular distance of astaxanthin aggregates ranges from 0.45 nm to 0.9 nm. Fluorescence analysis showed that between subbands, strong exciton coupling induced rapid relaxation of H-aggregates. This coupling generated larger Stokes shift than monomers and J-aggregates.

Amyloid-beta aggregates formed at polar-nonpolar interfaces differ from amyloid-beta protofibrils produced in aqueous buffers.

PubMed

Nichols, Michael R; Moss, Melissa A; Reed, Dana Kim; Hoh, Jan H; Rosenberry, Terrone L

2005-07-01

The deposition of aggregated amyloid-beta (Abeta) peptides in the brain as senile plaques is a pathological hallmark of Alzheimer's disease (AD). Several lines of evidence indicate that fibrillar and, in particular, soluble aggregates of these 40- and 42-residue peptides are important in the etiology of AD. Recent studies also stress that amyloid aggregates are polymorphic and that a single polypeptide can fold into multiple amyloid conformations. Here we review our recent reports that Abeta(1-40) in vitro can form soluble aggregates with predominant beta-structures that differ in stability and morphology. One class of aggregates involved soluble Abeta protofibrils, prepared by vigorous overnight agitation of monomeric Abeta(1-40) in low ionic strength buffers. These aggregates were quite stable and disaggregated to only a limited extent on dilution. A second class of soluble Abeta aggregates was generated at polar-nonpolar interfaces. Aggregation in a two-phase system of buffer over chloroform occurred more rapidly than in buffer alone. In buffered 2% hexafluoroisopropanol (HFIP), microdroplets of HFIP were formed and the half-time for aggregation was less than 10 minutes. Like Abeta protofibrils, these interfacial aggregates showed increased thioflavin T fluorescence and were rich in beta-structure by circular dichroism. However, electron microscopy and atomic force microscopy revealed very different morphologies. The HFIP aggregates formed initial globular clusters that progressed over several days to soluble fibrous aggregates. When diluted out of HFIP these aggregates initially were very unstable and disaggregated completely within 2 minutes. However, their stability increased as they progressed to fibers. It is important to determine whether similar interfacial Abeta aggregates are produced in vivo.

Variation of the shape and morphological properties of silica and metal oxide powders by electro homogeneous precipitation

DOEpatents

Harris, M.T.; Basaran, O.A.; Sisson, W.G.; Brunson, R.R.

1997-02-18

The present invention provides a method for preparing irreversible linear aggregates (fibrils) of metal oxide powders by utilizing static or pulsed DC electrical fields across a relatively non-conducting liquid solvent in which organometal compounds or silicon alkoxides have been dissolved. The electric field is applied to the relatively non-conducting solution throughout the particle formation and growth process promoting the formation of either linear aggregates (fibrils) or spherical shaped particles as desired. Thus the present invention provides a physical method for altering the size, shape and porosity of precursor hydrous metal oxide or hydrous silicon oxide powders for the development of advanced ceramics with improved strength and insulating capacity. 3 figs.

Cryochemical method for forming spherical metal oxide particles from metal salt solutions

DOEpatents

Tinkle, M.C.

1973-12-01

A method is described of preparing small metal oxide spheres cryochemically utilizing metal salts (e.g., nitrates) that cannot readily be dried and calcined without loss of sphericity of the particles. Such metal salts are cryochemically formed into small spheres, partially or completely converted to an insoluble salt, and dried and calcined. (Official Gazette)

Tuning of peptide assembly through force balance adjustment.

PubMed

Cao, Meiwen; Cao, Changhai; Zhang, Lijuan; Xia, Daohong; Xu, Hai

2013-10-01

Controlled self-assembly of amphiphilic tripeptides into distinct nanostructures is achieved via a controlled design of the molecular architecture. The tripeptide Ac-Phe-Phe-Lys-CONH2 (FFK), hardly soluble in water, forms long amyloid-like tubular structures with the aid of β-sheet hydrogen bonding and aromatic π-π stacking. Substitution of phenylalanine (F) with tyrosine (Y), that is, only a subtle structural variation in adding a hydroxyl group to the phenyl ring, results in great change in molecular self-assembly behavior. When one F is substituted with Y, the resulting molecules of FYK and YFK self-assemble into long thinner fibrils with high propensity for lateral association. When both Fs are substituted with Y, the resulting YYK molecule forms spherical aggregates. Introduction of hydroxyl groups into the molecule modifies aromatic interactions and introduces hydrogen bonding. Moreover, since the driving forces for peptide self-assembly including hydrogen bonding, electrostatic repulsion, and π-π stacking have high interdependence with each other, changes in aromatic interaction induce a Domino effect and cause a shift of force balance to a new state. This leads to significant variations in self-assembly behavior. Copyright © 2013 Elsevier Inc. All rights reserved.

Heat capacity anomaly in a self-aggregating system: Triblock copolymer 17R4 in water

NASA Astrophysics Data System (ADS)

Dumancas, Lorenzo V.; Simpson, David E.; Jacobs, D. T.

2015-05-01

The reverse Pluronic, triblock copolymer 17R4 is formed from poly(propylene oxide) (PPO) and poly(ethylene oxide) (PEO): PPO14 - PEO24 - PPO14, where the number of monomers in each block is denoted by the subscripts. In water, 17R4 has a micellization line marking the transition from a unimer network to self-aggregated spherical micelles which is quite near a cloud point curve above which the system separates into copolymer-rich and copolymer-poor liquid phases. The phase separation has an Ising-like, lower consolute critical point with a well-determined critical temperature and composition. We have measured the heat capacity as a function of temperature using an adiabatic calorimeter for three compositions: (1) the critical composition where the anomaly at the critical point is analyzed, (2) a composition much less than the critical composition with a much smaller spike when the cloud point curve is crossed, and (3) a composition near where the micellization line intersects the cloud point curve that only shows micellization. For the critical composition, the heat capacity anomaly very near the critical point is observed for the first time in a Pluronic/water system and is described well as a second-order phase transition resulting from the copolymer-water interaction. For all compositions, the onset of micellization is clear, but the formation of micelles occurs over a broad range of temperatures and never becomes complete because micelles form differently in each phase above the cloud point curve. The integrated heat capacity gives an enthalpy that is smaller than the standard state enthalpy of micellization given by a van't Hoff plot, a typical result for Pluronic systems.

Ru(II)-based metallosurfactant forming inverted aggregates.

PubMed

Domínguez-Gutiérrez, David; Surtchev, Marko; Eiser, Erika; Elsevier, Cornelis J

2006-02-01

Knowing the advantages of incorporating a transition metal into interfaces, we report on the first inverted aggregates formed using metallosurfactants. The metallosurfactant possesses four long linear tails that account for the shielding of the polar headgroup in apolar solvents. The nature of the so-formed aggregates changes dramatically from inverted vesicles (toluene) to inverted micelles (hexane). The size of the aggregates was determined using dynamic light scattering. Atomic force microscopy allowed us to study the dry structure of the vesicles on a glass surface.

Molecular aggregation of humic substances

USGS Publications Warehouse

Wershaw, R. L.

1999-01-01

Humic substances (HS) form molecular aggregates in solution and on mineral surfaces. Elucidation of the mechanism of formation of these aggregates is important for an understanding of the interactions of HS in soils arid natural waters. The HS are formed mainly by enzymatic depolymerization and oxidation of plant biopolymers. These reactions transform the aromatic and lipid plant components into amphiphilic molecules, that is, molecules that consist of separate hydrophobic (nonpolar) and hydrophilic (polar) parts. The nonpolar parts of the molecules are composed of relatively unaltered segments of plant polymers and the polar parts of carboxylic acid groups. These amphiphiles form membrane-like aggregates on mineral surfaces and micelle-like aggregates in solution. The exterior surfaces of these aggregates are hydrophilic, and the interiors constitute separate hydrophobic liquid-like phases.

Influence of pH and Metal Cations on Aggregative Growth of Non-Slime-forming Strains of Zoogloea ramigera

PubMed Central

Angelbeck, Donald I.; Kirsch, Edwin J.

1969-01-01

Aggregative growth of non-slime-forming strains of Zoogloea ramigera was induced by growing the organisms at a depressed pH. Calcium and magnesium ion was found to reverse aggregative growth of the organisms. Conversely, aggregation was stimulated when the available inorganic cation concentration of the growth medium was lowered by the use of a chelating agent. The aggregative effects of pH depression or cation depletion and the dispersal effects of cation supplementation were observed only during cellular growth. The data suggest that aggregate formation of non-slime-forming strains of Z. ramigera may be related to the calcium or magnesium metabolism of the organisms, or both. Images PMID:4976326

Tensor spherical harmonics theories on the exact nature of the elastic fields of a spherically anisotropic multi-inhomogeneous inclusion

NASA Astrophysics Data System (ADS)

Shodja, H. M.; Khorshidi, A.

2013-04-01

Eshelby's theories on the nature of the disturbance strains due to polynomial eigenstrains inside an isotropic ellipsoidal inclusion, and the form of homogenizing eigenstrains corresponding to remote polynomial loadings in the equivalent inclusion method (EIM) are not valid for spherically anisotropic inclusions and inhomogeneities. Materials with spherically anisotropic behavior are frequently encountered in nature, for example, some graphite particles or polyethylene spherulites. Moreover, multi-inclusions/inhomogeneities/inhomogeneous inclusions have abundant engineering and scientific applications and their exact theoretical treatment would be of great value. The present work is devoted to the development of a mathematical framework for the exact treatment of a spherical multi-inhomogeneous inclusion with spherically anisotropic constituents embedded in an unbounded isotropic matrix. The formulations herein are based on tensor spherical harmonics having orthogonality and completeness properties. For polynomial eigenstrain field and remote applied loading, several theorems on the exact closed-form expressions of the elastic fields associated with the matrix and all the phases of the inhomogeneous inclusion are stated and proved. Several classes of impotent eigenstrain fields associated to a generally anisotropic inclusion as well as isotropic and spherically anisotropic multi-inclusions are also introduced. The presented theories are useful for obtaining highly accurate solutions of desired accuracy when the constituent phases of the multi-inhomogeneous inclusion are made of functionally graded materials (FGMs).

Eshelby's problem of a spherical inclusion eccentrically embedded in a finite spherical body

PubMed Central

He, Q.-C.

2017-01-01

Resorting to the superposition principle, the solution of Eshelby's problem of a spherical inclusion located eccentrically inside a finite spherical domain is obtained in two steps: (i) the solution to the problem of a spherical inclusion in an infinite space; (ii) the solution to the auxiliary problem of the corresponding finite spherical domain subjected to appropriate boundary conditions. Moreover, a set of functions called the sectional and harmonic deviators are proposed and developed to work out the auxiliary solution in a series form, including the displacement and Eshelby tensor fields. The analytical solutions are explicitly obtained and illustrated when the geometric and physical parameters and the boundary condition are specified. PMID:28293141

Preparation of SiO2/(PMMA/Fe3O4) from monolayer linolenic acid modified Fe3O4 nanoparticles via miniemulsion polymerization.

PubMed

He, Lei; Li, Zhiyang; Fu, Jing; Deng, Yan; He, Nongyue; Wang, Zhifei; Wang, Hua; Shi, Zhiyang; Wang, Zunliang

2009-10-01

SiO2/(PMMA/Fe3O4) composite particles were prepared from linolenic acid (LA) instead of oleic acid (OA) modified Fe3O4 nanoparticles by miniemulsion polymerization. LA has three unsaturated double bonds with which it can polymerizate more easily than OA. And coating Fe3O4 with polymethyl methacrylate (PMMA) polymer beforehand can prevent magnetic nanoparticles from the aggregation that usually comes from the increasing of ionic strength during the hydrolyzation of tetraethoxysilane (TEOS) by the steric hindrance. Finally, the resulting PMMA/Fe3O4 nanoparticles were coated with silica, forming SiO2/(PMMA/Fe3O4) core-shell structure particles. The sizes of nanoparticles with core-shell structure were in the range from 300 to 600 nm. The nanoparticles were spherical particles and had consistent size. The result of magnetic measurement showed that the composite particles had superparamagnetic property.

Poorly Lytic Bacteriophage from Dactylosporangium thailandensis (Actinomycetales)

PubMed Central

Higgins, M. L.; Lechevalier, Mary P.

1969-01-01

Dactylosporangiophage A1 has a polygonal head (75 nm) with spherical capsomeres (3 nm) and a noncontractile tail (200 by 10 nm) with cross-striations which is terminated with at least three prongs which are used for attachment. It contains double-stranded deoxyribonucleic acid and produces very little lysis. Intracellular phage multiplication leads to the formation of crystalline aggregates of apparently complete virions. Plaques are formed only on certain substrains of Dactylosporangium thailandensis L1 and are always small (0.5 mm or less). They are clear on some substrains and turbid on others. Formation of plaques occurs only on one medium, Czapek agar with 0.2 to 0.4% yeast extract, 0.2% peptone, or a defined mixture of amino acids. Over 100 strains of bacteria, mainly actinomycetes, were screened in a futile attempt to find an indicator strain which is not a substrain of L1. The Dactylosporangium-phage system studied is considered to be a semiresistant carrier state. Images PMID:5774140

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

Shang Yazhuo; Hu Jun; Liu Honglai, E-mail: yazhuoshang@ecust.edu.c

Novel large-scale hollow ZnO spherical shells were synthesized by ionic liquids assisted hydrothermal oxidization of pure zinc powder without any catalyst at a relatively low temperature of 160 deg. C. X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX) and scanning electron microscopy (SEM) patterns show that the shells are composed of ZnO and the structure of the shells is very unique. Textured flower-like ZnO consisting of ZnO rods is grown on the outer surfaces of shells forming a triple assembly. Room-temperature photoluminescence spectra of the oxidized material show a sharp peak at 379 nm and a wider broad peak centeredmore » at 498 nm. The possible growth mechanism of the triple assembly of ZnO is discussed in detail. - Graphical abstract: A proposed growth mechanism of large scale hollow ZnO. Bubbles provide the aggregation center for ionic liquids that leads to the formation of hollow Zn particle-dotted shells, buoyancy promotes shells to go upward, the breach occurs when shells are subjected to overpressure.« less

Charge-conversional poly(amino acid)s derivatives as a drug delivery carrier in response to the tumor environment.

PubMed

Yoon, Se Rim; Yang, Hee-Man; Park, Chan Woo; Lim, Sujin; Chung, Bong Hyun; Kim, Jong-Duk

2012-08-01

A charge-converting and pH-dependent nanocarrier was achieved by conjugating 2,3-dimethylmaleic anhydride (DMMA) to the amino group of an octadecyl grafted poly (2-hydroxyethyl aspartamide) (PHEA-g-C(18)-NH(2)) backbone, thereby forming a spherical micelle. PHEA, a poly(amino acid)s derivative, was derived from poly(succinimide), which is biocompatible and biodegradable. DMMA, a detachable component at the tumor site, was added, preventing aggregation with negative blood serum and enhancing the nanocarrier's cellular uptake. The polymeric micelle was comprehensively characterized and doxorubicin was encapsulated successively. The cellular uptake and anticancer therapeutic effect were evaluated by flow cytometry, confocal laser scanning microscopy, and a MTT assay. The properties of the nanocarrier can further be exploited to develop an early detection module for cancer. The present work is also expected to advance the study of designing smart carriers for drug and gene delivery. Copyright © 2012 Wiley Periodicals, Inc.

Synthesis of size-controlled acid-resistant hybrid calcium carbonate microparticles as templates for fabricating "micelles-enhanced" polyelectrolyte capsules by the LBL technique.

PubMed

Li, Xiaodong; Hu, Qiaoling; Yue, Linhai; Shen, Jiacong

2006-07-24

Size-controlled, low-dispersed calcium carbonate microparticles were synthesized in the presence of the amphiphilic block copolymer polystyrene-b-poly(acrylic acid) (PS-b-PAA) by modulating the concentration of block copolymer in the reactive system. This type of hybrid microparticles have acid-resistant properties. By investigating the aggregation behaviors of PS-b-PAA micelles by transmission electron microscopy (TEM), the mechanism of hybrid calcium carbonate formation illustrated that the block copolymer served not only as "pseudonuclei" for the growth of calcium carbonate nanocrystals, but also forms the supramicelle congeries, a spherical framework, as templates for calcium carbonate nanocrystal growth into hybrid CaCO(3) particles. Moreover, this pilot study shows that the hybrid microparticle is a novel candidate as a template for fabricating multilayer polyelectrolyte capsules, in which the block copolymer is retained within the capsule interior after core removal under soft conditions. This not only facilitates the encapsulation of special materials, but also provides "micelles-enhanced" polyelectrolyte capsules.

Complex patchy colloids shaped from deformable seed particles through capillary interactions.

PubMed

Meester, V; Kraft, D J

2018-02-14

We investigate the mechanisms underlying the reconfiguration of random aggregates of spheres through capillary interactions, the so-called "colloidal recycling" method, to fabricate a wide variety of patchy particles. We explore the influence of capillary forces on clusters of deformable seed particles by systematically varying the crosslink density of the spherical seeds. Spheres with a poorly crosslinked polymer network strongly deform due to capillary forces and merge into large spheres. With increasing crosslink density and therefore rigidity, the shape of the spheres is increasingly preserved during reconfiguration, yielding patchy particles of well-defined shape for up to five spheres. In particular, we find that the aspect ratio between the length and width of dumbbells, L/W, increases with the crosslink density (cd) as L/W = B - A·exp(-cd/C). For clusters consisting of more than five spheres, the particle deformability furthermore determines the patch arrangement of the resulting particles. The reconfiguration pathway of clusters of six densely or poorly crosslinked seeds leads to octahedral and polytetrahedral shaped patchy particles, respectively. For seven particles several geometries were obtained with a preference for pentagonal dipyramids by the rigid spheres, while the soft spheres do rarely arrive in these structures. Even larger clusters of over 15 particles form non-uniform often aspherical shapes. We discuss that the reconfiguration pathway is largely influenced by confinement and geometric constraints. The key factor which dominates during reconfiguration depends on the deformability of the spherical seed particles.

The effects of glutamine/asparagine content on aggregation and heterologous prion induction by yeast prion-like domains.

PubMed

Shattuck, Jenifer E; Waechter, Aubrey C; Ross, Eric D

2017-07-04

Prion-like domains are low complexity, intrinsically disordered domains that compositionally resemble yeast prion domains. Many prion-like domains are involved in the formation of either functional or pathogenic protein aggregates. These aggregates range from highly dynamic liquid droplets to highly ordered detergent-insoluble amyloid-like aggregates. To better understand the amino acid sequence features that promote conversion to stable, detergent-insoluble aggregates, we used the prediction algorithm PAPA to identify predicted aggregation-prone prion-like domains with a range of compositions. While almost all of the predicted aggregation-prone domains formed foci when expressed in cells, the ability to form the detergent-insoluble aggregates was highly correlated with glutamine/asparagine (Q/N) content, suggesting that high Q/N content may specifically promote conversion to the amyloid state in vivo. We then used this data set to examine cross-seeding between prion-like proteins. The prion protein Sup35 requires the presence of a second prion, [PIN + ], to efficiently form prions, but this requirement can be circumvented by the expression of various Q/N-rich protein fragments. Interestingly, almost all of the Q/N-rich domains that formed SDS-insoluble aggregates were able to promote prion formation by Sup35, highlighting the highly promiscuous nature of these interactions.

Degradation of experimental composite materials and in vitro wear simulation

NASA Astrophysics Data System (ADS)

Givan, Daniel Allen

2001-12-01

The material, mechanical, and clinical aspects of surface degradation of resin composite dental restorative materials by in vitro wear simulation continues to be an area of active research. To investigate wear mechanisms, a series of experimental resin composites with variable and controlled filler particle shape and loading were studied by in vitro wear simulation. The current investigation utilized a simulation that isolated the wear environment, entrapped high and low modulus debris, and evaluated the process including machine and fluid flow dynamics. The degradation was significantly affected by filler particle shape and less by particle loading. The spherical particle composites demonstrated wear loss profiles suggesting an optimized filler loading may exist. This was also demonstrated by the trends in the mechanical properties. Very little difference in magnitude was noted for the wear of irregular particle composites as a function of particulate size; and as a group they were more wear resistant than spherical particle composites. This was the result of different mechanisms of wear that were correlated with the three-dimensional particle shape. The abrasive effects of the aggregate particles and the polymeric stabilization of the irregular shape versus the destabilization and "plucking" of the spherical particles resulted in an unprotected matrix that accounted for significantly greater wear of spherical composite. A model and analysis was developed to explain the events associated with the progressive material wear loss. The initial phase was explained by fatigue-assisted microcracking and loss of material segments in a zone of high stress immediately beneath a point of high stress contact. The early phase was characterized by the development of a small facet primarily by fatigue-assisted microcracking. Although the translation effects were minimal, some three-body and initial two-body wear events were also present. In the late phases, the abrasive effects of the debris aggregate predominated the wear process. The non-linear rate of wear loss was accelerated as the facet deepened. Physical effects, such as thermal fatigue, and chemical effects were less important but contributed to the degradation process. This study provides new insight into the role(s) of high modulus third body debris in the wear of dental composites.

Re-examination of the Possibility of Haze in Pluto's Atmosphere Based on Multi-Wavelength Observations of the Pluto Occultation of P131.1.

NASA Astrophysics Data System (ADS)

Thomas-Osip, J. E.; Elliot, J. L.; Clancy, K. B.

2002-12-01

Multi-wavelength observations of the occultation of P131.1 by Pluto (see Elliot et al., this conference) allow for a re-examination of the possibility of the existence of haze in Pluto's atmosphere. Models of the extinction efficiency of haze particles as a function of wavelength are being used investigate the potential for the existence of haze in the 2002 Pluto atmosphere. The existence of a haze layer in Pluto's atmosphere was postulated to explain the abrupt change in slope seen in the light curve of the 1988 stellar occultation by Pluto (Elliot and Young 1992, AJ, 103, 991). An alternative explanation (Hubbard et al. 1990, Icarus, 84, 1) includes a steep thermal gradient near the surface instead of, or in addition to, a haze layer. Modeling of the growth and sedimentation of photo-chemically produced spherical aerosols (Stansberry et al. 1989, Geophys. Res. Let., 16, 1221) suggested that an appropriate production rate is not sufficient to produce the opacity necessary to account for change in slope found in the 1988 light curve, if it were due solely to spherical particle haze extinction. Recent studies (see for example, Rannou et al. 1995, Icarus, 188, 355 and Thomas-Osip et al. 2002, Icarus, submitted) have shown that it is likely that photochemical hazes on Titan are aggregate in nature. Fractal aggregate particles can have larger extinction efficiencies than equivalent mass spheres of the same material (Rannou et al. 1999, Planet. Space Sci., 47,385). We are, therefore, also re-examining the effect of a haze with an aggregate morphology on modeling of the 1988 occultation observations. This research has been supported in part by NSF Grant AST-0073447 and NASA Grant NAG5-10444.

Studies of anti-fibrillogenic activity of phthalocyanines of zirconium containing out-of-plane ligands.

PubMed

Kovalska, Vladyslava; Losytskyy, Mykhaylo; Chernii, Viktor; Volkova, Kateryna; Tretyakova, Iryna; Cherepanov, Vsevolod; Yarmoluk, Sergiy; Volkov, Sergiy

2012-01-01

Series of phthalocyanines of zirconium containing lysine, citric, nonanoic acid residues and dibenzolylmethane groups as out-of-plane ligands are firstly studied as inhibitors of fibrillogenesis using cyanine-based fluorescent inhibitory assay. It was shown that studied phthalocyanines at concentration of 20μM inhibited aggregation reaction on 38.5-57.6% and inhibitory activity of phthalocyanines depended on the chemical nature of out-of-plane ligand. For the most active compound PcZrLys(2) (zirconium phthalocyanine containing lysine fragment) the efficient inhibitor concentration was estimated to be 37μM. AFM studies have shown that in the presence of PcZrLys(2) the inhibition of fibrils formation and formation of spherical oligomeric aggregates took place. Due to the ability of phthalocyanines to decrease efficiently protein aggregation into the amyloid fibrils, modification of phthalocyanine molecules via out-of-plane substitutions was proposed as approach for design of anti-fibrillogenic agents with required properties. Copyright © 2011. Published by Elsevier Ltd.

Mechanical Dissociation of Platelet Aggregates in Blood Stream

NASA Astrophysics Data System (ADS)

Hoore, Masoud; Fedosov, Dmitry A.; Gompper, Gerhard; Complex; Biological Fluids Group Team

2017-11-01

von Willebrand factor (VWF) and platelet aggregation is a key phenomenon in blood clotting. These aggregates form critically in high shear rates and dissolve reversibly in low shear rates. The emergence of a critical shear rate, beyond which aggregates form and below which they dissolve, has an interesting impact on aggregation in blood flow. As red blood cells (RBCs) migrate to the center of the vessel in blood flow, a RBC free layer (RBC-FL) is left close to the walls into which the platelets and VWFs are pushed back from the bulk flow. This margination process provides maximal VWF-platelet aggregation probability in the RBC-FL. Using mesoscale hydrodynamic simulations of aggregate dynamics in blood flow, it is shown that the aggregates form and grow in RBC-FL wherein shear rate is high for VWF stretching. By growing, the aggregates penetrate to the bulk flow and get under order of magnitude lower shear rates. Consequently, they dissolve and get back into the RBC-FL. This mechanical limitation for aggregates prohibits undesired thrombosis and vessel blockage by aggregates, while letting the VWFs and platelets to aggregate close to the walls where they are actually needed. The support by the DFG Research Unit FOR 1543 SHENC and CPU time Grant by the Julich Supercomputing Center are acknowledged.

Metal concentrations in aggregate interiors, exteriors, whole aggregates, and bulk of Costa Rican soils

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

Wilcke, W.; Kretzschmar, S.; Bundt, M.

1999-10-01

In many temperate soils the preferential weathering and leaching of aggregate surfaces and the nonaggregated material between aggregates depletes geogenic metals. It also shifts metals from strongly to more weakly bound metal forms. Deposited metals are sorbed preferentially on aggregate surfaces and between aggregates. The authors examined whether preferential desilication under tropical climate causes an enrichment in the aggregate exteriors in oxidic forms of metals. They also studied where deposited metals are bound in these soils. Aggregates (2--20 mm) were selected manually from the A horizons of eight Oxisols, six Andisols, two Mollisols, and two Inceptisols in Costa Rica. Allmore » samples were fractionated into interior and exterior portions and treated with a seven-step sequence to extract Al, Cd, Cu, Fe, Mn, Pb, and Zn. Total concentrations of all metals except Zn were higher in the aggregate exteriors than in the interiors. The average Cd and Pb concentrations in easily extractable fractions were significantly higher in the aggregate exteriors. There were no significant differences in metal partitioning between interiors and exteriors except for Pb, which had higher proportions in extractable forms with NH{sub 2}OH {center{underscore}dot} HCl {gt} NH{sub 4} - acetate, pH 6.0 {gt} EDTA in the exteriors. There were few significant differences in metal concentrations and partitioning between bulk soil and whole aggregates. The results may be explained by (i) preferential desilication of the aggregate exteriors and (ii) preferential sorption of deposited heavy metals mainly in easily extractable forms.« less

Light-induced aggregation of microbial exopolymeric substances.

PubMed

Sun, Luni; Xu, Chen; Zhang, Saijin; Lin, Peng; Schwehr, Kathleen A; Quigg, Antonietta; Chiu, Meng-Hsuen; Chin, Wei-Chun; Santschi, Peter H

2017-08-01

Sunlight can inhibit or disrupt the aggregation process of marine colloids via cleavage of high molecular weight compounds into smaller, less stable fragments. In contrast, some biomolecules, such as proteins excreted from bacteria can form aggregates via cross-linking due to photo-oxidation. To examine whether light-induced aggregation can occur in the marine environment, we conducted irradiation experiments on a well-characterized protein-containing exopolymeric substance (EPS) from the marine bacterium Sagitulla stellata. Our results show that after 1 h sunlight irradiation, the turbidity level of soluble EPS was 60% higher than in the dark control. Flow cytometry also confirmed that more particles of larger sized were formed by sunlight. In addition, we determined a higher mass of aggregates collected on filter in the irradiated samples. This suggests light can induce aggregation of this bacterial EPS. Reactive oxygen species hydroxyl radical and peroxide played critical roles in the photo-oxidation process, and salts assisted the aggregation process. The observation that Sagitulla stellata EPS with relatively high protein content promoted aggregation, was in contrast to the case where no significant differences were found in the aggregation of a non-protein containing phytoplankton EPS between the dark and light conditions. This, together with the evidence that protein-to-carbohydrate ratio of aggregates formed under light condition is significantly higher than that formed under dark condition suggest that proteins are likely the important component for aggregate formation. Light-induced aggregation provides new insights into polymer assembly, marine snow formation, and the fate/transport of organic carbon and nitrogen in the ocean. Copyright © 2017 Elsevier Ltd. All rights reserved.

Synthesis and studies of polypeptide materials: Self-assembled block copolypeptide amphiphiles, DNA-condensing block copolypeptides and membrane-interactive random copolypeptides

NASA Astrophysics Data System (ADS)

Wyrsta, Michael Dmytro

A new class of transition metal initiators for the controlled polymerization of alpha-aminoacid-N-carboxyanhydrides (alpha-NCAs), has been developed by Deming et al. This discovery has allowed for the synthesis of well-defined "protein-like" polymers. Using this chemistry we have made distinct block/random copolypeptides for biomedical applications. Drug delivery, gene delivery, and antimicrobial polymers were the focus of our research efforts. The motivation for the synthesis and study of synthetic polypeptide based materials comes from proteins. Natural proteins are able to adopt a staggeringly large amount of uniquely well-defined folded structures. These structures account for the diversity in properties of proteins. As catalysts (enzymes) natural proteins perform some of the most difficult chemistry with ease and precision at ambient pressures and temperatures. They also exhibit incredible structural properties that directly result from formation of complex hierarchical assemblies. Self-assembling block copolymers were synthesized with various compositions and architectures. In general, di- and tri-block amphiphiles were studied for their self-assembling properties. Both spherical and tubular vesicles were found to assemble from di- and tri-block amphiphiles, respectively. In addition to self-assembly, pH responsiveness was engineered into these amphiphiles by the incorporation of basic residues (lysine) into the hydrophobic block. Another form of self-assembly studied was the condensation of DNA using cationic block copolymers. It was found that cationic block copolymers could condense DNA into compact, ordered, water-soluble aggregates on the nanoscale. These aggregates sufficiently protected DNA from nucleases and yet were susceptible to proteases. These studies form the basis of a gene delivery platform. The ease with which NCAs are polymerized renders them completely amenable to parallel synthetic methods. We have employed this technique to discover new antimicrobial polypeptides. The polymers studied were themselves the antimicrobial agent, not a self-assembled aggregate that contained antibiotics. It was found that powerful antibacterial polymers could be readily prepared with simple binary compositions. Antibacterial activity was sensitive to copolymer composition, bacterial cell-wall type, and insensitive to chain length (within reason).

Compression dynamics of quasi-spherical wire arrays with different linear mass profiles

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

Mitrofanov, K. N., E-mail: mitrofan@triniti.ru; Aleksandrov, V. V.; Gritsuk, A. N.

Results of experimental studies of the implosion of quasi-spherical wire (or metalized fiber) arrays are presented. The goal of the experiments was to achieve synchronous three-dimensional compression of the plasma produced in different regions of a quasi-spherical array into its geometrical center. To search for optimal synchronization conditions, quasi-spherical arrays with different initial profiles of the linear mass were used. The following dependences of the linear mass on the poloidal angle were used: m{sub l}(θ) ∝ sin{sup –1}θ and m{sub l}(θ) ∝ sin{sup –2}θ. The compression dynamics of such arrays was compared with that of quasi-spherical arrays without linear massmore » profiling, m{sub l}(θ) = const. To verify the experimental data, the spatiotemporal dynamics of plasma compression in quasi-spherical arrays was studied using various diagnostics. The experiments on three-dimensional implosion of quasi-spherical arrays made it possible to study how the frozen-in magnetic field of the discharge current penetrates into the array. By measuring the magnetic field in the plasma of a quasi-spherical array, information is obtained on the processes of plasma production and formation of plasma flows from the wire/fiber regions with and without an additionally deposited mass. It is found that penetration of the magnetic flux depends on the initial linear mass profile m{sub l}(θ) of the quasi-spherical array. From space-resolved spectral measurements and frame imaging of plasma X-ray emission, information is obtained on the dimensions and shape of the X-ray source formed during the implosion of a quasi-spherical array. The intensity of this source is estimated and compared with that of the Z-pinch formed during the implosion of a cylindrical array.« less

A template-free method for stable CuO hollow microspheres fabricated from a metal organic framework (HKUST-1).

PubMed

Zhang, Suoying; Liu, Hong; Liu, Pengfei; Yang, Zhuhong; Feng, Xin; Huo, Fengwei; Lu, Xiaohua

2015-06-07

Uniform CuO hollow microspheres were successfully achieved from a non-uniform metal organic framework by using a template-free method. The process mechanism has been revealed to be spherical aggregation and Ostwald ripening. When tested in CO oxidation and heat treatment, these assembled microspheres exhibited an excellent catalytic performance and show a much better stability than the inherited hollow structure from MOFs.

Core-shell-corona polymeric micelles as a versatile template for synthesis of inorganic hollow nanospheres.

PubMed

Sasidharan, Manickam; Nakashima, Kenichi

2014-01-21

Hollow, inorganic nanoscale capsules have many applications, from the delivery of encapsulated products for cosmetic and medicinal purposes to use as lightweight composite materials. Early methods for producing inorganic hollow nanospheres using hard templates suffered from low product yield and shell weakness upon template removal. In the past decade, researchers have turned to amphiphilic copolymers to synthesize hollow nanostructures and ordered mesoporous materials. Amphiphilic molecules self-assemble into well-defined nanostructures including spherical micelles. Micelles formed from simple, two-component AB diblock and ABA triblock copolymers, however, have been difficult to work with to construct inorganic hollow nanoparticles, because the corona of the micelle, which serves as the template for the shell, becomes unstable as it absorbs inorganic shell precursors, causing aggregates to form. Newly developed, three-component ABC triblock copolymers may solve this problem. They provide nanoassemblies with more diverse morphological and functional features than AB diblock and ABA triblock copolymers. Micelles formed from ABC triblock copolymers in selective solvents that dissolve only one or two of the blocks provide templates for these improved nanoassemblies. By manipulating individual polymer blocks, one can "encode" additional features at the molecular level. For instance, modifying the functional groups or substitution patterns of the blocks allows better morphological and size control. Insights into polymer self-assembly gained over years of work in our group have set the stage to systematically engineer inorganic spherical hollow nanoparticles using ABC triblock copolymers. In this Account, we report our recent progress in producing diverse, inorganic hollow spherical nanospheres from asymmetric triblock copolymeric micelles with core-shell-corona architecture as templates. We discuss three classes of polymeric micelles-with neutral, cationic, and anionic shell structures-that allow fabrication of a variety of hollow nanoparticles. Importantly, we synthesized all of these particles in water, avoiding use of hazardous organic solvents. We have designed the precursor of the inorganic material to be selectively sorbed into the shell domain, leaving the corona free from the inorganic precursors that would destabilize the micelle. The core, meanwhile, is the template for the formation of the hollow void. By rationally tailoring experimental parameters, we readily and selectively obtained a variety of hollow nanoparticles including silica, hybrid silicas, metal-oxides, metal-carbonates, metal-sulfates, metal-borates, and metal-phosphates. Finally, we highlight the state-of-the-art techniques we used to characterize these nanoparticles, and describe experiments that demonstrate the potential of these hollow particles in drug delivery, and as anode and cathode materials for lithium-ion batteries.

The impact of the form of the Euler equations for radial flow in cylindrical and spherical coordinates on numerical conservation and accuracy

NASA Astrophysics Data System (ADS)

Crittenden, P. E.; Balachandar, S.

2018-07-01

The radial one-dimensional Euler equations are often rewritten in what is known as the geometric source form. The differential operator is identical to the Cartesian case, but source terms result. Since the theory and numerical methods for the Cartesian case are well-developed, they are often applied without modification to cylindrical and spherical geometries. However, numerical conservation is lost. In this article, AUSM^+-up is applied to a numerically conservative (discrete) form of the Euler equations labeled the geometric form, a nearly conservative variation termed the geometric flux form, and the geometric source form. The resulting numerical methods are compared analytically and numerically through three types of test problems: subsonic, smooth, steady-state solutions, Sedov's similarity solution for point or line-source explosions, and shock tube problems. Numerical conservation is analyzed for all three forms in both spherical and cylindrical coordinates. All three forms result in constant enthalpy for steady flows. The spatial truncation errors have essentially the same order of convergence, but the rate constants are superior for the geometric and geometric flux forms for the steady-state solutions. Only the geometric form produces the correct shock location for Sedov's solution, and a direct connection between the errors in the shock locations and energy conservation is found. The shock tube problems are evaluated with respect to feature location using an approximation with a very fine discretization as the benchmark. Extensions to second order appropriate for cylindrical and spherical coordinates are also presented and analyzed numerically. Conclusions are drawn, and recommendations are made. A derivation of the steady-state solution is given in the Appendix.

The impact of the form of the Euler equations for radial flow in cylindrical and spherical coordinates on numerical conservation and accuracy

NASA Astrophysics Data System (ADS)

Crittenden, P. E.; Balachandar, S.

2018-03-01

The radial one-dimensional Euler equations are often rewritten in what is known as the geometric source form. The differential operator is identical to the Cartesian case, but source terms result. Since the theory and numerical methods for the Cartesian case are well-developed, they are often applied without modification to cylindrical and spherical geometries. However, numerical conservation is lost. In this article, AUSM^+ -up is applied to a numerically conservative (discrete) form of the Euler equations labeled the geometric form, a nearly conservative variation termed the geometric flux form, and the geometric source form. The resulting numerical methods are compared analytically and numerically through three types of test problems: subsonic, smooth, steady-state solutions, Sedov's similarity solution for point or line-source explosions, and shock tube problems. Numerical conservation is analyzed for all three forms in both spherical and cylindrical coordinates. All three forms result in constant enthalpy for steady flows. The spatial truncation errors have essentially the same order of convergence, but the rate constants are superior for the geometric and geometric flux forms for the steady-state solutions. Only the geometric form produces the correct shock location for Sedov's solution, and a direct connection between the errors in the shock locations and energy conservation is found. The shock tube problems are evaluated with respect to feature location using an approximation with a very fine discretization as the benchmark. Extensions to second order appropriate for cylindrical and spherical coordinates are also presented and analyzed numerically. Conclusions are drawn, and recommendations are made. A derivation of the steady-state solution is given in the Appendix.

Interactions between ionic liquid surfactant [C12mim]Br and DNA in dilute brine.

PubMed

He, Yunfei; Shang, Yazhuo; Liu, Zhenhai; Shao, Shuang; Liu, Honglai; Hu, Ying

2013-01-01

Interactions between ionic liquid surfactant [C(12)mim]Br and DNA in dilute brine were investigated in terms of various experimental methods and molecular dynamics (MD) simulation. It was shown that the aggregation of [C(12)mim]Br on DNA chains is motivated not only by electrostatic attractions between DNA phosphate groups and [C(12)mim]Br headgroups but also by hydrophobic interactions among [C(12)mim]Br alkyl chains. Isothermal titration calorimetry analysis indicated that the [C(12)mim]Br aggregation in the presence and absence of DNA are both thermodynamically favored driven by enthalpy and entropy. DNA undergoes size transition and conformational change induced by [C(12)mim]Br, and the charges of DNA are neutralized by the added [C(12)mim]Br. Various microstructures were observed such as DNA with loose coil conformation in nature state, necklace-like structures, and compact spherical aggregates. MD simulation showed that the polyelectrolyte collapses upon the addition of oppositely charged surfactants and the aggregation of surfactants around the polyelectrolyte was reaffirmed. The simulation predicted the gradual neutralization of the negatively charged polyelectrolyte by the surfactant, consistent with the experimental results. Copyright © 2012 Elsevier B.V. All rights reserved.

Variation of Soil Aggregation along the Weathering Gradient: Comparison of Grain Size Distribution under Different Disruptive Forces.

PubMed

Wei, Yujie; Wu, Xinliang; Xia, Jinwen; Shen, Xue; Cai, Chongfa

2016-01-01

The formation and stabilization of soil aggregates play a key role in soil functions. To date, few studies have been performed on the variation of soil aggregation with increasing soil weathering degree. Here, soil aggregation and its influencing factors along the weathering gradient were investigated. Six typical zonal soils (derived from similar parent materials) were sampled from temperate to tropical regions. Grain size distribution (GSD) in aggregate fragmentation with increasing disruptive forces (air-dried, water dispersion and chemical dispersion) was determined by laser diffraction particle size analyzer. Different forms of sesquioxides were determined by selective chemical extraction and their contributions to soil aggregation were identified by multiple stepwise regression analysis. The high variability of sesquioxides in different forms appeared with increasing free oxide content (Fed and Ald) from the temperate to tropical soils. The transformation of GSD peak to small size varied with increasing disruptive forces (p<0.05). Although in different weathering degrees, zonal soils showed a similar fragmentation process. Aggregate water stability generally increased with increasing soil weathering (p<0.01), with higher stability in eluvium (A) horizon than in illuvium (B) horizon (p<0.01). Crystalline oxides and amorphous iron oxides (Feo), especially (Fed-Feo) contributed to the formation of air-dried macroaggregates and their stability against slaking (R2 = 55%, p<0.01), while fine particles (<50μm) and Feo (excluding the complex form Fep) played a positive role in the formation of water stable aggregates (R2 = 93%, p<0.01). Additionally, water stable aggregates (including stability, size distribution and specific surface area) were closely related with pH, organic matter, cation exchange capacity (CEC), bulk density (BD), and free oxides (including various forms) (p<0.05). The overall results indicate that soil aggregation conforms to aggregate hierarchy theory to some extent along the weathering gradient and different forms of sesquioxides perform their specific roles in the formation and stabilization of different size aggregates.

Variation of Soil Aggregation along the Weathering Gradient: Comparison of Grain Size Distribution under Different Disruptive Forces

PubMed Central

Wu, Xinliang; Xia, Jinwen; Shen, Xue; Cai, Chongfa

2016-01-01

The formation and stabilization of soil aggregates play a key role in soil functions. To date, few studies have been performed on the variation of soil aggregation with increasing soil weathering degree. Here, soil aggregation and its influencing factors along the weathering gradient were investigated. Six typical zonal soils (derived from similar parent materials) were sampled from temperate to tropical regions. Grain size distribution (GSD) in aggregate fragmentation with increasing disruptive forces (air-dried, water dispersion and chemical dispersion) was determined by laser diffraction particle size analyzer. Different forms of sesquioxides were determined by selective chemical extraction and their contributions to soil aggregation were identified by multiple stepwise regression analysis. The high variability of sesquioxides in different forms appeared with increasing free oxide content (Fed and Ald) from the temperate to tropical soils. The transformation of GSD peak to small size varied with increasing disruptive forces (p<0.05). Although in different weathering degrees, zonal soils showed a similar fragmentation process. Aggregate water stability generally increased with increasing soil weathering (p<0.01), with higher stability in eluvium (A) horizon than in illuvium (B) horizon (p<0.01). Crystalline oxides and amorphous iron oxides (Feo), especially (Fed-Feo) contributed to the formation of air-dried macroaggregates and their stability against slaking (R2 = 55%, p<0.01), while fine particles (<50μm) and Feo (excluding the complex form Fep) played a positive role in the formation of water stable aggregates (R2 = 93%, p<0.01). Additionally, water stable aggregates (including stability, size distribution and specific surface area) were closely related with pH, organic matter, cation exchange capacity (CEC), bulk density (BD), and free oxides (including various forms) (p<0.05). The overall results indicate that soil aggregation conforms to aggregate hierarchy theory to some extent along the weathering gradient and different forms of sesquioxides perform their specific roles in the formation and stabilization of different size aggregates. PMID:27529618

Atomizing apparatus for making polymer and metal powders and whiskers

DOEpatents

Otaigbe, Joshua U.; McAvoy, Jon M.; Anderson, Iver E.; Ting, Jason; Mi, Jia; Terpstra, Robert

2003-03-18

Method for making polymer particulates, such as spherical powder and whiskers, by melting a polymer material under conditions to avoid thermal degradation of the polymer material, atomizing the melt using gas jet means in a manner to form atomized droplets, and cooling the droplets to form polymer particulates, which are collected for further processing. Atomization parameters can be controlled to produce polymer particulates with controlled particle shape, particle size, and particle size distribution. For example, atomization parameters can be controlled to produce spherical polymer powders, polymer whiskers, and combinations of spherical powders and whiskers. Atomizing apparatus also is provided for atoomizing polymer and metallic materials.

Degradable polymeric nanoparticles by aggregation of thermoresponsive polymers and ``click'' chemistry

NASA Astrophysics Data System (ADS)

Dworak, Andrzej; Lipowska, Daria; Szweda, Dawid; Suwinski, Jerzy; Trzebicka, Barbara; Szweda, Roza

2015-10-01

This study describes a novel approach to the preparation of crosslinked polymeric nanoparticles of controlled sizes that can be degraded under basic conditions. For this purpose thermoresponsive copolymers containing azide and alkyne functions were obtained by ATRP of di(ethylene glycol) monomethyl ether methacrylate (D) and 2-aminoethyl methacrylate (A) followed by post polymerization modification. The amino groups of A were reacted with propargyl chloroformate or 2-azido-1,3-dimethylimidazolinium hexafluorophosphate, which led to two types of copolymers. Increasing the temperature of aqueous solutions of the mixed copolymers caused their aggregation into spherical nanoparticles composed of both types of chains. Their dimensions could be controlled by changing the concentration and heating rate of the solutions. Covalent stabilization of aggregated chains was performed by a ``click'' reaction between the azide and alkyne groups. Due to the presence of a carbamate bond the nanoparticles undergo pH dependent degradation under mild basic conditions. The proposed procedure opens a route to new carriers for the controlled release of active species.This study describes a novel approach to the preparation of crosslinked polymeric nanoparticles of controlled sizes that can be degraded under basic conditions. For this purpose thermoresponsive copolymers containing azide and alkyne functions were obtained by ATRP of di(ethylene glycol) monomethyl ether methacrylate (D) and 2-aminoethyl methacrylate (A) followed by post polymerization modification. The amino groups of A were reacted with propargyl chloroformate or 2-azido-1,3-dimethylimidazolinium hexafluorophosphate, which led to two types of copolymers. Increasing the temperature of aqueous solutions of the mixed copolymers caused their aggregation into spherical nanoparticles composed of both types of chains. Their dimensions could be controlled by changing the concentration and heating rate of the solutions. Covalent stabilization of aggregated chains was performed by a ``click'' reaction between the azide and alkyne groups. Due to the presence of a carbamate bond the nanoparticles undergo pH dependent degradation under mild basic conditions. The proposed procedure opens a route to new carriers for the controlled release of active species. Electronic supplementary information (ESI) available: GPC-MALLS chromatograms for P(D-co-A)_1 and P(D-co-A)_2 copolymers, absorbance spectra of P(D-co-A)_1, P(D-co-A)_2, P(D-co-A_Pr) and P(D-co-A_Az) after reaction with ninhydrine. See DOI: 10.1039/c5nr04448k

The influence of polymer architecture on the assembly of poly(ethylene oxide) grafted C60 fullerene clusters in aqueous solution: a molecular dynamics simulation study.

PubMed

Hooper, Justin B; Bedrov, Dmitry; Smith, Grant D

2009-03-28

The effect of polymer architecture on the aggregation behavior of C60 fullerenes tethered with a single chain of poly(ethylene oxide) (PEO) in aqueous solution has been investigated using coarse-grained, implicit solvent molecular dynamics simulations. The PEO-grafted fullerenes were comprised of a single tether of 60 repeat units represented as a linear polymer, a three-arm star (20 repeat units/arm) or a six-arm star (10 repeat units/arm). Additionally, the influence of arm length on self-assembly of the PEO-fullerene conjugates was investigated for the three-arm stars. Self-assembly is driven by favorable fullerene-fullerene and fullerene-PEO interactions. Our simulations reveal that it should be possible to control the size and geometry of the self-assembled fullerene aggregates in water through variation of PEO architecture and PEO molecular weight. We found that aggregate size and shape could be understood qualitatively in terms of the packing parameter concept that has been employed for diblock polymer and surfactant self-assembly. Higher molecular weight PEO (longer arms) and more compact PEO (more arms for the same molecular weight) resulted in greater steric repulsion between fullerenes, engendering greater aggregate surface curvature and hence the formation of smaller, more spherically shaped aggregates. Finally, weak attractive interactions between PEO and the fullerenes were found to play an important role in determining aggregate shape, size and the dynamics of self-assembly.

Models for randomly distributed nanoscopic domains on spherical vesicles

NASA Astrophysics Data System (ADS)

Anghel, Vinicius N. P.; Bolmatov, Dima; Katsaras, John

2018-06-01

The existence of lipid domains in the plasma membrane of biological systems has proven controversial, primarily due to their nanoscopic size—a length scale difficult to interrogate with most commonly used experimental techniques. Scattering techniques have recently proven capable of studying nanoscopic lipid domains populating spherical vesicles. However, the development of analytical methods able of predicting and analyzing domain pair correlations from such experiments has not kept pace. Here, we developed models for the random distribution of monodisperse, circular nanoscopic domains averaged on the surface of a spherical vesicle. Specifically, the models take into account (i) intradomain correlations corresponding to form factors and interdomain correlations corresponding to pair distribution functions, and (ii) the analytical computation of interdomain correlations for cases of two and three domains on a spherical vesicle. In the case of more than three domains, these correlations are treated either by Monte Carlo simulations or by spherical analogs of the Ornstein-Zernike and Percus-Yevick (PY) equations. Importantly, the spherical analog of the PY equation works best in the case of nanoscopic size domains, a length scale that is mostly inaccessible by experimental approaches such as, for example, fluorescent techniques and optical microscopies. The analytical form factors and structure factors of nanoscopic domains populating a spherical vesicle provide a new and important framework for the quantitative analysis of experimental data from commonly studied phase-separated vesicles used in a wide range of biophysical studies.

Measurement of the pore size distribution of limestone aggregates in concrete pavement cores : phase I.

DOT National Transportation Integrated Search

2012-04-01

Freeze-thaw damage is one of the common forms of distress for concrete pavements in Kansas. D-Cracking is a form of : freeze-thaw damage caused by aggregates with poor freeze-thaw durability. It is believed that pores in the aggregates below : 10 m...

Method and apparatus for forming ceramic oxide superconductors with ordered structure

DOEpatents

Nellis, W.J.; Maple, M.B.

1987-12-23

Disclosed are products and processes for making improved magnetic and superconducting articles from anisotropic starting materials by initially reducing the starting materials into a powdered form composed of particles of uniform directional crystal structures, forming a directionally uniform aggregate of particles by exposing the aggregate to a magnetic field of desired magnitude and direction, and then compacting the aggregate into an integral solid body. 2 Figs.

Nanocomposite and method of making thereof

DOEpatents

Tangirala, Ravisubhash; Milliron, Delia J.; Llordes, Anna

2016-03-15

An embodiment of an inorganic nanocomposite includes a nanoparticle phase and a matrix phase. The nanoparticle phase includes nanoparticles that are arranged in a repeating structure. In an embodiment, the nanoparticles have a spherical or pseudo-spherical shape and are incompatible with hydrazine. In another embodiment, the nanoparticles have neither a spherical nor pseudo-spherical shape. The matrix phase lies between the nanoparticles of the nanoparticle phase. An embodiment of a method of making an inorganic nanocomposite of the present invention includes forming a nanoparticle superlattice on a substrate. The nanoparticle superlattice includes nanoparticles. Each nanoparticle has organic ligands attached to a surface of the nanoparticle. The organic ligands separate adjacent nanoparticles within the nanoparticle superlattice. The method also includes forming a solution that includes an inorganic precursor. The nanoparticle superlattice is placed in the solution for a sufficient time for the inorganic precursor to replace the organic ligands.

Mounting Systems for Structural Members, Fastening Assemblies Thereof, and Vibration Isolation Systems Including the Same

NASA Technical Reports Server (NTRS)

Young, Ken (Inventor); Hindle, Timothy (Inventor); Barber, Tim Daniel (Inventor)

2016-01-01

Mounting systems for structural members, fastening assemblies thereof, and vibration isolation systems including the same are provided. Mounting systems comprise a pair of mounting brackets, each clamped against a fastening assembly forming a mounting assembly. Fastening assemblies comprise a spherical rod end comprising a spherical member having a through opening and an integrally threaded shaft, first and second seating members on opposite sides of the spherical member and each having a through opening that is substantially coaxial with the spherical member through opening, and a partially threaded fastener that threadably engages each mounting bracket forming the mounting assembly. Structural members have axial end portions, each releasably coupled to a mounting bracket by the integrally threaded shaft. Axial end portions are threaded in opposite directions for permitting structural member rotation to adjust a length thereof to a substantially zero strain position. Structural members may be vibration isolator struts in vibration isolation systems.

Formation of J-Aggregates of an Anionic Oxacarbocyanine Dye Upon Interaction with Proteins and Polyelectrolytes

NASA Astrophysics Data System (ADS)

Pronkin, P. G.; Tatikolov, A. S.

2017-05-01

J-aggregation of the anionic oxacarbocyanine dye 3,3'-di-(γ-sulfopropyl)-5,5'-diphenyl-9-ethyloxacarbocyanine betaine was studied in aqueous solutions in the presence of proteins (collagens, immunoglobulin G, serum albumins) and polyelectrolytes (polyethyleneimine, polyvinylpyrrolidone). It was found that denaturation of human serum albumin by urea stimulated J-aggregation of the dye. The dye formed two types of J-aggregates in the presence of denatured albumin and polyethyleneimine. J-aggregates formed in the presence of polyethyleneimine rearranged over time.

Stem Cells in Aggregate Form to Enhance Chondrogenesis in Hydrogels

PubMed Central

Sridharan, BanuPriya; Lin, Staphany M.; Hwu, Alexander T.; Laflin, Amy D.; Detamore, Michael S.

2015-01-01

There are a variety of exciting hydrogel technologies being explored for cartilage regenerative medicine. Our overall goal is to explore whether using stem cells in an aggregate form may be advantageous in these applications. 3D stem cell aggregates hold great promise as they may recapitulate the in vivo skeletal tissue condensation, a property that is not typically observed in 2D culture. We considered two different stem cell sources, human umbilical cord Wharton’s jelly cells (hWJCs, currently being used in clinical trials) and rat bone marrow-derived mesenchymal stem cells (rBMSCs). The objective of the current study was to compare the influence of cell phenotype, aggregate size, and aggregate number on chondrogenic differentiation in a generic hydrogel (agarose) platform. Despite being differing cell sources, both rBMSC and hWJC aggregates were consistent in outperforming cell suspension control groups in biosynthesis and chondrogenesis. Higher cell density impacted biosynthesis favorably, and the number of aggregates positively influenced chondrogenesis. Therefore, we recommend that investigators employing hydrogels consider using cells in an aggregate form for enhanced chondrogenic performance. PMID:26719986

Molecular dynamics study of di-CF4 based reverse micelles in supercritical CO2.

PubMed

Liu, Bing; Tang, Xinpeng; Fang, Wenjing; Li, Xiaoqi; Zhang, Jun; Zhang, Zhiliang; Shen, Yue; Yan, Youguo; Sun, Xiaoli; He, Jianying

2016-10-26

Reverse micelles (RMs) in supercritical CO 2 (scCO 2 ) are promising alternatives for organic solvents, especially when both polar and non-polar components are involved. Fluorinated surfactants, particularly double-chain fluorocarbon surfactants, are able to form well-structured RMs in scCO 2 . The inherent self-assembly mechanisms of surfactants in scCO 2 are still subject to discussion. In this study, molecular dynamics simulations are performed to investigate the self-aggregation behavior of di-CF4 based RMs in scCO 2 , and stable and spherical RMs are formed. The dynamics process and the self-assembly structure in the RMs reveal a three-step mechanism to form the RMs, that is, small RMs, rod-like RMs and fusion of the rod-like RMs. Hydrogen-bonds between headgroups and water molecules, and salt bridges linking Na + ions, headgroups and water molecules enhance the interfacial packing efficiency of the surfactant. The results show that di-CF4 molecules have a high surfactant coverage at the RM interface, implying a high CO 2 -philicity. This mainly results from bending of the short chain (C-COO-CH 2 -(CF2) 3 -CF3) due to the flexible carboxyl group. The microscopic insight provided in this study is helpful in understanding surfactant self-assembly phenomena and designing new CO 2 -philic surfactants.

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

Buitrago, C. Francisco; Bolintineanu, Dan; Seitz, Michelle E.

Designing acid- and ion-containing polymers for optimal proton, ion, or water transport would benefit profoundly from predictive models or theories that relate polymer structures with ionomer morphologies. Recently, atomistic molecular dynamics (MD) simulations were performed to study the morphologies of precise poly(ethylene-co-acrylic acid) copolymer and ionomer melts. Here, we present the first direct comparisons between scattering profiles, I(q), calculated from these atomistic MD simulations and experimental X-ray data for 11 materials. This set of precise polymers has spacers of exactly 9, 15, or 21 carbons between acid groups and has been partially neutralized with Li, Na, Cs, or Zn. Inmore » these polymers, the simulations at 120 °C reveal ionic aggregates with a range of morphologies, from compact, isolated aggregates (type 1) to branched, stringy aggregates (type 2) to branched, stringy aggregates that percolate through the simulation box (type 3). Excellent agreement is found between the simulated and experimental scattering peak positions across all polymer types and aggregate morphologies. The shape of the amorphous halo in the simulated I(q) profile is in excellent agreement with experimental I(q). We found that the modified hard-sphere scattering model fits both the simulation and experimental I(q) data for type 1 aggregate morphologies, and the aggregate sizes and separations are in agreement. Given the stringy structure in types 2 and 3, we develop a scattering model based on cylindrical aggregates. Both the spherical and cylindrical scattering models fit I(q) data from the polymers with type 2 and 3 aggregates equally well, and the extracted aggregate radii and inter- and intra-aggregate spacings are in agreement between simulation and experiment. Furthermore, these dimensions are consistent with real-space analyses of the atomistic MD simulations. By combining simulations and experiments, the ionomer scattering peak can be associated with the average distance between branches of type 2 or 3 aggregates. Furthermore, this direct comparison of X-ray scattering data to the atomistic MD simulations is a substantive step toward providing a comprehensive, predictive model for ionomer morphology, gives substantial support for this atomistic MD model, and provides new credibility to the presence of stringy, branched, and percolated ionic aggregates in precise ionomer melts.« less

The choosing of sleeping position in the overnight aggregation by the solitary bees Amegilla florea urens in Iriomote Island of Japan

NASA Astrophysics Data System (ADS)

Yokoi, Tomoyuki; Idogawa, Naoto; Kandori, Ikuo; Nikkeshi, Aoi; Watanabe, Mamoru

2017-04-01

In addition to the process of joining the sleeping aggregation, the choice of sleeping position is an important night-time behaviour of small diurnal insects because of the increased risk for predator attacks as well as bad weather. The aggregation behaviour of the solitary bee Amegilla florea urens was investigated to elucidate the choice of sleeping position on substrates. Male and female constructed single-sex aggregations on hanging leaves during May and June, respectively. Most individuals tended to form aggregations with other individuals while few individuals slept alone. During the aggregation forming, both the number of individuals that tried to join the aggregation and the completion time of aggregation increased with the number of sleeping individuals, whereas the success rate of joining was unaffected. The sleeping positions of subsequent arrivals on the substrates were higher than those of the first arrivals in female aggregations. Therefore, the first female to arrive tended to be located near the bottom of a hanging substrate. Dissecting sleeping females showed that they contained mature oocytes, indicating that sexually mature individuals formed aggregations. In male aggregations, however, we could not find a clear relationship between the position on substrates and the arrival sequence. We suggest that the purpose for sleeping in aggregations might be a dilution effect for nocturnal predation and that the females that finished both nesting and foraging quickly could choose the optimal positions in the aggregation when they arrived on the sleeping substrates.

Self-assembled mesoporous Co and Ni-ferrite spherical clusters consisting of spinel nanocrystals prepared using a template-free approach.

PubMed

Yu, Byong Yong; Kwak, Seung-Yeop

2011-10-21

Based on a self-assembly strategy, spherical mesoporous cobalt and nickel ferrite nanocrystal clusters with a large surface area and narrow size distribution were successfully synthesized for the first time via a template-free solvothermal process in ethylene glycol and subsequent heat treatment. In this work, the mesopores in the ferrite clusters were derived mainly from interior voids between aggregated primary nanoparticles (with crystallite size of less than 7 nm) and disordered particle packing domains. The concentration of sodium acetate is shown herein to play a crucial role in the formation of mesoporous ferrite spherical clusters. These ferrite clusters were characterized in detail using wide-angle X-ray diffraction, thermogravimetric-differential thermal analysis, (57)Fe Mössbauer spectroscopy, X-ray photoelectron spectroscopy, field-emission scanning electron microscopy, standard and high-resolution transmission electron microscopy, and other techniques. The results confirmed the formation of both pure-phase ferrite clusters with highly crystalline spinel structure, uniform size (about 160 nm) and spherical morphology, and worm-like mesopore structures. The BET specific surface areas and mean pore sizes of the mesoporous Co and Ni-ferrite clusters were as high as 160 m(2) g(-1) and 182 m(2) g(-1), and 7.91 nm and 6.87 nm, respectively. A model for the formation of the spherical clusters in our system is proposed on the basis of the results. The magnetic properties of both samples were investigated at 300 K, and it was found that these materials are superparamagnetic. This journal is © The Royal Society of Chemistry 2011

Cataract-associated P23T γD-crystallin retains a native-like fold in amorphous-looking aggregates formed at physiological pH

NASA Astrophysics Data System (ADS)

Boatz, Jennifer C.; Whitley, Matthew J.; Li, Mingyue; Gronenborn, Angela M.; van der Wel, Patrick C. A.

2017-05-01

Cataracts cause vision loss through the large-scale aggregation of eye lens proteins as a result of ageing or congenital mutations. The development of new treatments is hindered by uncertainty about the nature of the aggregates and their mechanism of formation. We describe the structure and morphology of aggregates formed by the P23T human γD-crystallin mutant associated with congenital cataracts. At physiological pH, the protein forms aggregates that look amorphous and disordered by electron microscopy, reminiscent of the reported formation of amorphous deposits by other crystallin mutants. Surprisingly, solid-state NMR reveals that these amorphous deposits have a high degree of structural homogeneity at the atomic level and that the aggregated protein retains a native-like conformation, with no evidence for large-scale misfolding. Non-physiological destabilizing conditions used in many in vitro aggregation studies are shown to yield qualitatively different, highly misfolded amyloid-like fibrils.

Reverse Micelle Based Synthesis of Microporous Materials in Microgravity

NASA Technical Reports Server (NTRS)

Dutta, Prabir K.

1995-01-01

Formation of zincophosphates from zinc and phosphate containing reverse micelles (water droplets in hexane) has been examined. The frameworks formed resemble that made by conventional hydrothermal synthesis. Dynamics of crystal growth are however quite different, and form the main focus of this study. In particular, the formation of zincophosphate with the sodalite framework was examined in detail. The intramicellar pH was found to have a strong influence on crystal growth. Crystals with a cubic morphology were formed directly from the micelles, without an apparent intermediate amorphous phase over a period of four days by a layer-bylayer growth at the intramicellar pH of 7.6. At a pH of 6.8, an amorphous precipitate rapidly sediments in hours. Sodalite was eventually formed from this settled phase via surface diffusion and reconstruction within four days. With a rotating cell, it was possible to minimize sedimentation and crystals were found to grow epitaxially from the spherical, amorphous particles. Intermediate pH's of 7.2 led to formation of aggregated sodalite crystals prior to settling, again without any indication of an intermediate amorphous phase. These diverse pathways were possible due to changes in intramicellar supersaturation conditions by minor changes in pH. In contrast, conventional syntheses in this pH range all proceeded by similar crystallization pathways through an amorphous gel. This study establishes that synthesis of microporous frameworks is not only possible in reverse micellar systems, but they also allow examination of possible crystallization pathways.

Preparation of Hollow Fe2O3 Nanorods and Nanospheres by Nanoscale Kirkendall Diffusion, and Their Electrochemical Properties for Use in Lithium-Ion Batteries.

PubMed

Cho, Jung Sang; Park, Jin-Sung; Kang, Yun Chan

2016-12-13

A novel process for the preparation of aggregate-free metal oxide nanopowders with spherical (0D) and non-spherical (1D) hollow nanostructures was introduced. Carbon nanofibers embedded with iron selenide (FeSe) nanopowders with various nanostructures are prepared via the selenization of electrospun nanofibers. Ostwald ripening occurs during the selenization process, resulting in the formation of a FeSe-C composite nanofiber exhibiting a hierarchical structure. These nanofibers transform into aggregate-free hollow Fe 2 O 3 powders via the complete oxidation of FeSe and combustion of carbon. Indeed, the zero- (0D) and one-dimensional (1D) FeSe nanocrystals transform into the hollow-structured Fe 2 O 3 nanopowders via a nanoscale Kirkendall diffusion process, thus conserving their overall morphology. The discharge capacities for the 1000 th cycle of the hollow-structured Fe 2 O 3 nanopowders obtained from the FeSe-C composite nanofibers prepared at selenization temperatures of 500, 800, and 1000 °C at a current density of 1 A g -1 are 932, 767, and 544 mA h g -1 , respectively; and their capacity retentions from the second cycle are 88, 92, and 78%, respectively. The high structural stabilities of these hollow Fe 2 O 3 nanopowders during repeated lithium insertion/desertion processes result in superior lithium-ion storage performances.

Effect of Microwave Radiation Power on the Size of Aggregates of ZnO NPs Prepared Using Microwave Solvothermal Synthesis

PubMed Central

Chudoba, Tadeusz; Gierlotka, Stanisław; Lojkowski, Witold

2018-01-01

This paper reports the possibility of changing the size of zinc oxide nanoparticles (ZnO NPs) aggregates through a change of synthesis parameters. The effect of the changed power of microwave heating on the properties of ZnO NPs obtained by the microwave solvothermal synthesis from zinc acetate dissolved in ethylene glycol was tested for the first time. It was found that the size of ZnO aggregates ranged from 60 to 120 nm depending on the power of microwave radiation used in the synthesis of ZnO NPs. The increase in the microwave radiation power resulted in the reduction of the total synthesis time with simultaneous preservation of the constant size and shape of single ZnO NPs, which were synthesized at a pressure of 4 bar. All the obtained ZnO NPs samples were composed of homogeneous spherical particles that were single crystals with an average size of 27 ± 3 nm with a developed specific surface area of 40 m2/g and the skeleton density of 5.18 ± 0.03 g/cm3. A model of a mechanism explaining the correlation between the size of aggregates and the power of microwaves was proposed. This method of controlling the average size of ZnO NPs aggregates is presented for the first time and similar investigations are not found in the literature. PMID:29783651

Viscosity scaling in concentrated dispersions and its impact on colloidal aggregation.

PubMed

Nicoud, Lucrèce; Lattuada, Marco; Lazzari, Stefano; Morbidelli, Massimo

2015-10-07

Gaining fundamental knowledge about diffusion in crowded environments is of great relevance in a variety of research fields, including reaction engineering, biology, pharmacy and colloid science. In this work, we determine the effective viscosity experienced by a spherical tracer particle immersed in a concentrated colloidal dispersion by means of Brownian dynamics simulations. We characterize how the effective viscosity increases from the solvent viscosity for small tracer particles to the macroscopic viscosity of the dispersion when large tracer particles are employed. Our results show that the crossover between these two regimes occurs at a tracer particle size comparable to the host particle size. In addition, it is found that data points obtained in various host dispersions collapse on one master curve when the normalized effective viscosity is plotted as a function of the ratio between the tracer particle size and the mean host particle size. In particular, this master curve was obtained by varying the volume fraction, the average size and the polydispersity of the host particle distribution. Finally, we extend these results to determine the size dependent effective viscosity experienced by a fractal cluster in a concentrated colloidal system undergoing aggregation. We include this scaling of the effective viscosity in classical aggregation kernels, and we quantify its impact on the kinetics of aggregate growth as well as on the shape of the aggregate distribution by means of population balance equation calculations.

Simulation and experimental research on spherical dome by 3D laser forming of square feet

NASA Astrophysics Data System (ADS)

Yang, Lijun; Wang, Yang

2007-01-01

Laser forming is a technique of using the energy from a laser beam to modify and adjust the curvature of sheet metals or hard materials. 2-dimensional laser forming can reasonably accurately control bend angles with various materials. To advance this process further for realistic forming applications in a manufacturing industry, it is necessary to consider larger scale controlled 3-dimensional laser forming. However, this is a different situation for 3-dimensional laser forming. The work presented in this paper uses the spider scanning path to form the thin square sheet to spherical dome by laser forming. The explicit dynamic analysis on 3-dimentional laser forming is shown in the article. On the base of temperature gradient mechanism of 2-dimensional laser forming, depending on the geometry and the thermo-physical properties of stainless steel lCrl8Ni9Ti, develop the mechanism of laser forming of thin square sheet to the spherical dome. This paper discusses the interaction between moving laser beam and sheet, the temperature field on the sheet, and the step transition of stress and deformation in laser forming. In order to give the verification on the results of simulation, the correlative experiment has progressed with Lumonics JK7O2H Nd:YAG laser. The results of experiments are in accord with the simulation.

Cholinesterases and cell proliferation in "nonstratified" and "stratified" cell aggregates from chicken retina and tectum.

PubMed

Vollmer, G; Layer, P G

1987-12-01

Dissociated single cells from chicken retina or tectum kept in rotation-mediated cell culture aggregate, proliferate and establish a certain degree of histotypical cell-to-cell relationships ("sorting out"), but these systems never form highly laminated aggregates ("nonstratified" R- and T-aggregates). In contrast, a mixture of retinal plus pigment epithelial cells forms highly "stratified" aggregates ("RPE-aggregates", see Vollmer et al. 1984). The present comparative study of "stratified" and "nonstratified" aggregates enables us to investigate the process of cell proliferation uncoupled from that of tissue stratification. Here we try to relate these two basic neurogenetic processes with patterns of expression of cholinesterases (AChE, BChE) during formation of both types of aggregates. During early aggregate formation, in both "stratified" and "nonstratified" aggregates an increased butyrylcholinesterase activity is observed close to mitotically active cells. Quantitatively both phenomena show their maxima after 2-3 days in culture. In contrast, AChE-expression in all systems increases with incubation time. In nonproliferative areas, in the center of RPE-aggregates, the formation of plexiform layers is characterized initially by weak BChE- and then strong AChE-activity. These areas correspond with the inner (IPL) and outer (OPL) plexiform layers of the retina in vivo. Although by sucrose gradient centrifugation we find that the 6S- and the fiber-associated 11S-molecules of AChE are present in all types of aggregates, during the culture period the ratio of 11S/6S-forms increases only in RPE-aggregates, which again indicates the advanced degree of differentiation within these aggregates.(ABSTRACT TRUNCATED AT 250 WORDS)

Increase in the energy density of the pinch plasma in 3D implosion of quasi-spherical wire arrays

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

Aleksandrov, V. V., E-mail: alexvv@triniti.ru; Gasilov, V. A.; Grabovski, E. V.

Results are presented from experimental studies of the characteristics of the soft X-ray (SXR) source formed in the implosion of quasi-spherical arrays made of tungsten wires and metalized kapron fibers. The experiments were carried out at the Angara-5-1 facility at currents of up to 3 MA. Analysis of the spatial distribution of hard X-ray emission with photon energies above 20 keV in the pinch images taken during the implosion of quasi-spherical tungsten wire arrays (QTWAs) showed that a compact quasi-spherical plasma object symmetric with respect to the array axis formed in the central region of the array. Using a diffractionmore » grazing incidence spectrograph, spectra of SXR emission with wavelengths of 20–400 Å from the central, axial, and peripheral regions of the emission source were measured with spatial resolutions along the array radius and height in the implosion of QTWAs. It is shown that the emission spectra of the SXR sources formed under the implosion of quasi-spherical and cylindrical tungsten wire arrays at currents of up to 3 MA have a maximum in the wavelength range of 50–150 Å. It is found that, during the implosion of a QTWA with a profiled linear mass, a redistribution of energy in the emission spectrum takes place, which indicates that, during 3D implosion, the energy of longitudinal motion of the array material additionally contributes to the radiation energy. It is also found that, at close masses of the arrays and close values of the current in the range of 2.4{sup −3} MA, the average energy density in the emission source formed during the implosion of a quasi-spherical wire array is larger by a factor of 7 than in the source formed during the implosion of a cylindrical wire array. The experimental data were compared with results of 3D simulations of plasma dynamics and radiation generation during the implosion of quasi-spherical wire arrays with a profiled mass by using the MARPLE-3D radiative magnetohydrodynamic code, developed at the Keldysh Institute of Applied Mathematics, Russian Academy of Sciences.« less

Method of making polymer powders and whiskers as well as particulate products of the method and atomizing apparatus

DOEpatents

Otaigbe, Joshua U.; McAvoy, Jon M.; Anderson, Iver E.; Ting, Jason; Mi, Jia; Terpstra, Robert

2001-01-09

Method for making polymer particulates, such as spherical powder and whiskers, by melting a polymer material under conditions to avoid thermal degradation of the polymer material, atomizing the melt using gas jet means in a manner to form atomized droplets, and cooling the droplets to form polymer particulates, which are collected for further processing. Atomization parameters can be controlled to produce polymer particulates with controlled particle shape, particle size, and particle size distribution. For example, atomization parameters can be controlled to produce spherical polymer powders, polymer whiskers, and combinations of spherical powders and whiskers. Atomizing apparatus also is provided for atoomizing polymer and metallic materials.

Hollow spherical rotors fabricated by electroplating

NASA Technical Reports Server (NTRS)

Avery, H. W.; Conroy, T. F.

1966-01-01

Equatorial bands are fabricated to provide a locating fit for the hemispheres of hollow spherical rotors which are then jointed by electroplating. Several nonmagnetic materials may be used to form the joint, such as aluminum, copper, iron, gold, plantinum, and zinc.

Non-spherical Lobate Chondrules in CO3.0 Y-81020: General Implications for the Formation of Low-FeO Porphyritic Chondrules in CO Chondrites

NASA Technical Reports Server (NTRS)

Rubin, Alan E.; Wasson, John T.

2006-01-01

Non-spherical chondrules (arbitrarily defined as having aspect ratios greater than or equal to 1.20) in CO3.0 chondrites comprise multi-lobate, distended, and highly irregular objects with rounded margins; they constitute approx. 70% of the type-I (low-FeO) porphyritic chondrules in Y-81020, approx. 75% of such chondrules in ALHA77307, and approx. 60% of those in Colony. Although the proportion of non-spherical type-I chondrules in LL3.0 Semarkona is comparable (approx. 60%), multi-lobate OC porphyritic chondrules (with lobe heights equivalent to a significant fraction of the mean chondrule diameter) are rare. If the non-spherical type-I chondrules in CO chondrites had formed from totally molten droplets, calculations indicate that they would have collapsed into spheres within approx. 10(exp -3) s, too little time for their 20-micrometer-size olivine phenocrysts to have grown from the melt. These olivine grains must therefore be relicts from an earlier chondrule generation; the final heating episode experienced by the non-spherical chondrules involved only minor amounts of melting and crystallization. The immediate precursors of the individual non-spherical chondrules may have been irregularly shaped chondrule fragments whose fracture surfaces were rounded during melting. Because non-spherical chondrules and circular chondrules form a continuum in shape and have similar grain sizes, mineral and mesostasis compositions, and modal abundances of non-opaque phases, they must have formed by related processes. We conclude that a large majority of low-FeO chondrules in CO3 chondrites experienced a late, low-degree melting event. Previous studies have shown that essentially all type-II (high-FeO) porphyritic chondrules in Y-81020 formed by repeated episodes of low-degree melting. It thus appears that the type-I and type-II porphyritic chondrules in Y-81020 (and, presumably, all CO3 chondrites) experienced analogous formation histories. Because these two types constitute approx. 95% of all CO chondrules, it is clear that chondrule recycling was the rule in the CO chondrule-formation region and that most melting events produced only low degrees of melting. The rarity of significantly non-spherical, multi-lobate chondrules in Semarkona may reflect more-intense heating of chondrule precursors in the ordinary-chondrite region of the solar nebula.

Coacervation and aggregate transitions of a cationic ammonium gemini surfactant with sodium benzoate in aqueous solution.

PubMed

Wang, Ruijuan; Tian, Maozhang; Wang, Yilin

2014-03-21

Coacervation in an aqueous solution of cationic ammonium gemini surfactant hexamethylene-1,6-bis(dodecyldimethylammonium bromide) (C12C6C12Br2) with sodium benzoate (NaBz) has been investigated at 25 °C by turbidity titration, light microscopy, dynamic light scattering, cryogenic temperature transmission electron microscopy (Cryo-TEM), scanning electron microscopy (SEM), isothermal titration calorimetry, ζ potential and (1)H NMR measurements. There is a critical NaBz concentration of 0.10 M, only above which coacervation can take place. However, if the NaBz concentration is too large, coacervation also becomes difficult. Coacervation takes place at a very low concentration of C12C6C12Br2 and exists in a very wide concentration region of C12C6C12Br2. The phase behavior in the NaBz concentration from 0.15 to 0.50 M includes spherical micelles, threadlike micelles, coacervation, and precipitation. With increasing NaBz concentration, the phase boundaries of coacervation shift to higher C12C6C12Br2 concentration. Moreover, the C12C6C12Br2-NaBz aggregates in the coacervate are found to be close to charge neutralized. The Cryo-TEM and SEM images of the coacervate shows a layer-layer stacking structure consisting of a three-dimensional network formed by the assembly of threadlike micelles. Long, dense and almost uncharged threadlike micelles are the precursors of coacervation in the system.

Pore shape of honeycomb-patterned films: modulation and interfacial behavior.

PubMed

Wan, Ling-Shu; Ke, Bei-Bei; Zhang, Jing; Xu, Zhi-Kang

2012-01-12

The control of the pore size of honeycomb-patterned films has been more or less involved in most work on the topic of breath figures. Modulation of the pore shape was largely ignored, although it is important to applications in replica molding, filtration, particle assembly, and cell culture. This article reports a tunable pore shape for patterned films prepared from commercially available polystyrene (PS). We investigated the effects of solvents including tetrahydrofuran (THF) and chloroform (CF) and hydrophilic additives including poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA), poly(ethylene glycol) (PEG), and poly(N-vinyl pyrrolidone) (PVP). Water droplets on/in the polymer solutions were observed and analyzed for simulating the formation and stabilization of breath figures. Interfacial tensions of the studied systems were measured and considered as a main factor to modulate the pore shape. Results indicate that the pores gradually change from near-spherical to ellipsoidal with the increase of additive content when using CF as the solvent; however, only ellipsoidal pores are formed from the THF solution. It is demonstrated that the aggregation of the additives at the water/polymer solution interface is more efficient in the THF solution than that in the CF solution. This aggregation decreases the interfacial tension, stabilizes the condensed water droplets, and shapes the pores of the films. The results may facilitate our understanding of the dynamic breath figure process and provide a new pathway to prepare patterned films with different pore structures.

Density- and wavefunction-normalized Cartesian spherical harmonics for l ≤ 20

DOE PAGES

Michael, J. Robert; Volkov, Anatoliy

2015-03-01

The widely used pseudoatom formalism in experimental X-ray charge-density studies makes use of real spherical harmonics when describing the angular component of aspherical deformations of the atomic electron density in molecules and crystals. The analytical form of the density-normalized Cartesian spherical harmonic functions for up to l ≤ 7 and the corresponding normalization coefficients were reported previously by Paturle & Coppens. It was shown that the analytical form for normalization coefficients is available primarily forl ≤ 4. Only in very special cases it is possible to derive an analytical representation of the normalization coefficients for 4 < l ≤ 7.more » In most cases for l > 4 the density normalization coefficients were calculated numerically to within seven significant figures. In this study we review the literature on the density-normalized spherical harmonics, clarify the existing notations, use the Paturle–Coppens method in the Wolfram Mathematicasoftware to derive the Cartesian spherical harmonics for l ≤ 20 and determine the density normalization coefficients to 35 significant figures, and computer-generate a Fortran90 code. The article primarily targets researchers who work in the field of experimental X-ray electron density, but may be of some use to all who are interested in Cartesian spherical harmonics.« less

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

Levin, Johannes; German Center for Neurodegenerative Diseases – DZNE, Site Munich, Feodor-Lynen-Str. 17, 81377 Munich; Hillmer, Andreas S.

Synucleinopathies such as dementia with Lewy bodies or Parkinson’s disease are characterized by intracellular deposition of pathologically aggregated α-synuclein. The details of the molecular pathogenesis of PD and especially the conditions that lead to intracellular aggregation of α-synuclein and the role of these aggregates in cell death remain unknown. In cell free in vitro systems considerable knowledge about the aggregation processes has been gathered. In comparison, the knowledge about these aggregation processes in cells is far behind. In cells α-synuclein aggregates can be toxic. However, the crucial particle species responsible for decisive steps in pathogenesis such as seeding a continuing aggregationmore » process and triggering cell death remain to be identified. In order to understand the complex nature of intracellular α-synuclein aggregate formation, we analyzed fluorescent particles formed by venus and α-synuclein-venus fusion proteins and α-synuclein-hemi-venus fusion proteins derived from gently lyzed cells. With these techniques we were able to identify and characterize α-synuclein oligomers formed in cells. Especially the use of α-synuclein-hemi-venus fusion proteins enabled us to identify very small α-synuclein oligomers with high sensitivity. Furthermore, we were able to study the molecular effect of heat shock protein 70, which is known to inhibit α-synuclein aggregation in cells. Heat shock protein 70 does not only influence the size of α-synuclein oligomers, but also their quantity. In summary, this approach based on fluorescence single particle spectroscopy, that is suited for high throughput measurements, can be used to detect and characterize intracellularly formed α-synuclein aggregates and characterize the effect of molecules that interfere with α-synuclein aggregate formation. - Highlights: • Single particle spectroscopy detects intracellular formed α-synuclein aggregates. • Fusion proteins allow detection of protein aggregates at the oligomer level. • The technique detects molecules inhibiting α-synuclein aggregate formation. • Single particle spectroscopy is suited for high throughput measurements.« less

The single scattering properties of soot aggregates with concentric core-shell spherical monomers

NASA Astrophysics Data System (ADS)

Wu, Yu; Cheng, Tianhai; Gu, Xingfa; Zheng, Lijuan; Chen, Hao; Xu, Hui

2014-03-01

Anthropogenic soot aerosols are shown as complex, fractal-like aggregated structures with high light absorption efficiency. In atmospheric environment, soot monomers may tend to acquire a weakly absorbing coating, such as an organic coating, which introduces further complexity to the optical properties of the aggregates. The single scattering properties of soot aggregates can be significantly influenced by the coated status of these kinds of aerosols. In this article, the monomers of fractal soot aggregates are modelled as semi-external mixtures (physical contact) with constant radius of soot core and variable sizes of the coating for specific soot volume fractions. The single scattering properties of these coated soot particles, such as phase function, the cross sections of extinction and absorption, single scattering albedo (SSA) and asymmetry parameter (ASY), are calculated using the numerically exact superposition T-matrix method. The random-orientation averaging results have shown that the single scattering properties of these coated soot aggregates are significantly different from the single volume-equivalent core-shell sphere approximation using the Mie theory and the homogeneous aggregates with uncoated monomers using the effective medium theory, such as Maxwell-Garnett and Bruggemann approximations, which overestimate backscattering of coated soot. It is found that the SSA and cross sections of extinction and absorption are increased for soot aggregates with thicker weakly absorbing coating on the monomers. Especially, the SSA values of these simulated aggregates with less soot core volume fractions are remarkably (~50% for core volume fraction of soot aggregates of 0.5, ~100% for a core volume fraction of 0.2, at 0.67 μm) larger than for uncoated soot particles without consideration of coating. Moreover, the cross sections of extinction and absorption are underestimated by the computation of equivalent homogeneous fractal aggregate approximation (within 5% for the T-matrix method and 10-25% for the Rayleigh-Debye-Gans approximation due to different soot volume fractions). Further understanding of the optical properties of these coated soot aggregates would be helpful for both environment monitoring and climate studies.

Role of streams in myxobacteria aggregate formation

NASA Astrophysics Data System (ADS)

Kiskowski, Maria A.; Jiang, Yi; Alber, Mark S.

2004-10-01

Cell contact, movement and directionality are important factors in biological development (morphogenesis), and myxobacteria are a model system for studying cell-cell interaction and cell organization preceding differentiation. When starved, thousands of myxobacteria cells align, stream and form aggregates which later develop into round, non-motile spores. Canonically, cell aggregation has been attributed to attractive chemotaxis, a long range interaction, but there is growing evidence that myxobacteria organization depends on contact-mediated cell-cell communication. We present a discrete stochastic model based on contact-mediated signaling that suggests an explanation for the initialization of early aggregates, aggregation dynamics and final aggregate distribution. Our model qualitatively reproduces the unique structures of myxobacteria aggregates and detailed stages which occur during myxobacteria aggregation: first, aggregates initialize in random positions and cells join aggregates by random walk; second, cells redistribute by moving within transient streams connecting aggregates. Streams play a critical role in final aggregate size distribution by redistributing cells among fewer, larger aggregates. The mechanism by which streams redistribute cells depends on aggregate sizes and is enhanced by noise. Our model predicts that with increased internal noise, more streams would form and streams would last longer. Simulation results suggest a series of new experiments.

Why Huddle? Ecological Drivers of Chick Aggregations in Gentoo Penguins, Pygoscelis papua, across Latitudes

PubMed Central

Collen, Ben; Johnston, Daniel

2016-01-01

Aggregations of young animals are common in a range of endothermic and ectothermic species, yet the adaptive behavior may depend on social circumstance and local conditions. In penguins, many species form aggregations (aka. crèches) for a variety of purposes, whilst others have never been observed exhibiting this behavior. Those that do form aggregations do so for three known benefits: 1) reduced thermoregulatory requirements, 2) avoidance of unrelated-adult aggression, and 3) lower predation risk. In gentoo penguins, Pygoscelis papua, chick aggregations are known to form during the post-guard period, yet the cause of these aggregations is poorly understood. Here, for the first time, we study aggregation behavior in gentoo penguins, examining four study sites along a latitudinal gradient using time-lapse cameras to examine the adaptive benefit of aggregations to chicks. Our results support the idea that aggregations of gentoo chicks decrease an individual’s energetic expenditure when wet, cold conditions are present. However, we found significant differences in aggregation behavior between the lowest latitude site, Maiviken, South Georgia, and two of the higher latitude sites on the Antarctic Peninsula, suggesting this behavior may be colony specific. We provide strong evidence that more chicks aggregate and a larger number of aggregations occur on South Georgia, while the opposite occurs at Petermann Island in Antarctica. Future studies should evaluate multiple seabird colonies within one species before generalizing behaviors based on one location, and past studies may need to be re-evaluated to determine whether chick aggregation and other behaviors are in fact exhibited species-wide. PMID:26840252

Why Huddle? Ecological Drivers of Chick Aggregations in Gentoo Penguins, Pygoscelis papua, across Latitudes.

PubMed

Black, Caitlin; Collen, Ben; Johnston, Daniel; Hart, Tom

2016-01-01

Aggregations of young animals are common in a range of endothermic and ectothermic species, yet the adaptive behavior may depend on social circumstance and local conditions. In penguins, many species form aggregations (aka. crèches) for a variety of purposes, whilst others have never been observed exhibiting this behavior. Those that do form aggregations do so for three known benefits: 1) reduced thermoregulatory requirements, 2) avoidance of unrelated-adult aggression, and 3) lower predation risk. In gentoo penguins, Pygoscelis papua, chick aggregations are known to form during the post-guard period, yet the cause of these aggregations is poorly understood. Here, for the first time, we study aggregation behavior in gentoo penguins, examining four study sites along a latitudinal gradient using time-lapse cameras to examine the adaptive benefit of aggregations to chicks. Our results support the idea that aggregations of gentoo chicks decrease an individual's energetic expenditure when wet, cold conditions are present. However, we found significant differences in aggregation behavior between the lowest latitude site, Maiviken, South Georgia, and two of the higher latitude sites on the Antarctic Peninsula, suggesting this behavior may be colony specific. We provide strong evidence that more chicks aggregate and a larger number of aggregations occur on South Georgia, while the opposite occurs at Petermann Island in Antarctica. Future studies should evaluate multiple seabird colonies within one species before generalizing behaviors based on one location, and past studies may need to be re-evaluated to determine whether chick aggregation and other behaviors are in fact exhibited species-wide.

Relationship between morphological change and crystalline phase transitions of polyethylene-poly(ethylene oxide) diblock copolymers, revealed by the temperature-dependent synchrotron WAXD/SAXS and infrared/Raman spectral measurements.

PubMed

Weiyu, Cao; Tashiro, Kohji; Hanesaka, Makoto; Takeda, Shinichi; Masunaga, Hiroyasu; Sasaki, Sono; Takata, Masaki

2009-02-26

The phase transition behaviors of low-molecular-weight polyethylene-poly(ethylene oxide) (PE-b-PEO) diblock copolymers with the monomeric units of PE/PEO = 17/40 and 39/86 have been successfully investigated through the temperature-dependent measurements of wide-angle X-ray diffraction (WAXD), small-angle X-ray scattering (SAXS), infrared and Raman spectra, as well as thermal analysis. These diblock copolymers had been believed to show only order-to-disorder transition of lamellar morphology in a wide temperature region, but it has been found here for the first time that this copolymer clearly exhibits the three stages of transitions among lamella, gyroid, cylinder, and spherical phases in the heating and cooling processes. The WAXD and IR/Raman spectral measurements allowed us to relate these morphological changes to the microscopic changes in the aggregation states of PEO and PE segments. In the low-temperature region the PEO segments form the monoclinic crystal of (7/2) helical chain conformation and the PE segments of planar-zigzag form take the orthorhombic crystalline phase. These crystalline lamellae of PEO and PE segments are alternately stacked with the long period of 165 Angstroms. In a higher temperature region, where the PEO crystalline parts are on the way of melting but the PE parts are still in the orthorhombic phase, the gyroid morphology is detected in the SAXS data. By heating further, the gyroid morphology changes to the hexagonally packed cylindrical morphology, where the orthorhombic phase of PE segments is gradually disordered because of thermally activated molecular motion and finally transforms to the pseudohexagonal or rotator phase. Once the PE segments are perfectly melted, the higher-order structure changes from the cylinder to the spherical morphology. These morphological transitions might relate to the thermally activated motions of two short chain segments of the diblock copolymer, although the details of the transition mechanism are unclear at the present stage.

Luminescence studies of CdS spherical particles via hydrothermal synthesis

NASA Astrophysics Data System (ADS)

Xu, Guo Qin; Liu, Bing; Xu, Shi Jie; Chew, Chwee Har; Chua, Soo Jin; Gana, Leong Ming

2000-06-01

The spherical particles of CdS consisting of nanoparticles (∼100 nm) were synthesized by a hydrothermal process. The particle formation and growth depend on the rate of sulfide-ion generation and diffusion-controlled aggregation of nanoparticles. As demonstrated in the profiles of powder X-ray diffraction, the crystalline phases are governed by the reaction temperature. Photoluminescence studies on CdS particles show two emission bands at the room temperature. The red emission at 680 nm is due to sulfur vacancies, and a new infrared red (IR) emission at 760 nm is attributed to self-activated centers. A red shift of IR band with the decrease of temperature was explained with a configurational coordinate model. The different saturation limits for the red and IR bands are discussed in terms of the formation of donor-acceptor pairs and exciton in CdS particles.

Computational study of the effect of gradient magnetic field in navigation of spherical particles

NASA Astrophysics Data System (ADS)

Karvelas, E. G.; Lampropoulos, N. K.; Papadimitriou, D. I.; Karakasidis, T. E.; Sarris, I. E.

2017-11-01

The use of spherical magnetic nanoparticles that are coated with drugs and can be navigated in arteries to attack tumors is proposed as an alternative to chemotherapy. Navigation of particles is due to magnetic field gradients that may be produced in an MRI device. In the present work, a computational study for the evaluation of the magnitude of the gradient magnetic field for particles navigation in Y bifurcations is presented. For this purpose, the presented method solves for the fluid flow and includes all the important forces that act on the particles in their discrete motion. The method is based on an iteration algorithm that adjusts the gradient magnetic field to minimize the particles’ deviation from a desired trajectory. Using the above mentioned method, the appropriate range of the gradient magnetic field for optimum navigation of nanoparticles’s aggregation is found.

Structure of modified [epsilon]-polylysine micelles and their application in improving cellular antioxidant activity of curcuminoids

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

Yu, Hailong; Li, Ji; Shi, Ke

The micelle structure of octenyl succinic anhydride modified {var_epsilon}-polylysine (M-EPL), an anti-microbial surfactant prepared from natural peptide {var_epsilon}-polylysine in aqueous solution has been studied using synchrotron small-angle X-ray scattering (SAXS). Our results revealed that M-EPLs formed spherical micelles with individual size of 24-26 {angstrom} in aqueous solution which could further aggregate to form a larger dimension with averaged radius of 268-308 {angstrom}. Furthermore, M-EPL micelle was able to encapsulate curcuminoids, a group of poorly-soluble bioactive compounds from turmeric with poor oral bioavailability, and improve their water solubility. Three loading methods, including solvent evaporation, dialysis, and high-speed homogenization were compared. Themore » results indicated that the dialysis method generated the highest loading capacity and curcuminoids water solubility. The micelle encapsulation was confirmed as there were no free curcuminoid crystals detected in the differential scanning calorimetry analysis. It was also demonstrated that M-EPL encapsulation stabilized curcuminoids against hydrolysis at pH 7.4 and the encapsulated curcuminoids showed elevated cellular antioxidant activity compared with free curcuminoids. This work suggested that M-EPL could be used as new biopolymer micelles for delivering poorly soluble drugs/phytochemicals and improving their bioactivities.« less

Effects of environmental factors on MSP21-25 aggregation indicate the roles of hydrophobic and electrostatic interactions in the aggregation process.

PubMed

Zhang, Xuecheng; Dong, Yuanqiu; Yu, Jigang; Tu, Xiaoming

2014-01-01

Merozoite surface protein 2 (MSP2), one of the most abundant proteins on the merozoite surface of Plasmodium falciparum, is recognized to be important for the parasite's invasion into the host cell and is thus a promising malaria vaccine candidate. However, mediated mainly by its conserved N-terminal 25 residues (MSP21-25), MSP2 readily forms amyloid fibril-like aggregates under physiological conditions in vitro, which impairs its potential as a vaccine component. In addition, there is evidence that MSP2 exists in aggregated forms on the merozoite surface in vivo. To elucidate the aggregation mechanism of MSP21-25 and thereby understand the behavior of MSP2 in vivo and find ways to avoid the aggregation of relevant vaccine in vitro, we investigated the effects of agitation, pH, salts, 1-anilinonaphthalene-8-sulfonic acid (ANS), trimethylamine N-oxide dihydrate (TMAO), urea, and sub-micellar sodium dodecyl sulfate (SDS) on the aggregation kinetics of MSP21-25 using thioflavin T (ThT) fluorescence. The results showed that MSP21-25 aggregation was accelerated by agitation, while repressed by acidic pHs. The salts promoted the aggregation in an anion nature-dependent pattern. Hydrophobic surface-binding agent ANS and detergent urea repressed MSP21-25 aggregation, in contrast to hydrophobic interaction strengthener TMAO, which enhanced the aggregation. Notably, sub-micellar SDS, contrary to its micellar form, promoted MSP21-25 aggregation significantly. Our data indicated that hydrophobic interactions are the predominant driving force of the nucleation of MSP21-25 aggregation, while the elongation is controlled mainly by electrostatic interactions. A kinetic model of MSP21-25 aggregation and its implication were also discussed.

Comparative analysis of methods and optical-electronic equipment to control the form parameters of spherical mirrors

NASA Astrophysics Data System (ADS)

Nikitin, Alexander N.; Baryshnikov, Nikolay; Denisov, Dmitrii; Karasik, Valerii; Sakharov, Alexey; Romanov, Pavel; Sheldakova, Julia; Kudryashov, Alexis

2018-02-01

In this paper we consider two approaches widely used in testing of spherical optical surfaces: Fizeau interferometer and Shack-Hartmann wavefront sensor. Fizeau interferometer that is widely used in optical testing can be transformed to a device using Shack-Hartmann wavefront sensor, the alternative technique to check spherical optical components. We call this device Hartmannometer, and compare its features to those of Fizeau interferometer.

Lenticular accommodation in relation to ametropia: the chick model.

PubMed

Choh, Vivian; Sivak, Jacob G

2005-03-04

Our goal was to determine whether experimentally induced ametropias have an effect on lenticular accommodation and spherical aberration. Form-deprivation myopia and hyperopia were induced in one eye of hatchling chicks by application of a translucent goggle and +15 D lens, respectively. After 7 days, eyes were enucleated and lenses were optically scanned prior to accommodation, during accommodation, and after accommodation. Accommodation was induced by electrical stimulation of the ciliary nerve. Lenticular focal lengths for form-deprived eyes were significantly shorter than for their controls and accommodation-associated changes in focal length were significantly smaller in myopic eyes compared to their controls. For eyes imposed with +15 D blur, focal lengths were longer than those for their controls and accommodative changes were greater. Spherical aberration of the lens increased with accommodation in both form-deprived and lens-treated birds, but induction of ametropia had no effect on lenticular spherical aberration in general. Nonmonotonicity from lenticular spherical aberration increased during accommodation but effects of refractive error were equivocal. The crystalline lens contributes to refractive error changes of the eye both in the case of myopia and hyperopia. These changes are likely attributable to global changes in the size and shape of the eye.

Formation of the nitrogen aggregates in annealed diamond by neutron irradiation

NASA Astrophysics Data System (ADS)

Mita, Y.; Nisida, Y.; Okada, M.

2018-02-01

Neutron heavy irradiation was performed on synthetic diamonds contain nitrogen atoms in isolated substitutional form (called "type Ib diamond") and they were annealed under a pressure of 6 GPa. A large number of nitrogen B-aggregate which consists of four substitutional nitrogen atoms symmetrically surrounding a vacancy was formed within 30 m from single nitrogen atoms. Furthermore it is observed that, in these diamonds, single nitrogen atoms coexist with the B-aggregates, which is unexplainable by the simple nitrogen aggregation model.

Intrinsic Determinants of Neurotoxic Aggregate Formation by the Amyloid β Peptide

PubMed Central

Brorsson, Ann-Christin; Bolognesi, Benedetta; Tartaglia, Gian Gaetano; Shammas, Sarah L.; Favrin, Giorgio; Watson, Ian; Lomas, David A.; Chiti, Fabrizio; Vendruscolo, Michele; Dobson, Christopher M.; Crowther, Damian C.; Luheshi, Leila M.

2010-01-01

Abstract The extent to which proteins aggregate into distinct structures ranging from prefibrillar oligomers to amyloid fibrils is key to the pathogenesis of many age-related degenerative diseases. We describe here for the Alzheimer's disease-related amyloid β peptide (Aβ) an investigation of the sequence-based determinants of the balance between the formation of prefibrillar aggregates and amyloid fibrils. We show that by introducing single-point mutations, it is possible to convert the normally harmless Aβ40 peptide into a pathogenic species by increasing its relative propensity to form prefibrillar but not fibrillar aggregates, and, conversely, to abolish the pathogenicity of the highly neurotoxic E22G Aβ42 peptide by reducing its relative propensity to form prefibrillar species rather than mature fibrillar ones. This observation can be rationalized by the demonstration that whereas regions of the sequence of high aggregation propensity dominate the overall tendency to aggregate, regions with low intrinsic aggregation propensities exert significant control over the balance of the prefibrillar and fibrillar species formed, and therefore play a major role in determining the neurotoxicity of the Aβ peptide. PMID:20409489

Characterizing the mechanical behavior of the zebrafish germ layers

NASA Astrophysics Data System (ADS)

Kealhofer, David; Serwane, Friedhelm; Mongera, Alessandro; Rowghanian, Payam; Lucio, Adam; Campàs, Otger

Organ morphogenesis and the development of the animal body plan involve complex spatial and temporal control of tissue- and cell-level mechanics. A prime example is the generation of stresses by individual cells to reorganize the tissue. These processes have remained poorly understood due to a lack of techniques to characterize the local constitutive law of the material, which relates local cellular forces to the resulting tissue flows. We have developed a method for quantitative, local in vivo study of material properties in living tissue using magnetic droplet probes. We use this technique to study the material properties of the different zebrafish germ layers using aggregates of zebrafish mesendodermal and ectodermal cells as a model system. These aggregates are ideal for controlled studies of the mechanics of individual germ layers because of the homogeneity of the cell type and the simple spherical geometry. Furthermore, the numerous molecular tools and transgenic lines already developed for this model organism can be applied to these aggregates, allowing us to characterize the contributions of cell cortex tension and cell adhesion to the mechanical properties of the zebrafish germ layers.

Active motility in bimodular bacterial aggregates

NASA Astrophysics Data System (ADS)

Zeng, Yu; Liu, Bin

2017-11-01

Dispersal capability is essential for microorganisms to achieve long-distance translocation, thus crucial for their abundance in various environments. In general, active dispersals are attributed to the movements of self-powered planktonic cells, while sessile cells that live a colonial life often disperse passively through flow entrainments. Here, we report another means of active dispersal employed by aggregates of sessile cells. The spherical rosette colonies of the bacterium Caulobacter crescentus are aggregates of sessile stalked cells, of which a small proportion undergo cell division, grow active flagella and effect whole-rosette motility. We show that these rosettes actively disperse both in bulk water and near the solid-liquid interface. In particular, the proximity of a self-powered rosette to the solid surface promotes a rolling movement, leading to its persistent transportation along the solid boundary. The active dispersal of these rosettes demonstrated a novel mode of colonial transportation that is based on the division of labor between sessile and motile cells. The authors thank the support of National Science Foundation CREST: Center for Cellular and Biomolecular Machines at UC Merced (NSF-HRD-1547848).

High density flux of Co nanoparticles produced by a simple gas aggregation apparatus.

PubMed

Landi, G T; Romero, S A; Santos, A D

2010-03-01

Gas aggregation is a well known method used to produce clusters of different materials with good size control, reduced dispersion, and precise stoichiometry. The cost of these systems is relatively high and they are generally dedicated apparatuses. Furthermore, the usual sample production speed of these systems is not as fast as physical vapor deposition devices posing a problem when thick samples are needed. In this paper we describe the development of a multipurpose gas aggregation system constructed as an adaptation to a magnetron sputtering system. The cost of this adaptation is negligible and its installation and operation are both remarkably simple. The gas flow for flux in the range of 60-130 SCCM (SCCM denotes cubic centimeter per minute at STP) is able to completely collimate all the sputtered material, producing spherical nanoparticles. Co nanoparticles were produced and characterized using electron microscopy techniques and Rutherford back-scattering analysis. The size of the particles is around 10 nm with around 75 nm/min of deposition rate at the center of a Gaussian profile nanoparticle beam.

Sphericity determination using resonant ultrasound spectroscopy

DOEpatents

Dixon, Raymond D.; Migliori, Albert; Visscher, William M.

1994-01-01

A method is provided for grading production quantities of spherical objects, such as roller balls for bearings. A resonant ultrasound spectrum (RUS) is generated for each spherical object and a set of degenerate sphere-resonance frequencies is identified. From the degenerate sphere-resonance frequencies and known relationships between degenerate sphere-resonance frequencies and Poisson's ratio, a Poisson's ratio can be determined, along with a "best" spherical diameter, to form spherical parameters for the sphere. From the RUS, fine-structure resonant frequency spectra are identified for each degenerate sphere-resonance frequency previously selected. From each fine-structure spectrum and associated sphere parameter values an asphericity value is determined. The asphericity value can then be compared with predetermined values to provide a measure for accepting or rejecting the sphere.

Sphericity determination using resonant ultrasound spectroscopy

DOEpatents

Dixon, R.D.; Migliori, A.; Visscher, W.M.

1994-10-18

A method is provided for grading production quantities of spherical objects, such as roller balls for bearings. A resonant ultrasound spectrum (RUS) is generated for each spherical object and a set of degenerate sphere-resonance frequencies is identified. From the degenerate sphere-resonance frequencies and known relationships between degenerate sphere-resonance frequencies and Poisson's ratio, a Poisson's ratio can be determined, along with a 'best' spherical diameter, to form spherical parameters for the sphere. From the RUS, fine-structure resonant frequency spectra are identified for each degenerate sphere-resonance frequency previously selected. From each fine-structure spectrum and associated sphere parameter values an asphericity value is determined. The asphericity value can then be compared with predetermined values to provide a measure for accepting or rejecting the sphere. 14 figs.

Coagulation of grains in static and collapsing protostellar clouds

NASA Technical Reports Server (NTRS)

Weidenschilling, S. J.; Ruzmaikina, T. V.

1994-01-01

We simulate collisional evolution of grains in dense turbulent molecular cloud cores (or Bok globules) in static equilibrium and free-fall collapse, assuming spherical symmetry. Relative velocities are due to thermal motions, differential settling, and turbulence, with the latter dominant for sonic turbulence with an assumed Kolmogorov spectrum. Realistic criteria are used to determine outcomes of collisions (coagulation vs. destruction) as functions of particle size and velocity. Results are presented for a variety of cloud parameters (radial density profile, turbulent velocity) and particle properties (density, impact strength). Results are sensitive to the assumed mechanical properties (density and impact strength) of grain aggregates. Particle growth is enhanced if aggregates have low density or fractal structures. On a timescale of a few Myr, an initial population of 0.1 micrometers grains may produce dense compact particles approximately 1 micrometer in size, or fluffy aggregates approximately 100 micrometers. For impact strengths less than or equal to 10(exp 6) ergs/g, a steady state is reached between coagulation of small grains and collisional disruption of larger aggregates. Formation of macroscopic aggregates requires high mechanical strengths and low aggregate densities. We assume sonic turbulence during collapse, with varied eddy size scales determining the dissipation rate or turbulence strength. The degree of collisional evolution during collapse is sensitive to the assumed small-scale structure (inner sc ale) of the turbulence. Weak turbulence results in few collisions and preserves the precollapse particle size distribution with little change. Strong turbulence tends to produce net destruction, rather than particle growth, during infall, unless inpact strengths are greater than 10(exp 6)ergs/g.

A 31-residue peptide induces aggregation of tau's microtubule-binding region in cells

NASA Astrophysics Data System (ADS)

Stöhr, Jan; Wu, Haifan; Nick, Mimi; Wu, Yibing; Bhate, Manasi; Condello, Carlo; Johnson, Noah; Rodgers, Jeffrey; Lemmin, Thomas; Acharya, Srabasti; Becker, Julia; Robinson, Kathleen; Kelly, Mark J. S.; Gai, Feng; Stubbs, Gerald; Prusiner, Stanley B.; Degrado, William F.

2017-09-01

The self-propagation of misfolded conformations of tau underlies neurodegenerative diseases, including Alzheimer's. There is considerable interest in discovering the minimal sequence and active conformational nucleus that defines this self-propagating event. The microtubule-binding region, spanning residues 244-372, reproduces much of the aggregation behaviour of tau in cells and animal models. Further dissection of the amyloid-forming region to a hexapeptide from the third microtubule-binding repeat resulted in a peptide that rapidly forms fibrils in vitro. We show that this peptide lacks the ability to seed aggregation of tau244-372 in cells. However, as the hexapeptide is gradually extended to 31 residues, the peptides aggregate more slowly and gain potent activity to induce aggregation of tau244-372 in cells. X-ray fibre diffraction, hydrogen-deuterium exchange and solid-state NMR studies map the beta-forming region to a 25-residue sequence. Thus, the nucleus for self-propagating aggregation of tau244-372 in cells is packaged in a remarkably small peptide.

Enhanced DNA Sensing via Catalytic Aggregation of Gold Nanoparticles

PubMed Central

Huttanus, Herbert M.; Graugnard, Elton; Yurke, Bernard; Knowlton, William B.; Kuang, Wan; Hughes, William L.; Lee, Jeunghoon

2014-01-01

A catalytic colorimetric detection scheme that incorporates a DNA-based hybridization chain reaction into gold nanoparticles was designed and tested. While direct aggregation forms an inter-particle linkage from only ones target DNA strand, the catalytic aggregation forms multiple linkages from a single target DNA strand. Gold nanoparticles were functionalized with thiol-modified DNA strands capable of undergoing hybridization chain reactions. The changes in their absorption spectra were measured at different times and target concentrations and compared against direct aggregation. Catalytic aggregation showed a multifold increase in sensitivity at low target concentrations when compared to direct aggregation. Gel electrophoresis was performed to compare DNA hybridization reactions in catalytic and direct aggregation schemes, and the product formation was confirmed in the catalytic aggregation scheme at low levels of target concentrations. The catalytic aggregation scheme also showed high target specificity. This application of a DNA reaction network to gold nanoparticle-based colorimetric detection enables highly-sensitive, field-deployable, colorimetric readout systems capable of detecting a variety of biomolecules. PMID:23891867

Investigation of aggregation in solvent extraction of lanthanides by acidic extractants (organophosphorus and naphthenic acid)

USGS Publications Warehouse

Zhou, N.; Wu, J.; Yu, Z.; Neuman, R.D.; Wang, D.; Xu, G.

1997-01-01

Three acidic extractants (I) di(2-ethylhexyl) phosphoric acid (HDEHP), (II) 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (HEHPEHE) and (III) naphthenic acid were employed in preparing the samples for the characterization of the coordination structure of lanthanide-extractant complexes and the physicochemical nature of aggregates formed in the organic diluent of the solvent extraction systems. Photo correlation spectroscopy (PCS) results on the aggregates formed by the partially saponified HDEHP in n-heptane showed that the hydrodynamic radius of the aggregates was comparable to the molecular dimensions of HDEHP. The addition of 2-octanol into the diluent, by which the mixed solvent was formed, increased the dimensions of the corresponding aggregates. Aggregates formed from the lanthanide ions and HDEHP in the organic phase of the extraction systems were found very unstable. In the case of naphthenic acid, PCS data showed the formation of w/o microemulsion from the saponified naphthenic acid in the mixed solvent. The extraction of lanthanides by the saponified naphthenic acid in the mixed solvent under the given experimental conditions was a process of destruction of the w/o microemulsion. A possible mechanism of the breakdown of the w/o microemulsion droplets is discussed.

Bulk and monolayer ordering of block copolymer blends

NASA Astrophysics Data System (ADS)

Onikoyi, Adetunji J.

The control of the nanoscale structure or morphology of a block copolymer is a desired goal for nanolithography applications. In this work, we are particularly interested in providing guides for controlling domain size, domain shape and defect densities in block copolymers and their blends for thin film applications. To reach this goal, a sphere forming PS-b-P2VP (having a PS majority block) and its blends with PS homopolymer or cylinder forming PS-b-P2VP are studied in both the bulk and thin films. Structure characterization is performed using a variety of experimental techniques including small angle X-ray scattering, scanning force microscopy and transmission electron microscopy. In the bulk, the spherical domains of the pure, sphere forming PS-b-P2VP arrange on a BCC lattice. On adding PS homopolymer (hPS), the lattice parameter of the BCC spheres increases, while the order-to-disorder temperature (ODT) of the BCC lattice simultaneously decreases. At a given hPS composition, the use of larger sized hPS leads to larger increases in the lattice parameter and larger decreases in the ODT. In bulk blends of cylinder forming PS-b-P2VP with sphere forming PS-b-P2VP, the ordered morphology changes (e.g., cylindrical morphology → coexisting spherical and cylindrical morphologies → spherical morphology) as the sphere forming PS-b-P2VP volume fraction phis increases, while the ODT of the cylindrical morphology decreases. The phase boundaries of these morphologies in monolayers shift to lower phis compared to those of the bulk, apparently caused by a selective adsorption of the cylindrical PS-b-P2VP to form a brush on the substrate. This selective adsorption leads to a preference for spherical domains in diamond-shaped lateral confinements when cylindrical domains are stabilized outside the confinements on the same substrate. Finally, we explore the use of graphoepitaxy to order monolayers of sphere forming PS-b-P2VP and its blends with hPS. The probability of forming isolated dislocations, or of adding (or removing) a full row of spherical domains, in diamond-shaped lateral confinements is shown to be higher when the well size is incommensurate with the lattice parameter. Square-shaped lateral confinement leads to a preference for square sphere packing if the PS-b-P2VP is blended with appropriate amounts of hPS.

Solubilization of protein aggregates by the acid stress chaperones HdeA and HdeB.

PubMed

Malki, Abderrahim; Le, Hai-Tuong; Milles, Sigrid; Kern, Renée; Caldas, Teresa; Abdallah, Jad; Richarme, Gilbert

2008-05-16

The acid stress chaperones HdeA and HdeB of Escherichia coli prevent the aggregation of periplasmic proteins at acidic pH. We show in this report that they also form mixed aggregates with proteins that have failed to be solubilized at acidic pH and allow their subsequent solubilization at neutral pH. HdeA, HdeB, and HdeA and HdeB together display an increasing efficiency for the solubilization of protein aggregates at pH 3. They are less efficient for the solubilization of aggregates at pH 2, whereas HdeB is the most efficient. Increasing amounts of periplasmic proteins draw increasing amounts of chaperone into pellets, suggesting that chaperones co-aggregate with their substrate proteins. We observed a decrease in the size of protein aggregates in the presence of HdeA and HdeB, from very high molecular mass aggregates to 100-5000-kDa species. Moreover, a marked decrease in the exposed hydrophobicity of aggregated proteins in the presence of HdeA and HdeB was revealed by 1,1'-bis(4-anilino)naphtalene-5,5'-disulfonic acid binding experiments. In vivo, during the recovery at neutral pH of acid stressed bacterial cells, HdeA and HdeB allow the solubilization and renaturation of protein aggregates, including those formed by the maltose receptor MalE, the oligopeptide receptor OppA, and the histidine receptor HisJ. Thus, HdeA and HdeB not only help to maintain proteins in a soluble state during acid treatment, as previously reported, but also assist, both in vitro and in vivo, in the solubilization at neutral pH of mixed protein-chaperone aggregates formed at acidic pH, by decreasing the size of protein aggregates and the exposed hydrophobicity of aggregated proteins.

INTERDISCIPLINARY PHYSICS AND RELATED AREAS OF SCIENCE AND TECHNOLOGY: Competition Between Self-birth and Catalyzed Death in Aggregation Growth with Catalysis Injection

NASA Astrophysics Data System (ADS)

Chen, Dan; Lin, Zhen-Quan; Sun, Yun-Fei; Ke, Jian-Hong

2009-12-01

We propose two irreversible aggregation growth models of aggregates of two distinct species (A and B) to study the interactions between virus aggregates and medicine efficacy aggregates in the virus-medicine cooperative evolution system. The A-species aggregates evolve driven by self monomer birth and B-species aggregate-catalyzed monomer death in model I and by self birth, catalyzed death, and self monomer exchange reactions in model II, while the catalyst B-species aggregates are assumed to be injected into the system sustainedly or at a periodic time-dependent rate. The kinetic behaviors of the A-species aggregates are investigated by the rate equation approach based on the mean-field theory with the self birth rate kernel IA(k) = Ik, catalyzed death rate kernel JAB(k) = Jk and self exchange rate kernel KA (k, l) = Kkl. The kinetic behaviors of the A-species aggregates are mainly dominated by the competition between the two effects of the self birth (with the effective rate I) and the catalyzed death (with the effective rate JB0), while the effects of the self exchanges of the A-species aggregates which appear in an effective rate KA0 play important roles in the cases of I > JB0 and I = JB0. The evolution behaviors of the total mass MA1(t) and the total aggregate number MA0 (t) are obtained, and the aggregate size distribution αk (t) of species A is found to approach a generalized scaling form in the case of I >= JB0 and a special modified scaling form in the case of I < JB0. The periodical evolution of the B-monomers concentration plays an exponential form of the periodic modulation.

Cooperative structural transitions in amyloid-like aggregation

NASA Astrophysics Data System (ADS)

Steckmann, Timothy; Bhandari, Yuba R.; Chapagain, Prem P.; Gerstman, Bernard S.

2017-04-01

Amyloid fibril aggregation is associated with several horrific diseases such as Alzheimer's, Creutzfeld-Jacob, diabetes, Parkinson's, and others. Although proteins that undergo aggregation vary widely in their primary structure, they all produce a cross-β motif with the proteins in β-strand conformations perpendicular to the fibril axis. The process of amyloid aggregation involves forming myriad different metastable intermediate aggregates. To better understand the molecular basis of the protein structural transitions and aggregation, we report on molecular dynamics (MD) computational studies on the formation of amyloid protofibrillar structures in the small model protein ccβ, which undergoes many of the structural transitions of the larger, naturally occurring amyloid forming proteins. Two different structural transition processes involving hydrogen bonds are observed for aggregation into fibrils: the breaking of intrachain hydrogen bonds to allow β-hairpin proteins to straighten, and the subsequent formation of interchain H-bonds during aggregation into amyloid fibrils. For our MD simulations, we found that the temperature dependence of these two different structural transition processes results in the existence of a temperature window that the ccβ protein experiences during the process of forming protofibrillar structures. This temperature dependence allows us to investigate the dynamics on a molecular level. We report on the thermodynamics and cooperativity of the transformations. The structural transitions that occurred in a specific temperature window for ccβ in our investigations may also occur in other amyloid forming proteins but with biochemical parameters controlling the dynamics rather than temperature.

Biological framework for soil aggregation: Implications for ecological functions.

NASA Astrophysics Data System (ADS)

Ghezzehei, Teamrat; Or, Dani

2016-04-01

Soil aggregation is heuristically understood as agglomeration of primary particles bound together by biotic and abiotic cementing agents. The organization of aggregates is believed to be hierarchical in nature; whereby primary particles bond together to form secondary particles and subsequently merge to form larger aggregates. Soil aggregates are not permanent structures, they continuously change in response to internal and external forces and other drivers, including moisture, capillary pressure, temperature, biological activity, and human disturbances. Soil aggregation processes and the resulting functionality span multiple spatial and temporal scales. The intertwined biological and physical nature of soil aggregation, and the time scales involved precluded a universally applicable and quantifiable framework for characterizing the nature and function of soil aggregation. We introduce a biophysical framework of soil aggregation that considers the various modes and factors of the genesis, maturation and degradation of soil aggregates including wetting/drying cycles, soil mechanical processes, biological activity and the nature of primary soil particles. The framework attempts to disentangle mechanical (compaction and soil fragmentation) from in-situ biophysical aggregation and provides a consistent description of aggregate size, hierarchical organization, and life time. It also enables quantitative description of biotic and abiotic functions of soil aggregates including diffusion and storage of mass and energy as well as role of aggregates as hot spots of nutrient accumulation, biodiversity, and biogeochemical cycles.

Snowball gouge-aggregates formed in experimental fault gouges at seismic slip rates

NASA Astrophysics Data System (ADS)

Kim, J. H.; Ree, J. H.; Hirose, T.; Yang, K.; Kim, J. W.

2015-12-01

Clay-clast aggregates (CCA) have commonly been reported from experimental and natural fault gouges, but their formation process and mechanical meaning are not so clear. We call CCA snowball gouge aggregate (SGA) since its formation process is similar to that of snowball (see below) and CCA-like structure has been reported also from pure quartz and pure calcite gouges. Here, we discuss the formation process of SGA and its implication for faulting from experimental results of simulated gouges. We conducted high-velocity rotary shear experiments on Ca-bentonite gouges at a normal stress of 1 MPa, slip rate of 1.31 m/s, room temperature and room humidity conditions. Ca-bentonite gouge consists of montmorillonite (>95%) and other minor minerals including quartz and plagioclase. Upon displacement, the friction abruptly increases to the 1st peak (friction coefficient μ≈ 0.7) followed by slip weakening to reach a steady state (μ≈ 0.25~0.3). The simulated fault zone can be divided into slip-localization zone (SLZ) and low-slip-rate zone (LSZ) based on grain size. Spherical SGAs with their size ranging from 1 to 100 μm occur only in LSZ, and their proportion is more than 90%. Two types of SGA occur; SGA with and without a central clast. Both types of SGA show a concentric layering defined by the alternation of pore-rich (1-1.5 μm thick) and pore-poor layers (1.5-2 μm thick). Clay minerals locally exhibit a preferred orientation with their basal plane parallel to the layer boundary. We interpret that the pore-poor layers are clay-accumulated layers formed by rolling of SGA nuclei, and pore-rich layers correspond to the boundary between accumulated clay layers. Water produced from dehydration of clays due to frictional heating presumably acts as an adhesion agent of clay minerals during rolling of SGA. Since the number of layers within each SGA represents the number of rolling, the minimum displacement estimated from the number of layers and layer thickness of the largest SGA (with a diameter of 100 μm) is about 2.7 mm (slip rate≈ 170 μm/s) which is much less than the total displacement of 20 m, suggesting that most of the displacement occurred along the SLZ. Our results imply that SGA can be formed only in subseismic slip-rate zones and that minimum displacement and slip rate can be estimated from SGA.

Stability of Iowa mutant and wild type Aβ-peptide aggregates

NASA Astrophysics Data System (ADS)

Alred, Erik J.; Scheele, Emily G.; Berhanu, Workalemahu M.; Hansmann, Ulrich H. E.

2014-11-01

Recent experiments indicate a connection between the structure of amyloid aggregates and their cytotoxicity as related to neurodegenerative diseases. Of particular interest is the Iowa Mutant, which causes early-onset of Alzheimer's disease. While wild-type Amyloid β-peptides form only parallel beta-sheet aggregates, the mutant also forms meta-stable antiparallel beta sheets. Since these structural variations may cause the difference in the pathological effects of the two Aβ-peptides, we have studied in silico the relative stability of the wild type and Iowa mutant in both parallel and antiparallel forms. We compare regular molecular dynamics simulations with such where the viscosity of the samples is reduced, which, we show, leads to higher sampling efficiency. By analyzing and comparing these four sets of all-atom molecular dynamics simulations, we probe the role of the various factors that could lead to the structural differences. Our analysis indicates that the parallel forms of both wild type and Iowa mutant aggregates are stable, while the antiparallel aggregates are meta-stable for the Iowa mutant and not stable for the wild type. The differences result from the direct alignment of hydrophobic interactions in the in-register parallel oligomers, making them more stable than the antiparallel aggregates. The slightly higher thermodynamic stability of the Iowa mutant fibril-like oligomers in its parallel organization over that in antiparallel form is supported by previous experimental measurements showing slow inter-conversion of antiparallel aggregates into parallel ones. Knowledge of the mechanism that selects between parallel and antiparallel conformations and determines their relative stability may open new avenues for the development of therapies targeting familial forms of early-onset Alzheimer's disease.

Synthetic aggregate compositions derived from spent bed materials from fluidized bed combustion and fly ash

DOEpatents

Boyle, Michael J.

1994-01-01

Cementitious compositions useful as lightweight aggregates are formed from a blend of spent bed material from fluidized bed combustion and fly ash. The proportions of the blend are chosen so that ensuing reactions eliminate undesirable constituents. The blend is then mixed with water and formed into a shaped article. The shaped article is preferably either a pellet or a "brick" shape that is later crushed. The shaped articles are cured at ambient temperature while saturated with water. It has been found that if used sufficiently, the resulting aggregate will exhibit minimal dimensional change over time. The aggregate can be certified by also forming standardized test shapes, e.g., cylinders while forming the shaped articles and measuring the properties of the test shapes using standardized techniques including X-ray diffraction.

Assembling substrate-less plasmonic metacrystals at the oil/water interface for multiplex ultratrace analyte detection.

PubMed

Lee, Yih Hong; Lee, Hiang Kwee; Ho, Jonathan Yong Chew; Yang, Yijie; Ling, Xing Yi

2016-08-15

Current substrate-less SERS platforms are limited to uncontrolled aggregation of plasmonic nanoparticles or quasi-crystalline arrays of spherical nanoparticles, with no study on how the lattice structures formed by nanoparticle self-assembly affect their detection capabilities. Here, we organize Ag octahedral building blocks into two large-area plasmonic metacrystals at the oil/water interface, and investigate their in situ SERS sensing capabilities. Amphiphilic octahedra assemble into a hexagonal close-packed metacrystal, while hydrophobic octahedra assemble into an open square metacrystal. The lower packing density square metacrystal gives rise to much stronger SERS enhancement than the denser packing hexagonal metacrystal, arising from the larger areas of plasmonic hotspots within the square metacrystal at the excitation wavelength. We further demonstrate the ability of the square metacrystal to achieve quantitative ultratrace detection of analytes from both the aqueous and organic phases. Detection limits are at the nano-molar levels, with analytical enhancement factors reaching 10(8). In addition, multiplex detection across both phases can be achieved in situ without any loss of signal quantitation.

Interaction and formation mechanism of binary complex between zein and propylene glycol alginate.

PubMed

Sun, Cuixia; Dai, Lei; Gao, Yanxiang

2017-02-10

The anti-solvent co-precipitation method was used to fabricate the zein-propylene glycol alginate (PGA) binary complex with different mass ratios of zein to PGA (20:1, 10:1, 5:1, 2:1 and 1:1) at pH 4.0. Results showed that attractive electrostatic interaction between zein and PGA occurred and negatively charged binary complex with large size and high turbidity was formed due to the charge neutralization. Hydrogen bonding and hydrophobic effects were involved in the interactions between zein and PGA, leading to the changed secondary structure and improved thermal stability of zein. Aggregates in the irregular shape with large size were obviously observed in the AFM images. PGA alone exhibited a fine filamentous network structure, while zein-PGA binary complex showed a rough branch-like pattern and the surface of "branch" was closely adsorbed by lots of spherical zein particles. Q in zein-PGA binary complex dispersions presented the improved photochemical and thermal stability. The potential mechanism of a two-step process was proposed to explain the formation of zein-PGA binary complexes. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ideal form of optical plasma lenses

NASA Astrophysics Data System (ADS)

Gordon, D. F.; Stamm, A. B.; Hafizi, B.; Johnson, L. A.; Kaganovich, D.; Hubbard, R. F.; Richardson, A. S.; Zhigunov, D.

2018-06-01

The canonical form of an optical plasma lens is a parabolic density channel. This form suffers from spherical aberrations, among others. Spherical aberration is partially corrected by adding a quartic term to the radial density profile. Ideal forms which lead to perfect focusing or imaging are obtained. The fields at the focus of a strong lens are computed with high accuracy and efficiency using a combination of eikonal and full Maxwell descriptions of the radiation propagation. The calculations are performed using a new computer propagation code, SeaRay, which is designed to transition between various solution methods as the beam propagates through different spatial regions. The calculations produce the full Maxwell vector fields in the focal region.

Influence of the valine zipper region on the structure and aggregation of the basic leucine zipper (bZIP) domain of activating transcription factor 5 (ATF5).

PubMed

Ciaccio, Natalie A; Reynolds, T Steele; Middaugh, C Russell; Laurence, Jennifer S

2012-11-05

Protein aggregation is a major problem for biopharmaceuticals. While the control of aggregation is critically important for the future of protein pharmaceuticals, mechanisms of aggregate assembly, particularly the role that structure plays, are still poorly understood. Increasing evidence indicates that partially folded intermediates critically influence the aggregation pathway. We have previously reported the use of the basic leucine zipper (bZIP) domain of activating transcription factor 5 (ATF5) as a partially folded model system to investigate protein aggregation. This domain contains three regions with differing structural propensity: a N-terminal polybasic region, a central helical leucine zipper region, and a C-terminal extended valine zipper region. Additionally, a centrally positioned cysteine residue readily forms an intermolecular disulfide bond that reduces aggregation. Computational analysis of ATF5 predicts that the valine zipper region facilitates self-association. Here we test this hypothesis using a truncated mutant lacking the C-terminal valine zipper region. We compare the structure and aggregation of this mutant to the wild-type (WT) form under both reducing and nonreducing conditions. Our data indicate that removal of this region results in a loss of α-helical structure in the leucine zipper and a change in the mechanism of self-association. The mutant form displays increased association at low temperature but improved resistance to thermally induced aggregation.

Ion aggregation in high salt solutions. VII. The effect of cations on the structures of ion aggregates and water hydrogen-bonding network

NASA Astrophysics Data System (ADS)

Choi, Jun-Ho; Choi, Hyung Ran; Jeon, Jonggu; Cho, Minhaeng

2017-10-01

Ions in high salt solutions have a strong propensity to form polydisperse ion aggregates with broad size and shape distributions. In a series of previous comparative investigations using femtosecond IR pump-probe spectroscopy, molecular dynamics simulation, and graph theoretical analysis, we have shown that there exists a morphological difference in the structures of ion aggregates formed in various salt solutions. As salt concentration increases, the ions in high salt solutions form either cluster-like structures excluding water molecules or network-like structures entwined with water hydrogen-bonding networks. Interestingly, such morphological characteristics of the ion aggregates have been found to be in correlation with the solubility limits of salts. An important question that still remains unexplored is why certain salts with different cations have notably different solubility limits in water. Here, carrying out a series of molecular dynamics simulations of aqueous salt solutions and analyzing the distributions and connectivity patterns of ion aggregates with a spectral graph analysis method, we establish the relationship between the salt solubility and the ion aggregate morphology with a special emphasis on the cationic effects on water structures and ion aggregation. We anticipate that the understanding of large scale ion aggregate structures revealed in this study will be critical for elucidating the specific ion effects on the solubility and conformational stability of co-solute molecules such as proteins in water.

Selective tuning of the self-assembly and gelation of a hydrophilic poloxamine by cyclodextrins.

PubMed

González-Gaitano, Gustavo; da Silva, Marcelo A; Radulescu, Aurel; Dreiss, Cécile A

2015-05-26

Complexes formed between cyclodextrins (CDs) and polymers - pseudopolyrotaxanes (PPRs) - are the starting point of a multitude of supramolecular structures, which are proposed for a wide range of biomedical and technological applications. In this work, we investigate the complexation of a range of cyclodextrins with Tetronic T1307, a four-arm block copolymer of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) with a pH-responsive central ethylene diamine spacer, and its impact on micellization and the sol-gel transition. At low concentrations, small-angle neutron scattering (SANS) combined with dynamic light scattering (DLS) measurements show the presence of spherical micelles with a highly hydrated shell and a dehydrated core. Increasing the temperature leads to more compact micelles and larger aggregation numbers, whereas acidic conditions induce a shrinking of the micelles, with fewer unimers per micelle and a more hydrated corona. At high concentrations, T1307 undergoes a sol-gel transition, which is suppressed at pH below the pKa,1 (4.6). SANS data analysis reveals that the gels result from a random packing of the micelles, which have an increasing aggregation number and increasingly dehydrated shell and hydrated core with the temperature. Native CDs (α, β, γ-CD) can complex T1307, resulting in the precipitation of a PPR. Instead, modified CDs compete with micellization to an extent that is critically dependent on the nature of the substitution. (1)H and ROESY NMR combined with SANS demonstrate that dimethylated β-CD can thread onto the polymer, preferentially binding to the PO units, thus hindering self-aggregation by solubilizing the hydrophobic block. The various CDs are able to modulate the onset of gelation and the extent of the gel phase, and the effect correlates with the ability of the CDs to disrupt the micelles, with the exception of a sulfated sodium salt of β-CD, which, while not affecting the CMT, is able to fully suppress the gel phase.

Synthesis and biological imaging of cross-linked fluorescent polymeric nanoparticles with aggregation-induced emission characteristics based on the combination of RAFT polymerization and the Biginelli reaction.

PubMed

Dong, Jiande; Liu, Meiying; Jiang, Ruming; Huang, Hongye; Wan, Qing; Wen, Yuanqing; Tian, Jianwen; Dai, Yanfeng; Zhang, Xiaoyong; Wei, Yen

2018-05-17

Fluorescent probes have long been regarded as tools for imaging living organisms with advantages such as high sensitivity, good designability and multifunctional potential. Many fluorescent probes, especially the probes based on aggregation-induced emission (AIE) dyes, have received increasing attention since the AIE phenomenon was discovered. These AIE dye-based fluorescent probes could elegantly overcome the notorious quenching effect caused by aggregation of conventional organic dyes. However, it is still difficult to directly apply these AIE-active dyes for biomedical applications owing to their hydrophobic nature. Therefore, the development of novel and facile strategies to endow them with water dispersibility is of critical importance. In this work, we exploit an efficient and simple strategy to fabricate an AIE dye-based fluorescent copolymer through the combination of reversible addition-fragmentation chain transfer and the Biginelli reaction. Moreover, the copolymer can self-assemble to fluorescent polymeric nanoparticles (FPNs) in water solution. Hydrophilic poly(PEGMA-co-AEMA) was reacted with the AIE-active dye 4',4‴-(1,2-diphenylethene-1,2-diyl)bis([1,1'-biphenyl]-4-carbaldehyde (CHO-TPE-CHO) to form amphiphilic luminescent polymers using urea as the connection bridge. The successful synthesis of the final products (poly(PEGMA-co-AEMA-TPE) FPNs) was confirmed by various instruments. Furthermore, Transmission electron microscopy (TEM) images manifest that poly(PEGMA-co-AEMA-TPE) copolymers will self-assemble into spherical nanoparticles in aqueous environments with sizes between 100 nm and 200 nm. The cell uptake and bioimaging experiment confirm that poly(PEGMA-co-AEMA-TPE) FPNs have excellent biocompatibility and emit strong green fluorescence in a cellular environment. Thus, poly(PEGMA-co-AEMA-TPE) FPNs are excellent candidates for biomedical applications. Copyright © 2018. Published by Elsevier Inc.

Insight on agglomerates of gold nanoparticles in glass based on surface plasmon resonance spectrum: study by multi-spheres T-matrix method

NASA Astrophysics Data System (ADS)

Avakyan, L. A.; Heinz, M.; Skidanenko, A. V.; Yablunovski, K. A.; Ihlemann, J.; Meinertz, J.; Patzig, C.; Dubiel, M.; Bugaev, L. A.

2018-01-01

The formation of a localized surface plasmon resonance (SPR) spectrum of randomly distributed gold nanoparticles in the surface layer of silicate float glass, generated and implanted by UV ArF-excimer laser irradiation of a thin gold layer sputter-coated on the glass surface, was studied by the T-matrix method, which enables particle agglomeration to be taken into account. The experimental technique used is promising for the production of submicron patterns of plasmonic nanoparticles (given by laser masks or gratings) without damage to the glass surface. Analysis of the applicability of the multi-spheres T-matrix (MSTM) method to the studied material was performed through calculations of SPR characteristics for differently arranged and structured gold nanoparticles (gold nanoparticles in solution, particles pairs, and core-shell silver-gold nanoparticles) for which either experimental data or results of the modeling by other methods are available. For the studied gold nanoparticles in glass, it was revealed that the theoretical description of their SPR spectrum requires consideration of the plasmon coupling between particles, which can be done effectively by MSTM calculations. The obtained statistical distributions over particle sizes and over interparticle distances demonstrated the saturation behavior with respect to the number of particles under consideration, which enabled us to determine the effective aggregate of particles, sufficient to form the SPR spectrum. The suggested technique for the fitting of an experimental SPR spectrum of gold nanoparticles in glass by varying the geometrical parameters of the particles aggregate in the recurring calculations of spectrum by MSTM method enabled us to determine statistical characteristics of the aggregate: the average distance between particles, average size, and size distribution of the particles. The fitting strategy of the SPR spectrum presented here can be applied to nanoparticles of any nature and in various substances, and, in principle, can be extended for particles with non-spherical shapes, like ellipsoids, rod-like and other T-matrix-solvable shapes.

Influence of aggregate size on the binding and activation of the first component of human complement by soluble IgG aggregates.

PubMed Central

Doekes, G; Vanes, L A; Daha, M R

1982-01-01

The interaction between small aggregates of human IgG and the first component of human complement was studied. Stabilized soluble IgG aggregates of restricted size were prepared by heat aggregation of human IgG, followed by sucrose-density ultracentrifugation. Human C1 was isolated in its precursor form by euglobulin precipitation, followed by gel filtration and immunoadsorption. A C1 preparation was obtained of which more than 90% was still in its unactivated form. Soluble aggregates containing 20, 10 or 5 molecules IgG, and monomeric IgG were tested for their ability to bind and to activate C1. The binding of C1 was determined by C1 consumption, whereas the activation of C1 was measured as the increased ability of the C1 preparation to consume purified human C4 after the incubation with the aggregates. The three aggregates tested and monomeric IgG were all able to bind and to activate C1, but the efficiency of both processes markedly increased with increasing aggregate-size. Furthermore, it was found that all four preparations activated an appreciable amount of C1 at concentrations that did not result in any detectable C1 fixation. These results confirm earlier suggestion that C1 can be activated during a short, transient binding to small aggregates or immune complexes that have a low avidity for C1, after which the activated form, C1, is released into the medium. PMID:7068172

The effect of pH and concentration upon aggregation transitions in aqueous solutions of poloxamine T701.

PubMed

Armstrong, J K; Chowdhry, B Z; Snowden, M J; Dong, J; Leharne, S A

2001-10-23

Thermally induced aggregation transitions have been investigated for aqueous solutions of the poloxamine block copolymer T701-(OE(4)OP(13))(2)NCH(2)CH(2)N(OP(13)OE(4))(2)-using differential scanning calorimetry. The calorimetric signals obtained were fitted to a mass action model description of aggregation using a previously reported analytical procedure (Patterson et al., Langmuir 13 (1997) 2219). The presence of a central ethylene diamine moiety in the molecular structure renders the T701 molecule basic; this was confirmed and measured by acid/base titration. Basicity is shown to have an important impact upon aggregation. At low pH (2.5), the poloxamine exists in its protonated form and the bulk solution proton concentration is sufficient to suppress de-protonation, aggregation-as a consequence-is shifted to a higher temperature range. Any increase in pH reduces the temperature range over which aggregation occurs. The derived experimental calorimetric parameters, obtained from model fitting procedures, can be used to compute the fraction of poloxamine existing in an aggregated form, at any particular temperature. The data sets obtained were interpolated to show that at human body temperature (310.6 K) the fraction of poloxamine found in its aggregated form is zero at a pH of 2.5. However at a pH of 6.8, the percentage aggregation increases to about 85%. These aggregation characteristics of T701 have important implications for the design of drug delivery systems, which incorporate poloxamines.

Association of Spectrin-Like Proteins with the Actin-Organized Aggregate of Endoplasmic Reticulum in the Spitzenkörper of Gravitropically Tip-Growing Plant Cells1

PubMed Central

Braun, Markus

2001-01-01

Spectrin-like epitopes were immunochemically detected and immunofluorescently localized in gravitropically tip-growing rhizoids and protonemata of characean algae. Antiserum against spectrin from chicken erythrocytes showed cross-reactivity with rhizoid proteins at molecular masses of about 170 and 195 kD. Confocal microscopy revealed a distinct spherical labeling of spectrin-like proteins in the apices of both cell types tightly associated with an apical actin array and a specific subdomain of endoplasmic reticulum (ER), the ER aggregate. The presence of spectrin-like epitopes, the ER aggregate, and the actin cytoskeleton are strictly correlated with active tip growth. Application of cytochalasin D and A23187 has shown that interfering with actin or with the calcium gradient, which cause the disintegration of the ER aggregate and abolish tip growth, inhibits labeling of spectrin-like proteins. At the beginning of the graviresponse in rhizoids the labeling of spectrin-like proteins remained in its symmetrical position at the cell tip, but was clearly displaced to the upper flank in gravistimulated protonemata. These findings support the hypothesis that a displacement of the Spitzenkörper is required for the negative gravitropic response in protonemata, but not for the positive gravitropic response in rhizoids. It is evident that the actin/spectrin system plays a role in maintaining the organization of the ER aggregate and represents an essential part in the mechanism of gravitropic tip growth. PMID:11299343

Effects of Phytoplankton Growth Phase on the Formation and Properties of Marine Snow

NASA Astrophysics Data System (ADS)

Montgomery, Q. W.; Proctor, K. W.; Prairie, J. C.

2016-02-01

Marine snow aggregates often dominate carbon export from the upper mixed layer to the deep ocean. Thus, understanding the formation and the properties of these aggregates is essential to the study of the biological pump. Aggregate formation is determined by both the encounter rate and the stickiness of the particles that they are composed of. Stickiness of phytoplankton has been linked to production of transparent exopolymer particles (TEP), which has been previously shown to vary in concentration throughout different parts of the phytoplankton growth cycle. The objective of this study is to determine the effects of the growth phase of the diatom Thalassiosira weissflogii to both TEP production and the properties of the resulting aggregates produced. Cultures of T. weissflogii were stopped at separate phases of the phytoplankton growth curve and incubated in rotating cylindrical tanks to form aggregates. Aggregate properties such as size, density, and porosity were measured at the end of each period of roller incubation. Preliminary results describe little variation in the size of the aggregates formed from different parts of the growth phase, but show a significant effect of growth phase on aggregate density. Density is an important factor in the settling of marine aggregates. Therefore, variations in aggregate density during different growth phases may have large implications for the efficiency of the biological pump during different stages of a phytoplankton bloom. Further examination will be performed on the potential effects of TEP abundance on the properties of the aggregates formed at separate growth phases and the resulting implications for carbon flux.

Direct comparisons of X-ray scattering and atomistic molecular dynamics simulations for precise acid copolymers and ionomers

DOE PAGES

Buitrago, C. Francisco; Bolintineanu, Dan; Seitz, Michelle E.; ...

2015-02-09

Designing acid- and ion-containing polymers for optimal proton, ion, or water transport would benefit profoundly from predictive models or theories that relate polymer structures with ionomer morphologies. Recently, atomistic molecular dynamics (MD) simulations were performed to study the morphologies of precise poly(ethylene-co-acrylic acid) copolymer and ionomer melts. Here, we present the first direct comparisons between scattering profiles, I(q), calculated from these atomistic MD simulations and experimental X-ray data for 11 materials. This set of precise polymers has spacers of exactly 9, 15, or 21 carbons between acid groups and has been partially neutralized with Li, Na, Cs, or Zn. Inmore » these polymers, the simulations at 120 °C reveal ionic aggregates with a range of morphologies, from compact, isolated aggregates (type 1) to branched, stringy aggregates (type 2) to branched, stringy aggregates that percolate through the simulation box (type 3). Excellent agreement is found between the simulated and experimental scattering peak positions across all polymer types and aggregate morphologies. The shape of the amorphous halo in the simulated I(q) profile is in excellent agreement with experimental I(q). We found that the modified hard-sphere scattering model fits both the simulation and experimental I(q) data for type 1 aggregate morphologies, and the aggregate sizes and separations are in agreement. Given the stringy structure in types 2 and 3, we develop a scattering model based on cylindrical aggregates. Both the spherical and cylindrical scattering models fit I(q) data from the polymers with type 2 and 3 aggregates equally well, and the extracted aggregate radii and inter- and intra-aggregate spacings are in agreement between simulation and experiment. Furthermore, these dimensions are consistent with real-space analyses of the atomistic MD simulations. By combining simulations and experiments, the ionomer scattering peak can be associated with the average distance between branches of type 2 or 3 aggregates. Furthermore, this direct comparison of X-ray scattering data to the atomistic MD simulations is a substantive step toward providing a comprehensive, predictive model for ionomer morphology, gives substantial support for this atomistic MD model, and provides new credibility to the presence of stringy, branched, and percolated ionic aggregates in precise ionomer melts.« less

Effect of the surfactant Tween 80 on the detachment and dispersal of Salmonella enterica Thompson single cells and aggregates from cilantro leaves as revealed by image analysis

USDA-ARS?s Scientific Manuscript database

Biofilms formed by human enteric pathogens on plants are a great concern to the produce industry. Salmonella enterica has the ability to form biofilms and large aggregates on leaf surfaces, including on cilantro leaves. Aggregates that remained attached after rigorous washing of cilantro leaves and ...

In situ observation of melting and crystallization of Si on porous Si3N4 substrate that repels Si melt

NASA Astrophysics Data System (ADS)

Itoh, Hironori; Okamura, Hideyuki; Asanoma, Susumu; Ikemura, Kouhei; Nakayama, Masaharu; Komatsu, Ryuichi

2014-09-01

High temperature in situ observation of melting and crystallization of spherical Si droplets on a substrate with a porous surface was carried out for the first time using an original in situ observation apparatus. The contact angle between the Si melt and the substrate was measured to be 160°, with the Si melt forming spherical droplets on the substrate. During crystallization, a ring-like pattern was observed on the surface of the spherical Si melt droplets due to crystal growth at low levels of supercooling. The solidified spherical Si crystals consisted of single or twin grains. This demonstrates that high-quality spherical Si crystals can be prepared easily and stably by using a Si melt-repelling substrate.

In Situ Evaluation of Calcium Phosphate Nucleation Kinetics and Pathways during Intra- and Extrafibrillar Mineralization of Collagen Matrices

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

Kim, Doyoon; Lee, Byeongdu; Thomopoulos, Stavros

Calcium phosphate (CaP) nanocrystals nucleate and grow in intrafibrillar and/or extrafibrillar spaces of collagen fibrils during the mineralization of bones and teeth. Little is known about the early stages of CaP nucleation and distribution in fibrillar matrices, despite their significant influence on the physical and chemical structures of tissue-level constructs. Using in situ small angle X-ray scattering (SAXS), we examined the nucleation and growth of CaP within collagen matrices and elucidated how a nucleation inhibitor, polyaspartic acid (pAsp), governs mineralization kinetics and pathways at multiple length scales. In situ SAXS analysis clearly revealed that nucleation sites, kinetically-controlled by the nucleationmore » inhibitor, determined the pathways of CaP morphological transformation. Mineralization with pAsp led to intrafibrillar CaP plates with a spatial distribution gradient through the depth of the matrix. Mineralization without pAsp led initially to spherical aggregates of CaP in the entire extrafibrillar spaces. With time, the spherical aggregates transformed into plates at the outermost surface of the collagen matrix, preventing intrafibrillar mineralization inside. The results illuminate mineral nucleation kinetics and real-time nanoparticle distributions within organic matrices in solutions containing body fluid components. Because the macroscale mechanical properties of collagen matrices depend on their mineral content, phase, and arrangement at the nanoscale, this study contributes to better design and fabrication of biomaterials for regenerative medicine.« less

Spin-coated Films of Squarylium Dye J-Aggregates Exhibiting Ultrafast Optical Responses

NASA Astrophysics Data System (ADS)

Tatsuura, Satoshi; Tian, Minquan; Furuki, Makoto; Sato, Yasuhiro; Pu, Lyong Sun; Wada, Osamu

2000-08-01

The formation of J-aggregates of squarylium dye derivatives in spin-coated films is reported. Squarylium dye derivatives with dipropylamino bases are found to spontaneously aggregate in a spin-coated film. Aggregation is promoted when dye molecules are dispersed in a poly(vinyl alcohol) film, and when a spin-coated film of dye molecules is heated in the presence of acid vapor. In particular, J-aggregates formed by exposure to acetic acid vapor show the narrowest spectral width. J-aggregates formed by the acid treatment method are stable at room temperature and the spectral full-width at half maximum of the J-band is 20 nm. Optical response of the acid-treated film is confirmed to exhibit a short relaxation time of bleached absorption of 300 fs.

Fabrication of precision glass shells by joining glass rods

DOEpatents

Gac, Frank D.; Blake, Rodger D.; Day, Delbert E.; Haggerty, John S.

1988-01-01

A method for making uniform spherical shells. The present invention allows niform hollow spheres to be made by first making a void in a body of material. The material is heated so that the viscosity is sufficiently low so that the surface tension will transform the void into a bubble. The bubble is allowed to rise in the body until it is spherical. The excess material is removed from around the void to form a spherical shell with a uniform outside diameter.

Synthetic approaches to construct viral capsid-like spherical nanomaterials.

PubMed

Matsuura, Kazunori

2018-06-06

This feature article describes recent progress in synthetic strategies to construct viral capsid-like spherical nanomaterials using the self-assembly of peptides and/or proteins. By mimicking the self-assembly of spherical viral capsids and clathrin, trigonal peptide conjugates bearing β-sheet-forming peptides, glutathiones, or coiled-coil-forming peptides were developed to construct viral capsid-like particles. β-Annulus peptides from tomato bushy stunt virus self-assembled into viral capsid-like nanocapsules with a size of 30-50 nm, which could encapsulate various guest molecules and be decorated with different molecules on their surface. Rationally designed fusion proteins bearing symmetric assembling units afforded precise viral capsid-like polyhedral assemblies. These synthetic approaches to construct artificial viruses could become useful guidelines to develop novel drug carriers, vaccine platforms, nanotemplates and nanoreactors.

Estimation of Scatterer Diameter by Normalized Power Spectrum of High-Frequency Ultrasonic RF Echo for Assessment of Red Blood Cell Aggregation

NASA Astrophysics Data System (ADS)

Fukushima, Taku; Hasegawa, Hideyuki; Kanai, Hiroshi

2011-07-01

Red blood cell (RBC) aggregation, as one of the determinants of blood viscosity, plays an important role in blood rheology, including the condition of blood. RBC aggregation is induced by the adhesion of RBCs when the electrostatic repulsion between RBCs weakens owing to increases in protein and saturated fatty acid levels in blood, excessive RBC aggregation leads to various circulatory diseases. This study was conducted to establish a noninvasive quantitative method for assessment of RBC aggregation. The power spectrum of ultrasonic RF echoes from nonaggregating RBCs, which shows the frequency property of scattering, exhibits Rayleigh behavior. On the other hand, ultrasonic RF echoes from aggregating RBCs contain the components of reflection, which have no frequency dependence. By dividing the measured power spectrum of echoes from RBCs in the lumen by that of echoes from a posterior wall of the vein in the dorsum manus, the attenuation property of the propagating medium and the frequency responses of transmitting and receiving transducers are removed from the former spectrum. RBC aggregation was assessed by the diameter of a scatterer, which was estimated by minimizing the square difference between the measured normalized power spectrum and the theoretical power spectrum. In this study, spherical scatterers with diameters of 5, 11, 15, and 30 µm were measured in basic experiments. The estimated scatterer diameters were close to the actual diameters. Furthermore, the transient change of the scatterer diameters were measured in an in vivo experiment with respect to a 24-year-old healthy male during the avascularization using a cuff. The estimated diameters (12-22 µm) of RBCs during avascularization were larger than the diameters (4-8 µm) at rest and after recirculation. These results show the possibility of the use of the proposed method for noninvasive assessment of RBC aggregation.

Generation of Aggregates of Mouse Embryonic Stem Cells that Show Symmetry Breaking, Polarization and Emergent Collective Behaviour In Vitro.

PubMed

Baillie-Johnson, Peter; van den Brink, Susanne Carina; Balayo, Tina; Turner, David Andrew; Martinez Arias, Alfonso

2015-11-24

We have developed a protocol improving current Embryoid Body (EB) culture which allows the study of self-organization, symmetry breaking, axial elongation and cell fate specification using aggregates of mouse embryonic stem cells (mESCs) in suspension culture. Small numbers of mESCs are aggregated in basal medium for 48 hr in non-tissue-culture-treated, U-bottomed 96-well plates, after which they are competent to respond to experimental signals. Following treatment, these aggregates begin to show signs of polarized gene expression and gradually alter their morphology from a spherical mass of cells to an elongated, well organized structure in the absence of external asymmetry cues. These structures are not only able to display markers of the three germ layers, but actively display gastrulation-like movements, evidenced by a directional dislodgement of individual cells from the aggregate, which crucially occurs at one region of the elongated structure. This protocol provides a detailed method for the reproducible formation of these aggregates, their stimulation with signals such as Wnt/β-Catenin activation and BMP inhibition and their analysis by single time-point or time-lapse fluorescent microscopy. In addition, we describe modifications to current whole-mount mouse embryo staining procedures for immunocytochemical analysis of specific markers within fixed aggregates. The changes in morphology, gene expression and length of the aggregates can be quantitatively measured, providing information on how signals can alter axial fates. It is envisaged that this system can be applied both to the study of early developmental events such as axial development and organization, and more broadly, the processes of self-organization and cellular decision-making. It may also provide a suitable niche for the generation of cell types present in the embryo that are unobtainable from conventional adherent culture such as spinal cord and motor neurones.

Pulsed electric field (PEF)-induced aggregation between lysozyme, ovalbumin and ovotransferrin in multi-protein system.

PubMed

Wu, Li; Zhao, Wei; Yang, Ruijin; Yan, Wenxu

2015-05-15

The aggregation of multi-proteins is of great interest in food processing and a good understanding of the formation of aggregates during PEF processing is needed for the application of the process to pasteurize protein-based foods. The aggregates formation of a multi-protein system (containing ovalbumin, ovotransferrin and lysozyme) was studied through turbidity, size exclusion chromatography and SDS-PAGE patterns for interaction studies and binding forces. Results from size exclusion chromatography indicated that there was no soluble aggregates formed during PEF processing. The existence of lysozyme was important to form insoluble aggregates in the chosen ovalbumin solution. The results of SDS-PAGE patterns indicated that lysozyme was prone to precipitate, and was relatively the higher component of aggregates. Citric acid could be effective in inhibiting lysozyme from interacting with other proteins during PEF processing. Blocking the free sulphydryl by N-ethylmaleimide (NEM) did not affect aggregation inhibition. Copyright © 2014 Elsevier Ltd. All rights reserved.

Exploring the early steps of amyloid peptide aggregation by computers.

PubMed

Mousseau, Normand; Derreumaux, Philippe

2005-11-01

The assembly of normally soluble proteins into amyloid fibrils is a hallmark of neurodegenerative diseases. Because protein aggregation is very complex, involving a variety of oligomeric metastable intermediates, the detailed aggregation paths and structural characterization of the intermediates remain to be determined. Yet, there is strong evidence that these oligomers, which form early in the process of fibrillogenesis, are cytotoxic. In this paper, we review our current understanding of the underlying factors that promote the aggregation of peptides into amyloid fibrils. We focus here on the structural and dynamic aspects of the aggregation as observed in state-of-the-art computer simulations of amyloid-forming peptides with an emphasis on the activation-relaxation technique.

Photoluminescence spectral reliance on aggregation order of 1,1-Bis(2'-thienyl)-2,3,4,5-tetraphenylsilole.

PubMed

Chen, Junwu; Xu, Bin; Yang, Kaixia; Cao, Yong; Sung, Herman H Y; Williams, Ian D; Tang, Ben Zhong

2005-09-15

1,1-Bis(2'-thienyl)-2,3,4,5-tetraphenylsilole (1) was prepared and characterized crystallographically. Silole 1 exhibited aggregation-induced emission (AIE) behavior like other 2,3,4,5-tetraphenylsiloles. Unexpectedly, aggregates formed in water/acetone (6:4 by volume) mixture emitted a blue light that peaked at 474 nm, while aggregates formed in the mixtures with higher water fractions emitted green light that peaked at 500 nm. Transmission electron microscopy demonstrated that the aggregates formed in the mixture with water fraction of 60% were single crystals, while aggregates that formed in the mixture with water fraction of 90% were irregular and poorly ordered particles. The unusual PL spectral reliance on aggregation order was further confirmed by PL emissions of macroscopic crystal powders and amorphous powders of the silole in the dry state. PL spectral blue shifting was observed upon aging of the poorly ordered aggregates formed in mixtures with water fractions of 70-90%, and they finally exhibited the same blue emission as the crystalline aggregates. The as-deposited thin solid film was amorphous and it could be transformed to a transparent crystalline film upon treatment in the vapor of an ethanol/water (1:1 by volume) mixture, along with PL spectral blue shifting due to changing of aggregation order. It was also found that the crystalline film showed a blue-shifted absorption spectrum relative to the amorphous film and the shift of the absorption edge of the spectra could match that of corresponding PL spectra. The FT-IR spectrum of crystal powders of 1 displayed more vibration modes compared with that of amorphous powders, suggesting the existence of different pi-overlaps or different molecular conformations. The crystals of 1-methyl-1,2,3,4,5-pentaphenylsilole and hexaphenylsilole also showed blue-shifted PL emissions of their amorphous solids, with a comparable PL spectral shift of 1. Developing of a silole solution on a TLC plate readily brought about an amorphous thin layer. Our results suggest that crystalline films of AIE-active siloles are potential emissive layers for efficient blue OLEDs with stable color and long lifetime.

Misfolded rhodopsin mutants display variable aggregation properties.

PubMed

Gragg, Megan; Park, Paul S-H

2018-06-08

The largest class of rhodopsin mutations causing autosomal dominant retinitis pigmentosa (adRP) is mutations that lead to misfolding and aggregation of the receptor. The misfolding mutants have been characterized biochemically, and categorized as either partial or complete misfolding mutants. This classification is incomplete and does not provide sufficient information to fully understand the disease pathogenesis and evaluate therapeutic strategies. A Förster resonance energy transfer (FRET) method was utilized to directly assess the aggregation properties of misfolding rhodopsin mutants within the cell. Partial (P23H and P267L) and complete (G188R, H211P, and P267R) misfolding mutants were characterized to reveal variability in aggregation properties. The complete misfolding mutants all behaved similarly, forming aggregates when expressed alone, minimally interacting with the wild-type receptor when coexpressed, and were unresponsive to treatment with the pharmacological chaperone 9-cis retinal. In contrast, variability was observed between the partial misfolding mutants. In the opsin form, the P23H mutant behaved similarly as the complete misfolding mutants. In contrast, the opsin form of the P267L mutant existed as both aggregates and oligomers when expressed alone and formed mostly oligomers with the wild-type receptor when coexpressed. The partial misfolding mutants both reacted similarly to the pharmacological chaperone 9-cis retinal, displaying improved folding and oligomerization when expressed alone but aggregating with wild-type receptor when coexpressed. The observed differences in aggregation properties and effect of 9-cis retinal predict different outcomes in disease pathophysiology and suggest that retinoid-based chaperones will be ineffective or even detrimental. Copyright © 2018 Elsevier B.V. All rights reserved.

SAXS characterization of the interactions among digested food compounds and the anti-oxidant and anti-inflammatory activities of the formed nanocomplexes.

PubMed

Yang, Yingkang; Wang, Xiaoqi; Chen, Guijie; Zhou, Wenhua; Zeng, Xiaoxiong; Hu, Bing; Li, Yunqi; Huang, Qingrong

2018-06-06

In the present study, small angle X-ray scattering (SAXS) is applied to investigate the interaction between caseinophosphopeptides (CPP), the major digested product of milk protein, and chitosan (CS) under simulated gastrointestinal (GI) pH conditions. The change in pH value from the gastric to small intestinal environment induces complexation between CPP and CS, which is mainly driven by electrostatic interactions. The fractal dimension (Df) value of the domains inside the CPP-CS complexes is greater than 3, indicating the formation of dense particles/aggregates at the nanoscale. The Df value generally increases with an increase in the CS/CPP mass ratio. As a representative of polyphenols, (-)-epigallocatechin gallate (EGCG) associates with CS and CPP, forming nanocomplexes with a spherical shape and average particle size of around 208 nm. The formed CS-EGCG-CPP nanocomplexes do not affect the antioxidant activity of EGCG in the in vitro assays. Moreover, in the cellular assay, the nanocomplexes protect the RAW264.7 cells against H2O2-induced oxidative injury. In addition, the nanocomplexes significantly inhibit the lipopolysaccharide (LPS)-induced production of nitric oxide (NO), TNF-α, IL-1β and IL-6. Furthermore, they inhibit the expression of iNOS, phosphorylation and degradation of IκB, as well as the translocation of NF-κB p65; this indicates that the mechanism for their anti-inflammatory activity is via the mediation of the NF-κB signaling pathway.

Retrieval of Haze Properties in Pluto's Atmosphere from New Horizons Observations

NASA Astrophysics Data System (ADS)

Fan, S.; Gao, P.; Yung, Y. L.

2017-12-01

On July 14th, 2015, New Horizons performed its historic close approach of Pluto, giving humanity unprecedented observations of the dwarf planet's atmosphere. One of the amazing features seen was the multi-layered haze in its atmosphere. The haze was detected both at visible wavelengths by the Long Range Reconnaissance Imager (LORRI) from direct imaging and in the ultraviolet by the Alice spectrograph from solar occultations. Preliminary analysis using simplified models showed that neither spherical nor 2-dimensional aggregate particles could satisfy both sets of observations. In this work, we present a joint retrieval of haze particles using both LORRI and Alice data, which examines various size distributions and dimensions of aggregate particles. We map out the haze particles' phase function by the forward scattering and extinction properties by the occultation. With the combination of these two approaches, the Haze's properties of size and shape are constrained.

Second harmonic generation from small particle aggregates

NASA Astrophysics Data System (ADS)

Mochan, W. Luis; Ortiz, Guillermo P.; Mendoza, Bernardo S.; Brudny, Vera L.

2001-03-01

Novel nanofabrication techniques are capable of producing nanoparticles with controled structures which include small clusters, self-assembled particles, quantum dots, vesicles, etc. The non-linear optical scattering of these structures are important for applications, and can be used for their physical characterization. The second harmonic (SH) field radiated by a single small spherical particle has surface and bulk, dipolar and quadrupolar contributions of similar intensities and is strongly dependent of the local environment of the particle [1], in contrast to the linear case. In this work we calculate the nonlinear scattering by particle aggregates and we investigate the effects on the SH generation of the disorder induced field fluctuations and of the localization of light. We acknowledge the partial support from DGAPA-UNAM (grant IN110999), Conacyt (31120-E and 26651-E), CIP and UBACyT. [1] Vera L. Brudny, Bernardo S. Mendoza, and W. Luis Mochán, Phys. Rev. B 62, 11152 (2000).

Mesoscale simulation of concrete spall failure

NASA Astrophysics Data System (ADS)

Knell, S.; Sauer, M.; Millon, O.; Riedel, W.

2012-05-01

Although intensively studied, it is still being debated which physical mechanisms are responsible for the increase of dynamic strength and fracture energy of concrete observed at high loading rates, and to what extent structural inertia forces on different scales contribute to the observation. We present a new approach for the three dimensional mesoscale modelling of dynamic damage and cracking in concrete. Concrete is approximated as a composite of spherical elastic aggregates of mm to cm size embedded in an elastic cement stone matrix. Cracking within the matrix and at aggregate interfaces in the μm range are modelled with adaptively inserted—initially rigid—cohesive interface elements. The model is applied to analyse the dynamic tensile failure observed in Hopkinson-Bar spallation experiments with strain rates up to 100/s. The influence of the key mesoscale failure parameters of strength, fracture energy and relative weakening of the ITZ on macromechanic strength, momentum and energy conservation is numerically investigated.

The role of nonlinear viscoelasticity on the functionality of laminating shortenings

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

Macias-Rodriguez, Braulio A.; Peyronel, Fernanda; Marangoni, Alejandro G.

The rheology of fats is essential for the development of homogeneous and continuous layered structures of doughs. Here, we define laminating shortenings in terms of rheological behavior displayed during linear-to-nonlinear shear deformations, investigated by large amplitude oscillatory shear rheology. Likewise, we associate the rheological behavior of the shortenings with structural length scales elucidated by ultra-small angle x-ray scattering and cryo-electron microscopy. Shortenings exhibited solid-like viscoelastic and viscoelastoplastic behaviors in the linear and nonlinear regimes respectively. In the nonlinear region, laminating shortenings dissipated more viscous energy (larger normalized dynamic viscosities) than a cake bakery shortening. The fat solid-like network of laminatingmore » shortening displayed a three-hierarchy structure and layered crystal aggregates, in comparison to two-hierarchy structure and spherical-like crystal aggregates of a cake shortening. We argue that the observed rheology, correlated to the structural network, is crucial for optimal laminating performance of shortenings.« less

Stability of aggregates in the environment: role of solid bridging

NASA Astrophysics Data System (ADS)

Seiphoori, A.; Jerolmack, D. J.; Arratia, P. E.

2017-12-01

Colloids in suspension may form larger flocs under favorable conditions, via diffusion- or reaction-limited aggregation. In addition, the process of drying colloidal suspensions drives colloids together via hydrodynamic forces to form aggregates, that may be stable or unstable when subject to re-wetting and transport. Channel banks, shorelines and hillslopes are examples where the periodic wetting and drying results in the aggregation of muds. If aggregates disperse, the mud structure is unstable to subsequent wetting or fluid shear and can easily be detached and transported to rivers and coasts. The effective friction that governs hillslope and channel-bank soil creep rates also depends on the stability of the soil aggregates. Yet, few studies probe the particle-scale assembly or stability of aggregates subject to environmental loads, and the effects of shape or size heterogeneity have not been examined in detail. Here we investigate the formation and stability of aggregates subject to passive re-wetting (by misting) and shearing using a simple Poiseuille flow in a microfluidic device. We study the kinetics of a wide range of silicate colloids of different size and surface charge properties using in situ microscopy and particle tracking. We find that negatively charged silica microspheres are dragged by the retreating edge of an evaporating drop and are resuspended easily on re-wetting, showing that aggregates are unstable. In contrast, a bi-disperse suspension created by the addition of silica nanoparticles forms stable deposits, where nanoparticles bind larger particles by bridging the interparticle space, a mechanism similar to capillary bridging that we refer to as "solid bridging." Although aggregate structure and dynamics of the bi-disperse system changes quantitatively with surface-charge of the nanoparticles, smaller particles always conferred stability on the aggregates. Investigation of other colloids, including asbestos fibers and various clays, reveals that this solid bridging effect is robust across variations in particle shape and material composition. These experiments suggest that natural mud and soil may form more stable aggregates than would naively be expected by considering the charge effects alone, because their inherent size heterogeneity is conducive to solid bridging.

A preliminary assessment of asteroid shapes produced by impact disruption and re-creation: Application to the AIDA target.

NASA Astrophysics Data System (ADS)

Barnouin, Olivier; Michel, Patrick; Richardson, Derek

2016-04-01

In order to understand the origin of the 65803 Didymos, the target of the Asteroid Impact and Deflection Assessment mission, and gain insights on the origin and evolution of the asteroid's162173 Ryugu and 101955 Bennu, we investigate systematically the shapes of all re-accumulated fragments produced by the catastrophic disruption of a parent body that is 1 km in diameter or larger. These new fragments eventually become new asteroids of the size that current sample-return missions plan to explore. We choose a range of impact conditions by varying the parent bodies' strength, size and porosity, and the velocity and size of the projectile. Impact conditions range from near the catastrophic threshold, usually designated by Q*, where half of the target's mass escapes, to far greater values above this threshold. Our numerical investigations of the catastrophic disruption, which are undertaken using an SPH hydrocode, include a model of fragmentation for porous materials. The gravitationally dominated phase of reaccumulation of our asteroids is computed using the N-body code pkdgrav. At sufficiently slow impact speeds in the N-body model, particles are permitted to stick, forming irregular, competent pieces that can gather into non-idealized rubble piles as a result of re-accumulation. Shape and spin information of re-accumulated bodies are thus preserved. Due to numerical expense, this first study uses what we call a hard-sphere model, rather than a soft-sphere spring and dashpot model. This latter model is more commonly used in granular flow simulations for which detailed treatment of the multicontact physics is needed, which is not the case here, and comes at the expense of much smaller timesteps. With the hard-sphere model, there are three supported collision outcomes for bonded aggregates: sticking on contact (to grow the aggregate); bouncing (computed for these generally non-central impacts); and fragmentation (wherein the particles involved become detached from their respective aggregates and proceed to bounce as rigid spheres, possibly releasing more particles). We adjusted the strength of the forming aggregates to the measured strength of materials in the lab, scaled to the aggregate size, by using strength size scaling rules. In the future we expect to compare our hard-sphere models to a few soft-sphere for reasonable granular materials to best characterize differences between the two approaches, if any. Our results indicate that while 25143 Itokawa-like potato-shaped asteroids are typically the outcome of disruption, often more spherical or "top-shaped" asteroids can also be produced. Our results confirm what others have already noted, namely that a "top-shaped" or diamond shaped asteroid is not necessarily the result of the formation of YORP spin-up. Other criteria besides just shape need to be developed to determine whether or not the evolution of an asteroid and its surface geology have been dominated by YORP-related processes or by impact-derived re-accretion.

A 31-residue peptide induces aggregation of tau’s microtubule-binding region in cells

PubMed Central

Stöhr, Jan; Wu, Haifan; Nick, Mimi; Wu, Yibing; Bhate, Manasi; Condello, Carlo; Johnson, Noah; Rodgers, Jeffrey; Lemmin, Thomas; Achyraya, Srabasti; Becker, Julia; Robinson, Kathleen; Kelly, Mark J.S.; Gai, Feng; Stubbs, Gerald; Prusiner, Stanley B.; DeGrado, William F.

2018-01-01

The self-propagation of misfolded conformations of tau underlies neurodegenerative diseases, including Alzheimer’s disease. There is considerable interest in discovering the minimal sequence and active conformational nucleus that defines this self-propagating event. The microtubule-binding region, spanning residues 244-372, reproduces much of the aggregation behavior of tau in cells and animal models. Further dissection of the amyloid-forming region to a hexapeptide from the third microtubule-binding repeat resulted in a peptide that rapidly forms fibrils in vitro. We show here that this peptide lacks the ability to seed aggregation of tau244-372 in cells. However, as the hexapeptide is gradually extended to 31 residues, the peptides aggregate more slowly and gain potent activity to induce aggregation of tau244-372 in cells. X-ray fiber diffraction, hydrogen-deuterium exchange and solids NMR studies map the beta-forming region to a 25-residue sequence. Thus, the nucleus for self-propagating aggregation of tau244-372 in cells is packaged in a remarkably small peptide. PMID:28837163

COMPUTER SIMULATION STUDY OF AMYLOID FIBRIL FORMATION BY PALINDROMIC SEQUENCES IN PRION PEPTIDES

PubMed Central

Wagoner, Victoria; Cheon, Mookyung; Chang, Iksoo; Hall, Carol

2011-01-01

We simulate the aggregation of large systems containing palindromic peptides from the Syrian hamster prion protein SHaPrP 113–120 (AGAAAAGA) and the mouse prion protein MoPrP 111–120 (VAGAAAAGAV) and eight sequence variations: GAAAAAAG, (AG)4, A8, GAAAGAAA, A10, V10, GAVAAAAVAG, and VAVAAAAVAV The first two peptides are thought to act as the Velcro that holds the parent prion proteins together in amyloid structures and can form fibrils themselves. Kinetic events along the fibrillization pathway influence the types of structures that occur and variations in the sequence affect aggregation kinetics and fibrillar structure. Discontinuous molecular dynamics simulations using the PRIME20 force field are performed on systems containing 48 peptides starting from a random coil configuration. Depending on the sequence, fibrillar structures form spontaneously over a range of temperatures, below which amorphous aggregates form and above which no aggregation occurs. AGAAAAGA forms well organized fibrillar structures whereas VAGAAAAGAV forms less well organized structures that are partially fibrillar and partially amorphous. The degree of order in the fibrillar structure stems in part from the types of kinetic events leading up to its formation, with AGAAAAGA forming less amorphous structures early in the simulation than VAGAAAAGAV. The ability to form fibrils increases as the chain length and the length of the stretch of hydrophobic residues increase. However as the hydrophobicity of the sequence increases, the ability to form well-ordered structures decreases. Thus, longer hydrophobic sequences form slightly disordered aggregates that are partially fibrillar and partially amorphous. Subtle changes in sequence result in slightly different fibril structures. PMID:21557317

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

Alred, Erik J.; Scheele, Emily G.; Berhanu, Workalemahu M.

Recent experiments indicate a connection between the structure of amyloid aggregates and their cytotoxicity as related to neurodegenerative diseases. Of particular interest is the Iowa Mutant, which causes early-onset of Alzheimer's disease. While wild-type Amyloid β-peptides form only parallel beta-sheet aggregates, the mutant also forms meta-stable antiparallel beta sheets. Since these structural variations may cause the difference in the pathological effects of the two Aβ-peptides, we have studied in silico the relative stability of the wild type and Iowa mutant in both parallel and antiparallel forms. We compare regular molecular dynamics simulations with such where the viscosity of the samplesmore » is reduced, which, we show, leads to higher sampling efficiency. By analyzing and comparing these four sets of all-atom molecular dynamics simulations, we probe the role of the various factors that could lead to the structural differences. Our analysis indicates that the parallel forms of both wild type and Iowa mutant aggregates are stable, while the antiparallel aggregates are meta-stable for the Iowa mutant and not stable for the wild type. The differences result from the direct alignment of hydrophobic interactions in the in-register parallel oligomers, making them more stable than the antiparallel aggregates. The slightly higher thermodynamic stability of the Iowa mutant fibril-like oligomers in its parallel organization over that in antiparallel form is supported by previous experimental measurements showing slow inter-conversion of antiparallel aggregates into parallel ones. Knowledge of the mechanism that selects between parallel and antiparallel conformations and determines their relative stability may open new avenues for the development of therapies targeting familial forms of early-onset Alzheimer's disease.« less

Formation of soluble amyloid oligomers and amyloid fibrils by the multifunctional protein vitronectin

PubMed Central

Shin, Thuzar M; Isas, J Mario; Hsieh, Chia-Ling; Kayed, Rakez; Glabe, Charles G; Langen, Ralf; Chen, Jeannie

2008-01-01

Background The multifunctional protein vitronectin is present within the deposits associated with Alzheimer disease (AD), age-related macular degeneration (AMD), atherosclerosis, systemic amyloidoses, and glomerulonephritis. The extent to which vitronectin contributes to amyloid formation within these plaques, which contain misfolded, amyloidogenic proteins, and the role of vitronectin in the pathophysiology of the aforementioned diseases is currently unknown. The investigation of vitronectin aggregation is significant since the formation of oligomeric and fibrillar structures are common features of amyloid proteins. Results We observed vitronectin immunoreactivity in senile plaques of AD brain, which exhibited overlap with the amyloid fibril-specific OC antibody, suggesting that vitronectin is deposited at sites of amyloid formation. Of particular interest is the growing body of evidence indicating that soluble nonfibrillar oligomers may be responsible for the development and progression of amyloid diseases. In this study we demonstrate that both plasma-purified and recombinant human vitronectin readily form spherical oligomers and typical amyloid fibrils. Vitronectin oligomers are toxic to cultured neuroblastoma and retinal pigment epithelium (RPE) cells, possibly via a membrane-dependent mechanism, as they cause leakage of synthetic vesicles. Oligomer toxicity was attenuated in RPE cells by the anti-oligomer A11 antibody. Vitronectin fibrils contain a C-terminal protease-resistant fragment, which may approximate the core region of residues essential to amyloid formation. Conclusion These data reveal the propensity of vitronectin to behave as an amyloid protein and put forth the possibilities that accumulation of misfolded vitronectin may contribute to aggregate formation seen in age-related amyloid diseases. PMID:18939994

Polymeric nanoparticles of cholesterol-modified glycol chitosan for doxorubicin delivery: preparation and in-vitro and in-vivo characterization.

PubMed

Yu, Jing-Mou; Li, Yong-Jie; Qiu, Li-Yan; Jin, Yi

2009-06-01

Polymeric nanoparticles have been extensively studied as drug carriers. Chitosan and its derivatives have attracted significant attention in this regard but have limited application because of insolubility in biological solution. In this work, we attempted to utilize cholesterol-modified glycol chitosan (CHGC) self-aggregated nanoparticles to increase aqueous solubility, and to reduce side effects and enhance the antitumour efficacy of the anticancer drug doxorubicin. Methods CHGC nanoparticles were loaded with doxorubicin by a dialysis method, and their characteristics were determined by transmission electron microscopy examination, light-scattering study, in-vitro drug-release study, pharmacokinetic study in rats and in-vivo antitumour activity in mice. The resulting doxorubicin-loaded CHGC nanoparticles (DCNs) formed self-assembled aggregates in aqueous medium. From the observation by transmission electron microscopy, DCNs were almost spherical in shape. The mean diameters of these nanoparticles determined by dynamic light scattering were in the range of 237-336 nm as the doxorubicin-loading content increased from 1.73% to 9.36%. In-vitro data indicated that doxorubicin release from DCNs was much faster in phosphate-buffered saline at pH 5.5 than at pH 6.5 and 7.4, and the release rate was dependent on the loading content of doxorubicin in these nanoparticles. It was observed that DCN-16 (drug loaded content: 9.36%) exhibited prolonged circulation time in rat plasma and showed higher antitumour efficacy against S180-bearing mice than free doxorubicin. These results indicated that CHGC nanoparticles had potential as a carrier for insoluble anticancer drugs in cancer therapy.

Creation of catalytically active particles from enzymes crosslinked with a natural bifunctional agent--homocysteine thiolactone.

PubMed

Stroylova, Yulia Y; Semenyuk, Pavel I; Asriyantz, Regina A; Gaillard, Cedric; Haertlé, Thomas; Muronetz, Vladimir I

2014-09-01

The current study describes an approach to creation of catalytically active particles with increased stability from enzymes by N-homocysteinylation, a naturally presented protein modification. Enzymatic activities and properties of two globular tetrameric enzymes glyceraldehyde-3-phosphate dehydrogenase (GAPDH) and lactate dehydrogenase (LDH) were studied before and after N-homocysteinylation. Modification of these proteins concerns the accessible lysine residues and introduces an average of 2-2,5 homocysteine residues per protein monomer. Formation of a range of aggregates was observed for both enzymes, which assemble via formation of intermolecular noncovalent bonds and by disulfide bonds. It was demonstrated that both studied enzymes retain their catalytic activities on modification and the subsequent formation of oligomeric forms. At low concentrations of homocysteine thiolactone, modification of GAPDH leads not only to prevention of spontaneous inactivation but also increases thermal stability of this enzyme on heating to 80°C. A moderate reduction of the activity of GAPDH observed in case of its crosslinking with 50-fold excess of homocysteine thiolactone per lysine is probably caused by hindered substrate diffusion. Spherical particles of 100 nm and larger diameters were observed by transmission electron microscopy and atomic force microscope techniques after modification of GAPDH with different homocysteine thiolactone concentrations. In case of LDH, branched fibril-like aggregates were observed under the same conditions. Interestingly, crosslinked samples of both proteins were found to have reversible thermal denaturation profiles, indicating that modification with homocysteine thiolactone stabilizes the spatial structure of these enzymes. © 2014 Wiley Periodicals, Inc.

Stirring Up Acceptor Phase and Controlling Morphology via Choosing Appropriate Rigid Aryl Rings as Lever Arms in Symmetry-Breaking Benzodithiophene for High-Performance Fullerene and Fullerene-Free Polymer Solar Cells.

PubMed

Liu, Deyu; Wang, Junyi; Gu, Chunyang; Li, Yonghai; Bao, Xichang; Yang, Renqiang

2018-02-01

Two series of new polymers with medium and wide bandgaps to match fullerene (PC 71 BM) and fullerene-free 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene (ITIC) acceptors are designed and synthesized, respectively. For constructing the key donor building blocks, the effective symmetry-breaking strategy is employed. Two common aromatic rings (thiophene and benzene) are chosen as one side substituted groups in the asymmetric benzodithiophene (BDT) monomers. In addition, another rigid benzene ring is inserted between aryl and thioether in the side chains, which results in larger twisting and destroying the aggregation and forming longer lever arms. As a result, highly ordered polymers (PBDTsTh-FBT and PBDTsPh-FBT) with strong aggregation properties can blend well with roughly spherical PC 71 BM, while amorphous polymers (PBDTsThPh-BDD and PBDTsPhPh-BDD) with long and rigid aryl rings show good miscibility with elongated ITIC, and finally, both devices exhibit excellent power conversion efficiencies over 10%. Thus, it clearly shows that the asymmetric BDT unit is an excellent donor building block to construct highly efficient photovoltaic polymers. Meanwhile, this work demonstrates that it is not necessary that high-performance fullerene-free polymer solar cells (PSCs) require highly ordered microstructures in the blending films, different from the fullerene-based PSCs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorption of Amelogenin onto Self-Assembled and Fluoroapatite Surfaces

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

Tarasevich, Barbara J.; Lea, Alan S.; Bernt, William

Abstract. The interactions of proteins at surfaces are of great importance to biomineralizaton processes and to the development and function of biomaterials. Amelogenin is a unique biomineralization protein because it self-assembles to form supramolecular structures called “nanospheres,” spherical aggregates of monomers that are 20-60 nm in diameter. Although the nanosphere quaternary structure has been observed in solution, the quaternary structure of amelogenin adsorbed onto surfaces is also of great interest because the surface structure is critical to its function. We report studies of the adsorption of the amelogenin onto self-assembled monolayers (SAMs) with COOH and CH3 end group functionality andmore » single crystal fluoroapatite (FAP). Dynamic light scattering (DLS) experiments showed that the solutions contained nanospheres and aggregates of nanospheres. Protein adsorption onto the various substrates was evidenced by null ellipsometry, x-ray photoelectron spectroscopy (XPS), and external reflectance Fourier transform infrared spectroscopy (ERFTIR). Although only nanospheres were observed in solution, ellipsometry and atomic force microscopy (AFM) indicated that the protein adsorbates were much smaller structures than the original nanospheres, from monomers to small oligomers in size. Monomer adsorption was promoted onto the CH3 surfaces and small oligomer adsorption was promoted onto the COOH and FAP substrates. In some cases, remnants of the original nanospheres adsorbed as multilayers on top of the underlying subnanosphere layers. This work suggests that amelogenin can adsorb by the “shedding” or disassembling of substructures from the nanospheres onto substrates and indicates that amelogenin may have a range of possible quaternary structures depending on whether it is in solution or interacting with surfaces.« less

Diatom-associated bacteria are required for aggregation of Thalassiosira weissflogii

PubMed Central

Gärdes, Astrid; Iversen, Morten H; Grossart, Hans-Peter; Passow, Uta; Ullrich, Matthias S

2011-01-01

Aggregation of algae, mainly diatoms, is an important process in marine systems leading to the settling of particulate organic carbon predominantly in the form of marine snow. Exudation products of phytoplankton form transparent exopolymer particles (TEP), which acts as the glue for particle aggregation. Heterotrophic bacteria interacting with phytoplankton may influence TEP formation and phytoplankton aggregation. This bacterial impact has not been explored in detail. We hypothesized that bacteria attaching to Thalassiosira weissflogii might interact in a yet-to-be determined manner, which could impact TEP formation and aggregate abundance. The role of individual T. weissflogii-attaching and free-living new bacterial isolates for TEP production and diatom aggregation was investigated in vitro. T. weissflogii did not aggregate in axenic culture, and striking differences in aggregation dynamics and TEP abundance were observed when diatom cultures were inoculated with either diatom-attaching or free-living bacteria. The data indicated that free-living bacteria might not influence aggregation whereas bacteria attaching to diatom cells may increase aggregate formation. Interestingly, photosynthetically inactivated T. weissflogii cells did not aggregate regardless of the presence of bacteria. Comparison of aggregate formation, TEP production, aggregate sinking velocity and solid hydrated density revealed remarkable differences. Both, photosynthetically active T. weissflogii and specific diatom-attaching bacteria were required for aggregation. It was concluded that interactions between heterotrophic bacteria and diatoms increased aggregate formation and particle sinking and thus may enhance the efficiency of the biological pump. PMID:20827289

Wetting of nonconserved residue-backbones: A feature indicative of aggregation associated regions of proteins.

PubMed

Pradhan, Mohan R; Pal, Arumay; Hu, Zhongqiao; Kannan, Srinivasaraghavan; Chee Keong, Kwoh; Lane, David P; Verma, Chandra S

2016-02-01

Aggregation is an irreversible form of protein complexation and often toxic to cells. The process entails partial or major unfolding that is largely driven by hydration. We model the role of hydration in aggregation using "Dehydrons." "Dehydrons" are unsatisfied backbone hydrogen bonds in proteins that seek shielding from water molecules by associating with ligands or proteins. We find that the residues at aggregation interfaces have hydrated backbones, and in contrast to other forms of protein-protein interactions, are under less evolutionary pressure to be conserved. Combining evolutionary conservation of residues and extent of backbone hydration allows us to distinguish regions on proteins associated with aggregation (non-conserved dehydron-residues) from other interaction interfaces (conserved dehydron-residues). This novel feature can complement the existing strategies used to investigate protein aggregation/complexation. © 2015 Wiley Periodicals, Inc.

Protein aggregate turbidity: Simulation of turbidity profiles for mixed-aggregation reactions.

PubMed

Hall, Damien; Zhao, Ran; Dehlsen, Ian; Bloomfield, Nathaniel; Williams, Steven R; Arisaka, Fumio; Goto, Yuji; Carver, John A

2016-04-01

Due to their colloidal nature, all protein aggregates scatter light in the visible wavelength region when formed in aqueous solution. This phenomenon makes solution turbidity, a quantity proportional to the relative loss in forward intensity of scattered light, a convenient method for monitoring protein aggregation in biochemical assays. Although turbidity is often taken to be a linear descriptor of the progress of aggregation reactions, this assumption is usually made without performing the necessary checks to provide it with a firm underlying basis. In this article, we outline utilitarian methods for simulating the turbidity generated by homogeneous and mixed-protein aggregation reactions containing fibrous, amorphous, and crystalline structures. The approach is based on a combination of Rayleigh-Gans-Debye theory and approximate forms of the Mie scattering equations. Crown Copyright © 2015. Published by Elsevier Inc. All rights reserved.

Analytical expression for a class of spherically symmetric solutions in Lorentz-breaking massive gravity

NASA Astrophysics Data System (ADS)

Li, Ping; Li, Xin-zhou; Xi, Ping

2016-06-01

We present a detailed study of the spherically symmetric solutions in Lorentz-breaking massive gravity. There is an undetermined function { F }(X,{w}1,{w}2,{w}3) in the action of Stückelberg fields {S}φ ={{{Λ }}}4\\int {{{d}}}4x\\sqrt{-g}{ F }, which should be resolved through physical means. In general relativity, the spherically symmetric solution to the Einstein equation is a benchmark and its massive deformation also plays a crucial role in Lorentz-breaking massive gravity. { F } will satisfy the constraint equation {T}01=0 from the spherically symmetric Einstein tensor {G}01=0, if we maintain that any reasonable physical theory should possess the spherically symmetric solutions. The Stückelberg field {φ }i is taken as a ‘hedgehog’ configuration {φ }i=φ (r){x}i/r, whose stability is guaranteed by the topological one. Under this ansätz, {T}01=0 is reduced to d{ F }=0. The functions { F } for d{ F }=0 form a commutative ring {R}{ F }. We obtain an expression of the solution to the functional differential equation with spherical symmetry if { F }\\in {R}{ F }. If { F }\\in {R}{ F } and \\partial { F }/\\partial X=0, the functions { F } form a subring {S}{ F }\\subset {R}{ F }. We show that the metric is Schwarzschild, Schwarzschild-AdS or Schwarzschild-dS if { F }\\in {S}{ F }. When { F }\\in {R}{ F } but { F }\

Geometrical characterization of fluorescently labelled surfaces from noisy 3D microscopy data.

PubMed

Shelton, Elijah; Serwane, Friedhelm; Campàs, Otger

2018-03-01

Modern fluorescence microscopy enables fast 3D imaging of biological and inert systems alike. In many studies, it is important to detect the surface of objects and quantitatively characterize its local geometry, including its mean curvature. We present a fully automated algorithm to determine the location and curvatures of an object from 3D fluorescence images, such as those obtained using confocal or light-sheet microscopy. The algorithm aims at reconstructing surface labelled objects with spherical topology and mild deformations from the spherical geometry with high accuracy, rather than reconstructing arbitrarily deformed objects with lower fidelity. Using both synthetic data with known geometrical characteristics and experimental data of spherical objects, we characterize the algorithm's accuracy over the range of conditions and parameters typically encountered in 3D fluorescence imaging. We show that the algorithm can detect the location of the surface and obtain a map of local mean curvatures with relative errors typically below 2% and 20%, respectively, even in the presence of substantial levels of noise. Finally, we apply this algorithm to analyse the shape and curvature map of fluorescently labelled oil droplets embedded within multicellular aggregates and deformed by cellular forces. © 2017 The Authors Journal of Microscopy © 2017 Royal Microscopical Society.

Plasmonic Spherical Heterodimers: Reversal of Optical Binding Force Based on the Forced Breaking of Symmetry.

PubMed

Mahdy, M R C; Danesh, Md; Zhang, Tianhang; Ding, Weiqiang; Rivy, Hamim Mahmud; Chowdhury, Ariful Bari; Mehmood, M Q

2018-02-16

The stimulating connection between the reversal of near-field plasmonic binding force and the role of symmetry-breaking has not been investigated comprehensively in the literature. In this work, the symmetry of spherical plasmonic heterodimer-setup is broken forcefully by shining the light from a specific side of the set-up instead of impinging it from the top. We demonstrate that for the forced symmetry-broken spherical heterodimer-configurations: reversal of lateral and longitudinal near-field binding force follow completely distinct mechanisms. Interestingly, the reversal of longitudinal binding force can be easily controlled either by changing the direction of light propagation or by varying their relative orientation. This simple process of controlling binding force may open a novel generic way of optical manipulation even with the heterodimers of other shapes. Though it is commonly believed that the reversal of near-field plasmonic binding force should naturally occur for the presence of bonding and anti-bonding modes or at least for the Fano resonance (and plasmonic forces mostly arise from the surface force), our study based on Lorentz-force dynamics suggests notably opposite proposals for the aforementioned cases. Observations in this article can be very useful for improved sensors, particle clustering and aggregation.

Dynamics of mutated GFAP aggregates revealed by real-time imaging of an astrocyte model of Alexander disease.

PubMed

Mignot, Cyril; Delarasse, Cécile; Escaich, Séverine; Della Gaspera, Bruno; Noé, Eric; Colucci-Guyon, Emma; Babinet, Charles; Pekny, Milos; Vicart, Patrick; Boespflug-Tanguy, Odile; Dautigny, André; Rodriguez, Diana; Pham-Dinh, Danielle

2007-08-01

Alexander disease (AxD) is a rare neurodegenerative disorder characterized by large cytoplasmic aggregates in astrocytes and myelin abnormalities and caused by dominant mutations in the gene encoding glial fibrillary acidic protein (GFAP), the main intermediate filament protein in astrocytes. We tested the effects of three mutations (R236H, R76H and L232P) associated with AxD in cells transiently expressing mutated GFAP fused to green fluorescent protein (GFP). Mutated GFAP-GFP expressed in astrocytes formed networks or aggregates similar to those found in the brains of patients with the disease. Time-lapse recordings of living astrocytes showed that aggregates of mutated GFAP-GFP may either disappear, associated with cell survival, or coalesce in a huge juxtanuclear structure associated with cell death. Immunolabeling of fixed cells suggested that this gathering of aggregates forms an aggresome-like structure. Proteasome inhibition and immunoprecipitation assays revealed mutated GFAP-GFP ubiquitination, suggesting a role of the ubiquitin-proteasome system in the disaggregation process. In astrocytes from wild-type-, GFAP-, and vimentin-deficient mice, mutated GFAP-GFP aggregated or formed a network, depending on qualitative and quantitative interactions with normal intermediate filament partners. Particularly, vimentin displayed an anti-aggregation effect on mutated GFAP. Our data indicate a dynamic and reversible aggregation of mutated GFAP, suggesting that therapeutic approaches may be possible.

How Spherical Are the Archimedean Solids and Their Duals?

ERIC Educational Resources Information Center

Aravind, P. K.

2011-01-01

The Isoperimetric Quotient, or IQ, introduced by G. Polya, characterizes the degree of sphericity of a convex solid. This paper obtains closed form expressions for the surface area and volume of any Archimedean polyhedron in terms of the integers specifying the type and number of regular polygons occurring around each vertex. Similar results are…

Correlations among the parameters of the spherical model for eclipsing binaries

NASA Technical Reports Server (NTRS)

Sobieski, S.; White, J. E.

1971-01-01

Correlation coefficients were computed to investigate the parameters for describing the spherical model of an eclipsing binary system. Regions in parameter hyperspace were identified where strong correlations exist and, by implication, the solution determinacy is low. The results are presented in tabular form for a large number of system configurations.

Folded-path optical analysis gas cell

DOEpatents

Carangelo, R.M.; Wright, D.D.

1995-08-08

A folded-path gas cell employs an elliptical concave mirror in confronting relationship to two substantially spherical concave mirrors. At least one of the spherical mirrors, and usually both, are formed with an added cylindrical component to increase orthogonal foci coincidence and thereby to increase the radiation energy throughput characteristic of the cell. 10 figs.

Spherical-wave expansions of piston-radiator fields.

PubMed

Wittmann, R C; Yaghjian, A D

1991-09-01

Simple spherical-wave expansions of the continuous-wave fields of a circular piston radiator in a rigid baffle are derived. These expansions are valid throughout the illuminated half-space and are useful for efficient numerical computation in the near-field region. Multipole coefficients are given by closed-form expressions which can be evaluated recursively.

Sequence dependent aggregation of peptides and fibril formation

NASA Astrophysics Data System (ADS)

Hung, Nguyen Ba; Le, Duy-Manh; Hoang, Trinh X.

2017-09-01

Deciphering the links between amino acid sequence and amyloid fibril formation is key for understanding protein misfolding diseases. Here we use Monte Carlo simulations to study the aggregation of short peptides in a coarse-grained model with hydrophobic-polar (HP) amino acid sequences and correlated side chain orientations for hydrophobic contacts. A significant heterogeneity is observed in the aggregate structures and in the thermodynamics of aggregation for systems of different HP sequences and different numbers of peptides. Fibril-like ordered aggregates are found for several sequences that contain the common HPH pattern, while other sequences may form helix bundles or disordered aggregates. A wide variation of the aggregation transition temperatures among sequences, even among those of the same hydrophobic fraction, indicates that not all sequences undergo aggregation at a presumable physiological temperature. The transition is found to be the most cooperative for sequences forming fibril-like structures. For a fibril-prone sequence, it is shown that fibril formation follows the nucleation and growth mechanism. Interestingly, a binary mixture of peptides of an aggregation-prone and a non-aggregation-prone sequence shows the association and conversion of the latter to the fibrillar structure. Our study highlights the role of a sequence in selecting fibril-like aggregates and also the impact of a structural template on fibril formation by peptides of unrelated sequences.

Formation of thermally induced aggregates of the soya globulin beta-conglycinin.

PubMed

Mills, E N; Huang, L; Noel, T R; Gunning, A P; Morris, V J

2001-06-11

The effect of ionic strength (I) on the formation of thermally induced aggregates by the 7S globular storage protein of soya, beta-conglycinin, has been studied using atomic force microscopy. Aggregates were only apparent when I> or =0.1, and had a fibrous appearance, with a height (diameter) of 8-11 nm. At high ionic strength (I=1.0) the aggregates appeared to associate into clumps. When aggregate formation was studied at I=0.2, it was clear that aggregation only began at temperatures above the main thermal transition for the protein at 75 degrees C, as determined by differential scanning calorimetry. This coincided with a small change in secondary structure, as indicated by circular dichroism spectroscopy, suggesting that a degree of unfolding was necessary for aggregation to proceed. Despite prolonged heating the size of the aggregates did not increase indefinitely, suggesting that certain beta-conglycinin isoforms were able to act as chain terminators. At higher protein concentrations (1% w/v) the linear aggregates appeared to form large macroaggregates, which may be the precursors of protein gel formation. The ability of beta-conglycinin to form such distinctive aggregates is discussed in relation to the presence of acidic inserts in certain of the beta-conglycinin subunits, which may play an important role in limiting aggregate length.

Cylindrical and spherical solitary waves in an electron-acoustic plasma with vortex electron distribution

NASA Astrophysics Data System (ADS)

Demiray, Hilmi; El-Zahar, Essam R.

2018-04-01

We consider the nonlinear propagation of electron-acoustic waves in a plasma composed of a cold electron fluid, hot electrons obeying a trapped/vortex-like distribution, and stationary ions. The basic nonlinear equations of the above described plasma are re-examined in the cylindrical (spherical) coordinates by employing the reductive perturbation technique. The modified cylindrical (spherical) KdV equation with fractional power nonlinearity is obtained as the evolution equation. Due to the nature of nonlinearity, this evolution equation cannot be reduced to the conventional KdV equation. A new family of closed form analytical approximate solution to the evolution equation and a comparison with numerical solution are presented and the results are depicted in some 2D and 3D figures. The results reveal that both solutions are in good agreement and the method can be used to obtain a new progressive wave solution for such evolution equations. Moreover, the resulting closed form analytical solution allows us to carry out a parametric study to investigate the effect of the physical parameters on the solution behavior of the modified cylindrical (spherical) KdV equation.

Method for preparing spherical ferrite beads and use thereof

DOEpatents

Lauf, Robert J.; Anderson, Kimberly K.; Montgomery, Frederick C.; Collins, Jack L.

2002-01-01

The invention allows the fabrication of small, dense, highly polished spherical beads of hexagonal ferrites with selected compositions for use in nonreciprocal microwave and mm-wave devices as well as in microwave absorbent or reflective coatings, composites, and the like. A porous, generally spherical bead of hydrous iron oxide is made by a sol-gel process to form a substantially rigid bead having a generally fine crystallite size and correspondingly finely distributed internal porosity. The resulting gel bead is washed and hydrothermally reacted with a soluble alkaline earth salt (typically Ba or Sr) under conditions of elevated temperature and pressure to convert the bead into a mixed hydrous iron-alkaline earth oxide while retaining the generally spherical shape. This mixed oxide bead is then washed, dried, and calcined to produce the desired (BaFe.sub.12 O.sub.19 or SrFe.sub.12 O.sub.19) crystal structure. The calcined bead is then sintered to form a dense bead of the BaFe.sub.12 O.sub.19 and SrFe.sub.12 O.sub.19 phase suitable for polishing and incorporation into various microwave devices and components.

Rate Kinetics and Molecular Dynamics of the Structural Transitions in Amyloidogenic Proteins

NASA Astrophysics Data System (ADS)

Steckmann, Timothy M.

Amyloid fibril aggregation is associated with several horrific diseases such as Alzheimer's, Creutzfeld-Jacob, diabetes, Parkinson's and others. The process of amyloid aggregation involves forming myriad different metastable intermediate aggregates. Amyloid fibrils are composed of proteins that originate in an innocuous alpha-helix or random-coil structure. The alpha-helices convert their structure to beta-strands that aggregate into beta-sheets, and then into protofibrils, and ultimately into fully formed amyloid fibrils. On the basis of experimental data, I have developed a mathematical model for the kinetics of the reaction pathways and determined rate parameters for peptide secondary structural conversion and aggregation during the entire fibrillogenesis process from random coil to fibrils, including the molecular species that accelerate the conversions. The specific steps of the model and the rate constants that are determined by fitting to experimental data provide insight on the molecular species involved in the fibril formation process. To better understand the molecular basis of the protein structural transitions and aggregation, I report on molecular dynamics (MD) computational studies on the formation of amyloid protofibrillar structures in the small model protein ccbeta, which undergoes many of the structural transitions of the larger, naturally occurring amyloid forming proteins. Two different structural transition processes involving hydrogen bonds are observed for aggregation into fibrils: the breaking of intrachain hydrogen bonds to allow beta-hairpin proteins to straighten, and the subsequent formation of interchain hydrogen bonds during aggregation into amyloid fibrils. For my MD simulations, I found that the temperature dependence of these two different structural transition processes results in the existence of a temperature window that the ccbeta protein experiences during the process of forming protofibrillar structures. Both the mathematical modeling of the kinetics and the MD simulations show that molecular structural heterogeneity is a major factor in the process. The MD simulations also show that intrachain and interchain hydrogen bonds breaking and forming is strongly correlated to the process of amyloid formation.

Microstructure and Mechanical Properties of Ti-6Al-4V Fabricated by Selective Laser Melting of Powder Produced by Granulation-Sintering-Deoxygenation Method

NASA Astrophysics Data System (ADS)

Sun, Pei; Fang, Z. Zak; Zhang, Ying; Xia, Yang

2017-12-01

Commercial spherical Ti powders for additive manufacturing applications are produced today by melt-atomization methods at relatively high costs. A meltless production method, called granulation-sintering-deoxygenation (GSD), was developed recently to produce spherical Ti alloy powder at a significantly reduced cost. In this new process, fine hydrogenated Ti particles are agglomerated to form spherical granules, which are then sintered to dense spherical particles. After sintering, the solid fully dense spherical Ti alloy particles are deoxygenated using novel low-temperature deoxygenation processes with either Mg or Ca. This technical communication presents results of 3D printing using GSD powder and the selective laser melting (SLM) technique. The results showed that tensile properties of parts fabricated from spherical GSD Ti-6Al-4V powder by SLM are comparable with typical mill-annealed Ti-6Al-4V. The characteristics of 3D printed Ti-6Al-4V from GSD powder are also compared with that of commercial materials.

Method for making fine and ultrafine spherical particles of zirconium titanate and other mixed metal oxide systems

DOEpatents

Hu, Michael Z.

2006-05-23

Disclosed is a method for making amorphous spherical particles of zirconium titanate and crystalline spherical particles of zirconium titanate comprising the steps of mixing an aqueous solution of zirconium salt and an aqueous solution of titanium salt into a mixed solution having equal moles of zirconium and titanium and having a total salt concentration in the range from 0.01 M to about 0.5 M. A stearic dispersant and an organic solvent is added to the mixed salt solution, subjecting the zirconium salt and the titanium salt in the mixed solution to a coprecipitation reaction forming a solution containing amorphous spherical particles of zirconium titanate wherein the volume ratio of the organic solvent to aqueous part is in the range from 1 to 5. The solution of amorphous spherical particles is incubated in an oven at a temperature .ltoreq.100.degree. C. for a period of time .ltoreq.24 hours converting the amorphous particles to fine or ultrafine crystalline spherical particles of zirconium titanate.

Synthesis, surface modification and biological imaging of aggregation-induced emission (AIE) dye doped silica nanoparticles

NASA Astrophysics Data System (ADS)

Mao, Liucheng; Liu, Meiying; Xu, Dazhuang; Wan, Qing; Huang, Qiang; Jiang, Ruming; Shi, Yingge; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

2017-05-01

Fluorescent silica nanoparticles (FSNPs) have been extensively investigated for various biomedical applications in recently years. However, the aggregation of organic dyes in silica nanoparticles also leads the significant fluorescence quenching owing to the aggregation caused quenching effects of organic dyes. Herein, we developed a rather facile strategy to fabricate FSNPs with desirable fluorescent properties through non-covalent incorporation of fluorophores with aggregation-induced emission (AIE) feature into silica nanoparticles, which were subsequently modified with functional polymers. The resultant FSNPs polymer nanocomposites (named as FSNPs-poly(IA-co-PEGMA)) exhibited uniform spherical morphology, high water dispersiity, and bright red fluorescence. Cytotoxicity results indicate that FSNPs-poly(IA-co-PEGMA) possess excellent biocompatibility. Cell uptake behavior suggests FSNPs-poly(IA-co-PEGMA) are of great potential for biological imaging applications. Taken together, we have reported a facile method for the fabrication of FSNPs through non-covalent encapsulation using an AIE-active dye. These FSNPs can be further functionalized with functional polymers through ring-opening reaction and the resultant FSNPs-poly(IA-co-PEGMA) showed great potential for biological imaging. More importantly, we believe that many other functional components could also be integrated into these FSNPs through the facile ring-opening reaction. Therefore, this method should be a facile and general tool for fabrication of polymer functionalized AIE-active FSNPs.

Aggregation of peptides in the tube model with correlated sidechain orientations

NASA Astrophysics Data System (ADS)

Hung, Nguyen Ba; Hoang, Trinh Xuan

2015-06-01

The ability of proteins and peptides to aggregate and form toxic amyloid fibrils is associated with a range of diseases including BSE (or mad cow), Alzheimer's and Parkinson's Diseases. In this study, we investigate the the role of amino acid sequence in the aggregation propensity by using a modified tube model with a new procedure for hydrophobic interaction. In this model, the amino acid sidechains are not considered explicitly, but their orientations are taken into account in the formation of hydrophobic contact. Extensive Monte Carlo simulations for systems of short peptides are carried out with the use of parallel tempering technique. Our results show that the propensity to form and the structures of the aggregates strongly depend on the amino acid sequence and the number of peptides. Some sequences may not aggregate at all at a presumable physiological temperature while other can easily form fibril-like, β-sheet struture. Our study provides an insight into the principles of how the formation of amyloid can be governed by amino acid sequence.

The effect of different desolvating agents on BSA nanoparticle properties and encapsulation of curcumin

NASA Astrophysics Data System (ADS)

Sadeghi, R.; Moosavi-Movahedi, A. A.; Emam-jomeh, Z.; Kalbasi, A.; Razavi, S. H.; Karimi, M.; Kokini, J.

2014-09-01

The desolvation method was successfully used to prepare nanoparticles from bovine serum albumin (BSA) using ethanol, acetone, and their mixtures (70:30 and 50:50, respectively). Ethanol and mixtures of ethanol and acetone led to the most spherical nanoparticles, while using pure acetone resulted in a mixture of spherical and rod shape nanoparticle. Acetone was the solvent with higher encapsulation efficiency equal to 99.2 ± 0.36 %. The polydispersity values of BSA NPs in this study were 0.045 ± 0.007, 0.065 ± 0.013, 0.091 ± 0.012, and 0.120 ± 0.016 for ethanol (100) 4×, Et:Ac (70:30) 4×, Et:Ac (50:50) 4×, and acetone (100) 3×, respectively. Encapsulation efficiencies of curcumin inside BSA NPs were 19.4 ± 2.2 and 19.8 ± 1.6 % for 1.0 and 1.5 molar ratios of curcumin to BSA, respectively. Crosslinking using glutaraldehyde improved the stability of BSA NPs and curcumin-loaded BSA NPs and both groups of nanoparticles were stable for 1 month; the lyophilized curcumin-loaded BSA NPs were able to redisperse in water. The particle size and polydispersity index of redispersed NPs were higher than the original NPs before lyophilization. The size distribution study shows that after 10 s of sonication most nanoparticles were well dispersed; however, a small but significant fraction formed aggregates. Sonication for 10 s decreased the effective diameter and polydispersity of the redispersed nanoparticles, while increasing the sonication time to 20 s did not show significant changes. In vitro release study of curcumin from BSA NPs showed that these biocompatible nanoparticles have the ability to be used as a carrier to improve controlled release of curcumin.

Elementary Theoretical Forms for the Spatial Power Spectrum of Earth's Crustal Magnetic Field

NASA Technical Reports Server (NTRS)

Voorhies, C.

1998-01-01

The magnetic field produced by magnetization in Earth's crust and lithosphere can be distinguished from the field produced by electric currents in Earth's core because the spatial magnetic power spectrum of the crustal field differs from that of the core field. Theoretical forms for the spectrum of the crustal field are derived by treating each magnetic domain in the crust as the point source of a dipole field. The geologic null-hypothesis that such moments are uncorrelated is used to obtain the magnetic spectrum expected from a randomly magnetized, or unstructured, spherical crust of negligible thickness. This simplest spectral form is modified to allow for uniform crustal thickness, ellipsoidality, and the polarization of domains by an periodically reversing, geocentric axial dipole field from Earth's core. Such spectra are intended to describe the background crustal field. Magnetic anomalies due to correlated magnetization within coherent geologic structures may well be superimposed upon this background; yet representing each such anomaly with a single point dipole may lead to similar spectral forms. Results from attempts to fit these forms to observational spectra, determined via spherical harmonic analysis of MAGSAT data, are summarized in terms of amplitude, source depth, and misfit. Each theoretical spectrum reduces to a source factor multiplied by the usual exponential function of spherical harmonic degree n due to geometric attenuation with attitude above the source layer. The source factors always vary with n and are approximately proportional to n(exp 3) for degrees 12 through 120. The theoretical spectra are therefore not directly proportional to an exponential function of spherical harmonic degree n. There is no radius at which these spectra are flat, level, or otherwise independent of n.

Super-tough, ultra-stretchable and strongly compressive hydrogels with core-shell latex particles inducing efficient aggregation of hydrophobic chains.

PubMed

Ren, Xiuyan; Huang, Chang; Duan, Lijie; Liu, Baijun; Bu, Lvjun; Guan, Shuang; Hou, Jiliang; Zhang, Huixuan; Gao, Guanghui

2017-05-14

Toughness, strechability and compressibility for hydrogels were ordinarily balanced for their use as mechanically responsive materials. For example, macromolecular microsphere composite hydrogels with chemical crosslinking exhibited excellent compression strength and strechability, but poor tensile stress. Here, a novel strategy for the preparation of a super-tough, ultra-stretchable and strongly compressive hydrogel was proposed by introducing core-shell latex particles (LPs) as crosslinking centers for inducing efficient aggregation of hydrophobic chains. The core-shell LPs always maintained a spherical shape due to the presence of a hard core even by an external force and the soft shell could interact with hydrophobic chains due to hydrophobic interactions. As a result, the hydrogels reinforced by core-shell LPs exhibited not only a high tensile strength of 1.8 MPa and dramatic elongation of over 20 times, but also an excellent compressive performance of 13.5 MPa at a strain of 90%. The Mullins effect was verified for the validity of core-shell LP-reinforced hydrogels by inducing aggregation of hydrophobic chains. The novel strategy strives to provide a better avenue for designing and developing a new generation of hydrophobic association tough hydrogels with excellent mechanical properties.

On cooperative effects and aggregation of GNNQQNY and NNQQNY peptides

NASA Astrophysics Data System (ADS)

Nochebuena, Jorge; Ireta, Joel

2015-10-01

Some health disturbances like neurodegenerative diseases are associated to the presence of amyloids. GNNQQNY and NNQQNY peptides are considered as prototypical examples for studying the formation of amyloids. These exhibit quite different aggregation behaviors despite they solely differ in size by one residue. To get insight into the reasons for such difference, we have examined association energies of aggregates (parallel β-sheets, fibril-spines, and crystal structures) from GNNQQNY and NNQQY using density functional theory. As we found that GNNQQNY tends to form a zwitterion in the crystal structure, we have investigated the energetics of parallel β-sheets and fibril-spines in the canonical and zwitterionic states. We found that the formation of GNNQQNY aggregates is energetically more favored than the formation of the NNQQNY ones. We show that the latter is connected to the network of hydrogen bonds formed by each aggregate. Moreover, we found that the formation of some NNQQNY aggregates is anticooperative, whereas cooperative with GNNQQNY. These results have interesting implications for deciphering the factors determining peptide aggregation propensities.

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

Ben-Naim, Eli; Krapivsky, Paul

Here we generalize the ordinary aggregation process to allow for choice. In ordinary aggregation, two random clusters merge and form a larger aggregate. In our implementation of choice, a target cluster and two candidate clusters are randomly selected and the target cluster merges with the larger of the two candidate clusters.We study the long-time asymptotic behavior and find that as in ordinary aggregation, the size density adheres to the standard scaling form. However, aggregation with choice exhibits a number of different features. First, the density of the smallest clusters exhibits anomalous scaling. Second, both the small-size and the large-size tailsmore » of the density are overpopulated, at the expense of the density of moderate-size clusters. Finally, we also study the complementary case where the smaller candidate cluster participates in the aggregation process and find an abundance of moderate clusters at the expense of small and large clusters. Additionally, we investigate aggregation processes with choice among multiple candidate clusters and a symmetric implementation where the choice is between two pairs of clusters.« less

Spherical accretion of matter by charged black holes on f(T) Gravity

NASA Astrophysics Data System (ADS)

Rodrigues, M. E.; Junior, E. L. B.

2018-03-01

We studied the spherical accretion of matter by charged black holes on f(T) Gravity. Considering the accretion model of a isentropic perfect fluid we obtain the general form of the Hamiltonian and the dynamic system for the fluid. We have analysed the movements of an isothermal fluid model with p=ω e and where p is the pressure and e the total energy density. The analysis of the cases shows the possibility of spherical accretion of fluid by black holes, revealing new phenomena as cyclical movement inside the event horizon.

Strongly localized image states of spherical graphitic particles.

PubMed

Gumbs, Godfrey; Balassis, Antonios; Iurov, Andrii; Fekete, Paula

2014-01-01

We investigate the localization of charged particles by the image potential of spherical shells, such as fullerene buckyballs. These spherical image states exist within surface potentials formed by the competition between the attractive image potential and the repulsive centripetal force arising from the angular motion. The image potential has a power law rather than a logarithmic behavior. This leads to fundamental differences in the nature of the effective potential for the two geometries. Our calculations have shown that the captured charge is more strongly localized closest to the surface for fullerenes than for cylindrical nanotube.

Patterns of [PSI+] aggregation allow insights into cellular organization of yeast prion aggregates

PubMed Central

Tyedmers, Jens

2012-01-01

The yeast prion phenomenon is very widespread and mounting evidence suggests that it has an impact on cellular regulatory mechanisms related to phenotypic responses to changing environments. Studying the aggregation patterns of prion amyloids during different stages of the prion life cycle is a first key step to understand major principles of how and where cells generate, organize and turn-over prion aggregates. The induction of the [PSI+] state involves the actin cytoskeleton and quality control compartments such as the Insoluble Protein Deposit (IPOD). An initially unstable transitional induction state can be visualized by overexpression of the prion determinant and displays characteristic large ring- and ribbon-shaped aggregates consisting of poorly fragmented bundles of very long prion fibrils. In the mature prion state, the aggregation pattern is characterized by highly fragmented, shorter prion fibrils that form aggregates, which can be visualized through tagging with fluorescent proteins. The number of aggregates formed varies, ranging from a single large aggregate at the IPOD to multiple smaller ones, depending on several parameters discussed. Aggregate units below the resolution of light microscopy that are detectable by fluorescence correlation spectroscopy are in equilibrium with larger aggregates in this stage and can mediate faithful inheritance of the prion state. Loss of the prion state is often characterized by reduced fragmentation of prion fibrils and fewer, larger aggregates. PMID:22449721

Kinetics of Aggregation with Choice

DOE PAGES

Ben-Naim, Eli; Krapivsky, Paul

2016-12-01

Here we generalize the ordinary aggregation process to allow for choice. In ordinary aggregation, two random clusters merge and form a larger aggregate. In our implementation of choice, a target cluster and two candidate clusters are randomly selected and the target cluster merges with the larger of the two candidate clusters.We study the long-time asymptotic behavior and find that as in ordinary aggregation, the size density adheres to the standard scaling form. However, aggregation with choice exhibits a number of different features. First, the density of the smallest clusters exhibits anomalous scaling. Second, both the small-size and the large-size tailsmore » of the density are overpopulated, at the expense of the density of moderate-size clusters. Finally, we also study the complementary case where the smaller candidate cluster participates in the aggregation process and find an abundance of moderate clusters at the expense of small and large clusters. Additionally, we investigate aggregation processes with choice among multiple candidate clusters and a symmetric implementation where the choice is between two pairs of clusters.« less

Exciton–exciton annihilation as a probe of interchain interactions in PPV–oligomer aggregates

DOE PAGES

Peteanu, Linda A.; Chowdhury, Sanchari; Wildeman, Jurjen; ...

2017-01-20

One measure of exciton mobility in an aggregate is the efficiency of exciton–exciton annihilation (EEA). Both exciton mobilities and EEA are enhanced for aggregate morphologies in which the distances between chromophores and their relative orientations are favorable for Förster energy transfer. Here this principle is applied to gauge the strength of interchain interactions in aggregates of two substituted PPV oligomers of 7 (OPPV7) and 13 (OPPV13) phenylene rings. These are models of the semiconducting conjugated polymer MEH–PPV. The aggregates were formed by adding a poor solvent (methanol or water) to the oligomers dissolved in a good solvent. Aggregates formed frommore » the longer-chain oligomer and/or by addition of the more polar solvent showed the largest contribution of EEA in their emission decay dynamics. This was found to correlate with the degree to which the steady-state emission spectrum of the monomer is altered by aggregation. Furthermore, the wavelength dependence of the EEA signal was also shown to be useful in differentiating emission features due to monomeric and aggregated chains when their spectra overlap significantly.« less

Exciton-Exciton Annihilation as a Probe of Interchain Interactions in PPV-Oligomer Aggregates.

PubMed

Peteanu, Linda A; Chowdhury, Sanchari; Wildeman, Jurjen; Sfeir, Matthew Y

2017-02-23

One measure of exciton mobility in an aggregate is the efficiency of exciton-exciton annihilation (EEA). Both exciton mobilities and EEA are enhanced for aggregate morphologies in which the distances between chromophores and their relative orientations are favorable for Förster energy transfer. Here this principle is applied to gauge the strength of interchain interactions in aggregates of two substituted PPV oligomers of 7 (OPPV7) and 13 (OPPV13) phenylene rings. These are models of the semiconducting conjugated polymer MEH-PPV. The aggregates were formed by adding a poor solvent (methanol or water) to the oligomers dissolved in a good solvent. Aggregates formed from the longer-chain oligomer and/or by addition of the more polar solvent showed the largest contribution of EEA in their emission decay dynamics. This was found to correlate with the degree to which the steady-state emission spectrum of the monomer is altered by aggregation. The wavelength dependence of the EEA signal was also shown to be useful in differentiating emission features due to monomeric and aggregated chains when their spectra overlap significantly.

CROSS-DISCIPLINARY PHYSICS AND RELATED AREAS OF SCIENCE AND TECHNOLOGY: Kinetics of catalytically activated duplication in aggregation growth

NASA Astrophysics Data System (ADS)

Wang, Hai-Feng; Lin, Zhen-Quan; Gao, Yan; Xu, Chao

2009-08-01

We propose a catalytically activated duplication model to mimic the coagulation and duplication of the DNA polymer system under the catalysis of the primer RNA. In the model, two aggregates of the same species can coagulate themselves and a DNA aggregate of any size can yield a new monomer or double itself with the help of RNA aggregates. By employing the mean-field rate equation approach we analytically investigate the evolution behaviour of the system. For the system with catalysis-driven monomer duplications, the aggregate size distribution of DNA polymers ak(t) always follows a power law in size in the long-time limit, and it decreases with time or approaches a time-independent steady-state form in the case of the duplication rate independent of the size of the mother aggregates, while it increases with time increasing in the case of the duplication rate proportional to the size of the mother aggregates. For the system with complete catalysis-driven duplications, the aggregate size distribution ak(t) approaches a generalized or modified scaling form.

METHOD OF PREPARATION OF MATERIAL FOR NEUTRON BOMBARDMENT

DOEpatents

Ura, C.L.; Sisman, O.; Briggs, R.B.

1959-02-01

A method is presented for forming slugs or cartridges of sample material to be proeessed in a neutronic reactor. Aceording to this invention, the sample material is originally in the fcrm of powder. The powder is placed within a tube formed of a metallic foil. The material encased in the foil is then placed in a die and compressed under sufficient pressure to form a rigid cartridge. The cartridge is then sealed in a metallic can. As a result of this process, crumbling of the compact during handling is eliminated and it is not necessary to clean ana relubricate the die after compression of each cartridge. ~ A method is presented for producing small spherical shot-type pellets from ceramic or refractory materials. According to this process the material to be pelletized is first formed into a powder. The powdered material is then suspended in a liquid carrier or vehicle. Small drops of the suspension, produced by a capillary-drop apparatus, are deposited on the surfacc of a liquid repellent powder, which causes the drops to assume a spherical shape. The liquid is then evaporated from the spherical pellets and tbe pellets are collected and fired to produce the finished product.

Nanoscale studies link amyloid maturity with polyglutamine diseases onset

NASA Astrophysics Data System (ADS)

Ruggeri, F. S.; Vieweg, S.; Cendrowska, U.; Longo, G.; Chiki, A.; Lashuel, H. A.; Dietler, G.

2016-08-01

The presence of expanded poly-glutamine (polyQ) repeats in proteins is directly linked to the pathogenesis of several neurodegenerative diseases, including Huntington’s disease. However, the molecular and structural basis underlying the increased toxicity of aggregates formed by proteins containing expanded polyQ repeats remain poorly understood, in part due to the size and morphological heterogeneity of the aggregates they form in vitro. To address this knowledge gap and technical limitations, we investigated the structural, mechanical and morphological properties of fibrillar aggregates at the single molecule and nanometer scale using the first exon of the Huntingtin protein as a model system (Exon1). Our findings demonstrate a direct correlation of the morphological and mechanical properties of Exon1 aggregates with their structural organization at the single aggregate and nanometric scale and provide novel insights into the molecular and structural basis of Huntingtin Exon1 aggregation and toxicity.

Hydrogen-bonded aggregates in precise acid copolymers

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

Lueth, Christopher A.; Bolintineanu, Dan S.; Stevens, Mark J., E-mail: msteve@sandia.gov

2014-02-07

We perform atomistic molecular dynamics simulations of melts of four precise acid copolymers, two poly(ethylene-co-acrylic acid) (PEAA) copolymers, and two poly(ethylene-co-sulfonic acid) (PESA) copolymers. The acid groups are spaced by either 9 or 21 carbons along the polymer backbones. Hydrogen bonding causes the acid groups to form aggregates. These aggregates give rise to a low wavevector peak in the structure factors, in agreement with X-ray scattering data for the PEAA materials. The structure factors for the PESA copolymers are very similar to those for the PEAA copolymers, indicating a similar distance between aggregates which depends on the spacer length butmore » not on the nature of the acid group. The PEAA copolymers are found to form more dimers and other small aggregates than do the PESA copolymers, while the PESA copolymers have both more free acid groups and more large aggregates.« less

Preparation of ultra-fine powders from polysaccharide-coated solid lipid nanoparticles and nanostructured lipid carriers by innovative nano spray drying technology.

PubMed

Wang, Taoran; Hu, Qiaobin; Zhou, Mingyong; Xue, Jingyi; Luo, Yangchao

2016-09-10

In this study, five polysaccharides were applied as natural polymeric coating materials to prepare solid lipid nanoparticles (SLN) and nanostructure lipid carriers (NLC), and then the obtained lipid colloidal particles were transformed to solid powders by the innovative nano spray drying technology. The feasibility and suitability of this new technology to generate ultra-fine lipid powder particles were evaluated and the formulation was optimized. The spray dried SLN powder exhibited the aggregated and irregular shape and dimension, but small, uniform, well-separated spherical powder particles of was obtained from NLC. The optimal formulation of NLC was prepared by a 20-30% oleic acid content with carrageenan or pectin as coating material. Therefore, nano spray drying technology has a potential application to produce uniform, spherical, and sub-microscale lipid powder particles when the formulation of lipid delivery system is appropriately designed. Copyright © 2016 Elsevier B.V. All rights reserved.

Structural transformation study of TiO2 nanoparticles annealing at different temperatures and the photodegradation process of eosin-Y

NASA Astrophysics Data System (ADS)

Pandi, P.; Gopinathan, C.

2018-04-01

Hydrothermal method was used to prepare TiO2 nanoparticles with annealing temperature at 500 °C-700 °C. The mixture of anatase-rutile phase was investigated by powerful tool of X-ray diffraction (XRD). The structural parameters of anatase and rutile mixture phaseTiO2 nanoparticles were calculated from the Rietveld refinement. The transformation rate of rutile was increased linearly with an annealing temperature of 500 °C-700 °C. The spherical morphology of the anatase and rutile mixed phase were obtained by scanning electron microscope and transmission electron microscope. The spherical particle of the anatase and rutile TiO2 shows with great aggregation with different size and within the range of few tens nm. The EDAX study revealed the presence of titanium and oxygen. The best photocatalytic activity was identified as the 87.04% of anatase and 12.96% of rutile mixer phase of TiO2. Various factors could be involved for a better photocatalytic activity.

Conformations of low-molecular-weight lignin polymers in water

DOE PAGES

Petridis, Loukas; Smith, Jeremy C.

2016-01-13

Low-molecular-weight lignin binds to cellulose during the thermochemical pretreatment of biomass for biofuel production, which prevents the efficient hydrolysis of the cellulose to sugars. The binding properties of lignin are influenced strongly by the conformations it adopts. Here, we use molecular dynamics simulations in aqueous solution to investigate the dependence of the shape of lignin polymers on chain length and temperature. Lignin is found to adopt collapsed conformations in water at 300 and 500 K. However, at 300 K, a discontinuous transition is found in the shape of the polymer as a function of the chain length. Below a criticalmore » degree of polymerization, N c=15, the polymer adopts less spherical conformations than above N c. The transition disappears at high temperatures (500 K) at which only spherical shapes are adopted. As a result, an implication relevant to cellulosic biofuel production is that lignin will self-aggregate even at high pretreatment temperatures.« less

Conformations of Low-Molecular-Weight Lignin Polymers in Water.

PubMed

Petridis, Loukas; Smith, Jeremy C

2016-02-08

Low-molecular-weight lignin binds to cellulose during the thermochemical pretreatment of biomass for biofuel production, which prevents the efficient hydrolysis of the cellulose to sugars. The binding properties of lignin are influenced strongly by the conformations it adopts. Here, we use molecular dynamics simulations in aqueous solution to investigate the dependence of the shape of lignin polymers on chain length and temperature. Lignin is found to adopt collapsed conformations in water at 300 and 500 K. However, at 300 K, a discontinuous transition is found in the shape of the polymer as a function of the chain length. Below a critical degree of polymerization, Nc =15, the polymer adopts less spherical conformations than above Nc. The transition disappears at high temperatures (500 K) at which only spherical shapes are adopted. An implication relevant to cellulosic biofuel production is that lignin will self-aggregate even at high pretreatment temperatures. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Curcumin and kaempferol prevent lysozyme fibril formation by modulating aggregation kinetic parameters.

PubMed

Borana, Mohanish S; Mishra, Pushpa; Pissurlenkar, Raghuvir R S; Hosur, Ramakrishna V; Ahmad, Basir

2014-03-01

Interaction of small molecule inhibitors with protein aggregates has been studied extensively, but how these inhibitors modulate aggregation kinetic parameters is little understood. In this work, we investigated the ability of two potential aggregation inhibiting drugs, curcumin and kaempferol, to control the kinetic parameters of aggregation reaction. Using thioflavin T fluorescence and static light scattering, the kinetic parameters such as amplitude, elongation rate constant and lag time of guanidine hydrochloride-induced aggregation reactions of hen egg white lysozyme were studied. We observed a contrasting effect of inhibitors on the kinetic parameters when aggregation reactions were measured by these two probes. The interactions of these inhibitors with hen egg white lysozyme were investigated using fluorescence quench titration method and molecular dynamics simulations coupled with binding free energy calculations. We conclude that both the inhibitors prolong nucleation of amyloid aggregation through binding to region of the protein which is known to form the core of the protein fibril, but once the nucleus is formed the rate of elongation is not affected by the inhibitors. This work would provide insight into the mechanism of aggregation inhibition by these potential drug molecules. Copyright © 2014 Elsevier B.V. All rights reserved.

Dynamics of proteins aggregation. I. Universal scaling in unbounded media

NASA Astrophysics Data System (ADS)

Zheng, Size; Javidpour, Leili; Shing, Katherine S.; Sahimi, Muhammad

2016-10-01

It is well understood that in some cases proteins do not fold correctly and, depending on their environment, even properly-folded proteins change their conformation spontaneously, taking on a misfolded state that leads to protein aggregation and formation of large aggregates. An important factor that contributes to the aggregation is the interactions between the misfolded proteins. Depending on the aggregation environment, the aggregates may take on various shapes forming larger structures, such as protein plaques that are often toxic. Their deposition in tissues is a major contributing factor to many neuro-degenerative diseases, such as Alzheimer's, Parkinson's, amyotrophic lateral sclerosis, and prion. This paper represents the first part in a series devoted to molecular simulation of protein aggregation. We use the PRIME, a meso-scale model of proteins, together with extensive discontinuous molecular dynamics simulation to study the aggregation process in an unbounded fluid system, as the first step toward MD simulation of the same phenomenon in crowded cellular environments. Various properties of the aggregates have been computed, including dynamic evolution of aggregate-size distribution, mean aggregate size, number of peptides that contribute to the formation of β sheets, number of various types of hydrogen bonds formed in the system, radius of gyration of the aggregates, and the aggregates' diffusivity. We show that many of such quantities follow dynamic scaling, similar to those for aggregation of colloidal clusters. In particular, at long times the mean aggregate size S(t) grows with time as, S(t) ˜ tz, where z is the dynamic exponent. To our knowledge, this is the first time that the qualitative similarity between aggregation of proteins and colloidal aggregates has been pointed out.

Cluster structure of anaerobic aggregates of an expanded granular sludge bed reactor.

PubMed

Gonzalez-Gil, G; Lens, P N; Van Aelst, A; Van As, H; Versprille, A I; Lettinga, G

2001-08-01

The metabolic properties and ultrastructure of mesophilic aggregates from a full-scale expanded granular sludge bed reactor treating brewery wastewater are described. The aggregates had a very high methanogenic activity on acetate (17.19 mmol of CH(4)/g of volatile suspended solids [VSS].day or 1.1 g of CH(4) chemical oxygen demand/g of VSS.day). Fluorescent in situ hybridization using 16S rRNA probes of crushed granules showed that 70 and 30% of the cells belonged to the archaebacterial and eubacterial domains, respectively. The spherical aggregates were black but contained numerous whitish spots on their surfaces. Cross-sectioning these aggregates revealed that the white spots appeared to be white clusters embedded in a black matrix. The white clusters were found to develop simultaneously with the increase in diameter. Energy-dispersed X-ray analysis and back-scattered electron microscopy showed that the whitish clusters contained mainly organic matter and no inorganic calcium precipitates. The white clusters had a higher density than the black matrix, as evidenced by the denser cell arrangement observed by high-magnification electron microscopy and the significantly higher effective diffusion coefficient determined by nuclear magnetic resonance imaging. High-magnification electron microscopy indicated a segregation of acetate-utilizing methanogens (Methanosaeta spp.) in the white clusters from syntrophic species and hydrogenotrophic methanogens (Methanobacterium-like and Methanospirillum-like organisms) in the black matrix. A number of physical and microbial ecology reasons for the observed structure are proposed, including the advantage of segregation for high-rate degradation of syntrophic substrates.

Cluster Structure of Anaerobic Aggregates of an Expanded Granular Sludge Bed Reactor

PubMed Central

Gonzalez-Gil, G.; Lens, P. N. L.; Van Aelst, A.; Van As, H.; Versprille, A. I.; Lettinga, G.

2001-01-01

The metabolic properties and ultrastructure of mesophilic aggregates from a full-scale expanded granular sludge bed reactor treating brewery wastewater are described. The aggregates had a very high methanogenic activity on acetate (17.19 mmol of CH4/g of volatile suspended solids [VSS]·day or 1.1 g of CH4 chemical oxygen demand/g of VSS·day). Fluorescent in situ hybridization using 16S rRNA probes of crushed granules showed that 70 and 30% of the cells belonged to the archaebacterial and eubacterial domains, respectively. The spherical aggregates were black but contained numerous whitish spots on their surfaces. Cross-sectioning these aggregates revealed that the white spots appeared to be white clusters embedded in a black matrix. The white clusters were found to develop simultaneously with the increase in diameter. Energy-dispersed X-ray analysis and back-scattered electron microscopy showed that the whitish clusters contained mainly organic matter and no inorganic calcium precipitates. The white clusters had a higher density than the black matrix, as evidenced by the denser cell arrangement observed by high-magnification electron microscopy and the significantly higher effective diffusion coefficient determined by nuclear magnetic resonance imaging. High-magnification electron microscopy indicated a segregation of acetate-utilizing methanogens (Methanosaeta spp.) in the white clusters from syntrophic species and hydrogenotrophic methanogens (Methanobacterium-like and Methanospirillum-like organisms) in the black matrix. A number of physical and microbial ecology reasons for the observed structure are proposed, including the advantage of segregation for high-rate degradation of syntrophic substrates. PMID:11472948

Sphere forming method and apparatus

NASA Technical Reports Server (NTRS)

Youngberg, C. L.; Miller, C. G.; Stephens, J. B.; Finnerty, A. A. (Inventor)

1983-01-01

A system is provided for forming small accurately spherical objects. Preformed largely spherical objects are supported at the opening of a conduit on the update of hot gas emitted from the opening, so the object is in a molten state. The conduit is suddenly jerked away at a downward incline, to allow the molten object to drop in free fall, so that surface tension forms a precise sphere. The conduit portion that has the opening, lies in a moderate vacuum chamber, and the falling sphere passes through the chamber and through a briefly opened valve into a tall drop tower that contains a lower pressure, to allow the sphere to cool without deformation caused by falling through air.

Quantify ash aggregation associated to the 26 April 1979 Saint Vincent de la Soufrière eruption

NASA Astrophysics Data System (ADS)

Poret, Matthieu; Costa, Antonio; Folch, Arnau

2016-04-01

The 26 April 1979 an eruption occurred at Saint Vincent de la Soufrière volcano, West Indies, generating an extended tephra fallout deposit from the slope of the volcano toward the South of the island. This event was observed and studied by Brazier et al. (1982). This study provided a few tens of field observations that allowed an estimation of the tephra loading map and other observations on volcanological parameters such as eruptive column height, duration and erupted volume. They also provided information related to aggregation that was significant during the eruption. Here, the field observations and the meteorological fields are used in order to reconstruct the tephra dispersal by using the Fall3D model. The main goal is to better quantify the total mass of fine ash that aggregated during the eruption providing important information and constraints on aggregation processes. The preliminary results show that field observations are well captured using the simplified aggregation parameterization proposed by Cornell et al. (1983) whereas accretionary lapilli can be described adding a second aggregate class (with a diameter of 2 mm, a density of 2000 kg/m3 and a sphericity of 1) representing only a few percentage of the total amount of tephra. Such percentage was estimated by an empirical approach best fitting field observation. The simulation that best fit the field observations gives an estimation of the column height of about 12.5 km above the vent, a mass eruption rate of 6.0d+6 kg/s and a total mass of 2.2d+9 kg erupted. To go further we will use these results within the 1-D cross-section averaged eruption column model named FPLUME-1.0 based on the Buoyant Plume Theory (BPT) that considers aggregation processes within the plume.

Organoids with cancer stem cell-like properties secrete exosomes and HSP90 in a 3D nanoenvironment.

PubMed

Eguchi, Takanori; Sogawa, Chiharu; Okusha, Yuka; Uchibe, Kenta; Iinuma, Ryosuke; Ono, Kisho; Nakano, Keisuke; Murakami, Jun; Itoh, Manabu; Arai, Kazuya; Fujiwara, Toshifumi; Namba, Yuri; Murata, Yoshiki; Ohyama, Kazumi; Shimomura, Manami; Okamura, Hirohiko; Takigawa, Masaharu; Nakatsura, Tetsuya; Kozaki, Ken-Ichi; Okamoto, Kuniaki; Calderwood, Stuart K

2018-01-01

Ability to form cellular aggregations such as tumorspheres and spheroids have been used as a morphological marker of malignant cancer cells and in particular cancer stem cells (CSC). However, the common definition of the types of cellular aggregation formed by cancer cells has not been available. We examined morphologies of 67 cell lines cultured on three dimensional morphology enhancing NanoCulture Plates (NCP) and classified the types of cellular aggregates that form. Among the 67 cell lines, 49 cell lines formed spheres or spheroids, 8 cell lines formed grape-like aggregation (GLA), 8 cell lines formed other types of aggregation, and 3 cell lines formed monolayer sheets. Seven GLA-forming cell lines were derived from adenocarcinoma among the 8 lines. A neuroendocrine adenocarcinoma cell line PC-3 formed asymmetric GLA with ductal structures on the NCPs and rapidly growing asymmetric tumors that metastasized to lymph nodes in immunocompromised mice. In contrast, another adenocarcinoma cell line DU-145 formed spheroids in vitro and spheroid-like tumors in vivo that did not metastasize to lymph nodes until day 50 after transplantation. Culture in the 3D nanoenvironment and in a defined stem cell medium enabled the neuroendocrine adenocarcinoma cells to form slowly growing large organoids that expressed multiple stem cell markers, neuroendocrine markers, intercellular adhesion molecules, and oncogenes in vitro. In contrast, the more commonly used 2D serum-contained environment reduced intercellular adhesion and induced mesenchymal transition and promoted rapid growth of the cells. In addition, the 3D stemness nanoenvironment promoted secretion of HSP90 and EpCAM-exosomes, a marker of CSC phenotype, from the neuroendocrine organoids. These findings indicate that the NCP-based 3D environment enables cells to form stem cell tumoroids with multipotency and model more accurately the in vivo tumor status at the levels of morphology and gene expression.

Organoids with cancer stem cell-like properties secrete exosomes and HSP90 in a 3D nanoenvironment

PubMed Central

Okusha, Yuka; Uchibe, Kenta; Iinuma, Ryosuke; Ono, Kisho; Nakano, Keisuke; Murakami, Jun; Itoh, Manabu; Arai, Kazuya; Fujiwara, Toshifumi; Namba, Yuri; Murata, Yoshiki; Ohyama, Kazumi; Shimomura, Manami; Okamura, Hirohiko; Takigawa, Masaharu; Nakatsura, Tetsuya; Kozaki, Ken-ichi; Okamoto, Kuniaki; Calderwood, Stuart K.

2018-01-01

Ability to form cellular aggregations such as tumorspheres and spheroids have been used as a morphological marker of malignant cancer cells and in particular cancer stem cells (CSC). However, the common definition of the types of cellular aggregation formed by cancer cells has not been available. We examined morphologies of 67 cell lines cultured on three dimensional morphology enhancing NanoCulture Plates (NCP) and classified the types of cellular aggregates that form. Among the 67 cell lines, 49 cell lines formed spheres or spheroids, 8 cell lines formed grape-like aggregation (GLA), 8 cell lines formed other types of aggregation, and 3 cell lines formed monolayer sheets. Seven GLA-forming cell lines were derived from adenocarcinoma among the 8 lines. A neuroendocrine adenocarcinoma cell line PC-3 formed asymmetric GLA with ductal structures on the NCPs and rapidly growing asymmetric tumors that metastasized to lymph nodes in immunocompromised mice. In contrast, another adenocarcinoma cell line DU-145 formed spheroids in vitro and spheroid-like tumors in vivo that did not metastasize to lymph nodes until day 50 after transplantation. Culture in the 3D nanoenvironment and in a defined stem cell medium enabled the neuroendocrine adenocarcinoma cells to form slowly growing large organoids that expressed multiple stem cell markers, neuroendocrine markers, intercellular adhesion molecules, and oncogenes in vitro. In contrast, the more commonly used 2D serum-contained environment reduced intercellular adhesion and induced mesenchymal transition and promoted rapid growth of the cells. In addition, the 3D stemness nanoenvironment promoted secretion of HSP90 and EpCAM-exosomes, a marker of CSC phenotype, from the neuroendocrine organoids. These findings indicate that the NCP-based 3D environment enables cells to form stem cell tumoroids with multipotency and model more accurately the in vivo tumor status at the levels of morphology and gene expression. PMID:29415026

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

Salvucci, Michael

Research examined the thermal stability and propensity for aggregation of wild type and the C- and N-terminally modified forms of activase to determine if loss of activity under heat stress is dependent on protein aggregation. The results showed that 1) loss of activity at high temperature is independent of aggregation; 2) activase with both C- and N-terminal S-Tags are more susceptible to aggregation than wild type activase, 3) aggregation is highly dependent on the concentration of Mg2+ and 4) the ATP analog, ATPgammaS, protects against both thermal inactivation and aggregation.

Correlations among the parameters of the spherical model for eclipsing binaries.

NASA Technical Reports Server (NTRS)

Sobieski, S.; White, J.

1973-01-01

Correlation coefficients have been computed to investigate the parameters used to describe the spherical model of an eclipsing binary system. Regions in parameter hyperspace have been identified where strong correlations exist and, by implication, the solution determinacy is low. The results are presented in tabular form for a large number of system configurations.

Internalization of aggregated photosensitizers by tumor cells: subcellular time-resolved fluorescence spectroscopy on derivatives of pyropheophorbide-a ethers and chlorin e6 under femtosecond one- and two-photon excitations.

PubMed

Kelbauskas, L; Dietel, W

2002-12-01

Amphiphilic sensitizers self-associate in aqueous environments and form aggregated species that exhibit no or only negligible photodynamic activity. However, amphiphilic photosensitizers number among the most potent agents of photodynamic therapy. The processes by which these sensitizers are internalized into tumor cells have yet to be fully elucidated and thus remain the subject of debate. In this study the uptake of photosensitizer aggregates into tumor cells was examined directly using subcellular time-resolved fluorescence spectroscopy with a high temporal resolution (20-30 ps) and high sensitivity (time-correlated single-photon counting). The investigations were performed on selected sensitizers that exhibit short fluorescence decay times (< 50 ps) in aggregated form. Derivatives of pyropheophorbide-a ether and chlorin e6 with varying lipophilicity were used for the study. The characteristic fluorescence decay times and spectroscopic features of the sensitizer aggregates measured in aqueous solution also could be observed in A431 human endothelial carcinoma cells administered with these photosensitizers. This shows that tumor cells can internalize sensitizers in aggregated form. Uptake of aggregates and their monomerization inside cells were demonstrated directly for the first time by means of fluorescence lifetime imaging with a high temporal resolution. Internalization of the aggregates seems to be endocytosis mediated. The degree of their monomerization in tumor cells is strongly influenced by the lipophilicity of the compounds.

Molecular events during the early stages of aggregation of GNNQQNY: An all atom MD simulation study of randomly dispersed peptides.

PubMed

Srivastava, Alka; Balaji, Petety V

2015-12-01

This study probes the early events during lag phase of aggregation of GNNQQNY using all atom MD simulations in explicit solvent. Simulations were performed by varying system size, temperature and starting configuration. Peptides dispersed randomly in the simulation box come together early on in the simulation and form aggregates. These aggregates are dynamic implying the absence of stabilizing interactions. This facilitates the exploration of alternate arrangements. The constituent peptides sample a variety of conformations, frequently re-orient and re-arrange with respect to each other and dissociate from/re-associate with the aggregate. The size and lifetime of aggregates vary depending upon the number of inter-peptide backbone H-bonds. Most of the aggregates formed are amorphous but crystalline aggregates of smaller size (mainly 2-mers) do appear and sustain for varying durations of time. The peptides in crystalline 2-mers are mostly anti-parallel. The largest crystalline aggregate that appears is a 4-mer in a single sheet and a 4-, 5-, or 6-mer in double layered arrangement. Crystalline aggregates grow either by the sequential addition of peptides, or by the head-on or lateral collision-adhesion of 2-mers. The formation of various smaller aggregates suggests the polymorphic nature of oligomers and heterogeneity in the lag phase. Copyright © 2015 Elsevier Inc. All rights reserved.

Method for producing dustless graphite spheres from waste graphite fines

DOEpatents

Pappano, Peter J [Oak Ridge, TN; Rogers, Michael R [Clinton, TN

2012-05-08

A method for producing graphite spheres from graphite fines by charging a quantity of spherical media into a rotatable cylindrical overcoater, charging a quantity of graphite fines into the overcoater thereby forming a first mixture of spherical media and graphite fines, rotating the overcoater at a speed such that the first mixture climbs the wall of the overcoater before rolling back down to the bottom thereby forming a second mixture of spherical media, graphite fines, and graphite spheres, removing the second mixture from the overcoater, sieving the second mixture to separate graphite spheres, charging the first mixture back into the overcoater, charging an additional quantity of graphite fines into the overcoater, adjusting processing parameters like overcoater dimensions, graphite fines charge, overcoater rotation speed, overcoater angle of rotation, and overcoater time of rotation, before repeating the steps until graphite fines are converted to graphite spheres.

Scattering of clusters of spherical particles—Modeling and inverse problem solution in the Rayleigh-Gans approximation

NASA Astrophysics Data System (ADS)

Eliçabe, Guillermo E.

2013-09-01

In this work, an exact scattering model for a system of clusters of spherical particles, based on the Rayleigh-Gans approximation, has been parameterized in such a way that it can be solved in inverse form using Thikhonov Regularization to obtain the morphological parameters of the clusters. That is to say, the average number of particles per cluster, the size of the primary spherical units that form the cluster, and the Discrete Distance Distribution Function from which the z-average square radius of gyration of the system of clusters is obtained. The methodology is validated through a series of simulated and experimental examples of x-ray and light scattering that show that the proposed methodology works satisfactorily in unideal situations such as: presence of error in the measurements, presence of error in the model, and several types of unideallities present in the experimental cases.

The nuclear lamina promotes telomere aggregation and centromere peripheral localization during senescence of human mesenchymal stem cells.

PubMed

Raz, Vered; Vermolen, Bart J; Garini, Yuval; Onderwater, Jos J M; Mommaas-Kienhuis, Mieke A; Koster, Abraham J; Young, Ian T; Tanke, Hans; Dirks, Roeland W

2008-12-15

Ex vivo, human mesenchymal stem cells (hMSCs) undergo spontaneous cellular senescence after a limited number of cell divisions. Intranuclear structures of the nuclear lamina were formed in senescent hMSCs, which are identified by the presence of Hayflick-senescence-associated factors. Notably, spatial changes in lamina shape were observed before the Hayflick senescence-associated factors, suggesting that the lamina morphology can be used as an early marker to identify senescent cells. Here, we applied quantitative image-processing tools to study the changes in nuclear architecture during cell senescence. We found that centromeres and telomeres colocalised with lamina intranuclear structures, which resulted in a preferred peripheral distribution in senescent cells. In addition, telomere aggregates were progressively formed during cell senescence. Once formed, telomere aggregates showed colocalization with gamma-H2AX but not with TERT, suggesting that telomere aggregates are sites of DNA damage. We also show that telomere aggregation is associated with lamina intranuclear structures, and increased telomere binding to lamina proteins is found in cells expressing lamina mutants that lead to increases in lamina intranuclear structures. Moreover, three-dimensional image processing revealed spatial overlap between telomere aggregates and lamina intranuclear structures. Altogether, our data suggest a mechanical link between changes in lamina spatial organization and the formation of telomere aggregates during senescence of hMSCs, which can possibly contribute to changes in nuclear activity during cell senescence.

An Aß concatemer with altered aggregation propensities.

PubMed

Giehm, L; Dal Degan, F; Fraser, P; Klysner, S; Otzen, Daniel E

2010-10-01

We present an analysis of the conformational and aggregative properties of an Aß concatemer (Con-Alz) of interest for vaccine development against Alzheimer's disease. Con-Alz consists of 3 copies of the 43 residues of the Aß peptide separated by the P2 and P30 T-cell epitopes from the tetanus toxin. Even in the presence of high concentrations of denaturants or fluorinated alcohols, Con-Alz has a very high propensity to form aggregates which slowly coalesce over time with changes in secondary, tertiary and quaternary structure. Only micellar concentrations of SDS were able to inhibit aggregation. The increase in the ability to bind the fibril-binding dye ThT increases without lag time, which is characteristic of relatively amorphous aggregates. Confirming this, electron microscopy reveals that Con-Alz adopts a morphology resembling truncated protofibrils after prolonged incubation, but it is unable to assemble into classical amyloid fibrils. Despite its high propensity to aggregate, Con-Alz does not show any significant ability to permeabilize vesicles, which for fibrillating proteins is taken to be a key factor in aggregate cytotoxicity and is attributed to oligomers formed at an early stage in the fibrillation process. Physically linking multiple copies of the Aß-peptide may thus sterically restrict Con-Alz against forming cytotoxic oligomers, forcing it instead to adopt a less well-organized assembly of intermeshed polypeptide chains. Copyright © 2010 Elsevier B.V. All rights reserved.

Visible light-induced insulin aggregation on surfaces via photoexcitation of bound thioflavin T.

PubMed

Chouchane, Karim; Pignot-Paintrand, Isabelle; Bruckert, Franz; Weidenhaupt, Marianne

2018-04-01

Insulin is known to form amyloid aggregates when agitated in a hydrophobic container. Amyloid aggregation is routinely measured by the fluorescence of the conformational dye thioflavin T, which, when incorporated into amyloid fibers, fluoresces at 480 nm. The kinetics of amyloid aggregation in general is characterized by an initial lag-phase, during which aggregative nuclei form on the hydrophobic surface. These nuclei then lead to the formation of fibrils presenting a rapid growth during the elongation phase. Here we describe a novel mechanism of insulin amyloid aggregation which is surprisingly devoid of a lag-time for nucleation. The excitation of thioflavin T by visible light at 440 nm induces the aggregation of thioflavin T-positive insulin fibrils on hydrophobic surfaces in the presence of strong agitation and at physiological pH. This process is material surface-induced and depends on the fact that surface-adsorbed insulin can bind thioflavin T. Light-induced insulin aggregation kinetics is thioflavin T-mediated and is based on an energy transfer from visible light to the protein via thioflavin T. It relies on a constant supply of thioflavin T and insulin from the solution to the aggregate. The growth rate increases with the irradiance and with the concentration of thioflavin T. The supply of insulin seems to be the limiting factor of aggregate growth. This light-induced aggregation process allows the formation of local surface-bound aggregation patterns. Copyright © 2018 Elsevier B.V. All rights reserved.

Effects of Phytoplankton Growth Phase on Delayed Settling Behavior of Marine Snow Aggregates at Sharp Density Transitions

NASA Astrophysics Data System (ADS)

Proctor, K. W.; Montgomery, Q. W.; Prairie, J. C.

2016-02-01

Marine snow aggregates play a fundamental role in the marine carbon cycle. Since marine snow aggregates are larger and thus sink faster than individual phytoplankton, aggregates often dominate carbon flux. Previous studies have shown that marine snow aggregates will significantly decrease their settling velocity when passing through sharp density transitions within the ocean, a phenomenon defined as delayed settling. Given the importance of aggregate settling to carbon export, these small-scale changes in aggregate settling dynamics may have significant impacts on the efficiency of the biological pump. However, there is still a lack of knowledge about how different physical properties of aggregates can affect this delayed settling. In this study, we investigated the effect of phytoplankton growth phase on delayed settling behavior. Using phytoplankton cultures stopped at four different growth phases, we formed marine snow aggregates in the laboratory in rotating cylindrical tanks. We then observed individual aggregates as they settled through a stratified tank. We will present data which illustrates that aggregates experience greatly reduced settling rates when passing through sharp density gradients and that the growth phase of the phytoplankton used to form these aggregates has a significant effect on this delayed settling behavior. A thorough understanding of the impact of phytoplankton growth phase on the delayed settling behavior of marine snow will offer insight into the way phytoplankton growth phase may influence the efficiency of the biological pump, carbon flux, and the carbon cycle as a whole.

Superhydrophilic nanostructure

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

Mao, Samuel S; Zormpa, Vasileia; Chen, Xiaobo

2015-05-12

An embodiment of a superhydrophilic nanostructure includes nanoparticles. The nanoparticles are formed into porous clusters. The porous clusters are formed into aggregate clusters. An embodiment of an article of manufacture includes the superhydrophilic nanostructure on a substrate. An embodiment of a method of fabricating a superhydrophilic nanostructure includes applying a solution that includes nanoparticles to a substrate. The substrate is heated to form aggregate clusters of porous clusters of the nanoparticles.

Simulation, imaging, and mechanics of asphalt pavement (SIMAP) initiative

DOT National Transportation Integrated Search

1998-07-01

Asphalt concrete is a complex material that consists of aggregates, asphalt, and air voids. Aggregates are held together by asphalt and form a skeleton to support the weight of vehicles. The stiffer the asphalt, the tighter the aggregates are held to...

Complex Behavior of Aqueous α-Cyclodextrin Solutions. Interfacial Morphologies Resulting from Bulk Aggregation.

PubMed

Hernandez-Pascacio, Jorge; Piñeiro, Ángel; Ruso, Juan M; Hassan, Natalia; Campbell, Richard A; Campos-Terán, José; Costas, Miguel

2016-07-05

The spontaneous aggregation of α-cyclodextrin (α-CD) molecules in the bulk aqueous solution and the interactions of the resulting aggregates at the liquid/air interface have been studied at 283 K using a battery of techniques: transmission electron microscopy, dynamic light scattering, dynamic surface tensiometry, Brewster angle microscopy, neutron reflectometry, and ellipsometry. We show that α-CD molecules spontaneously form aggregates in the bulk that grow in size with time. These aggregates adsorb to the liquid/air interface with their size in the bulk determining the adsorption rate. The material that reaches the interface coalesces laterally to form two-dimensional domains on the micrometer scale with a layer thickness on the nanometer scale. These processes are affected by the ages of both the bulk and the interface. The interfacial layer formed is not in fast dynamic equilibrium with the subphase as the resulting morphology is locked in a kinetically trapped state. These results reveal a surprising complexity of the parallel physical processes taking place in the bulk and at the interface of what might have seemed initially like a simple system.

Organization of astaxanthin within oil bodies of Haematococcus pluvialis studied with polarization-dependent harmonic generation microscopy.

PubMed

Tokarz, Danielle; Cisek, Richard; El-Ansari, Omar; Espie, George S; Fekl, Ulrich; Barzda, Virginijus

2014-01-01

Nonlinear optical microscopy was used to image the localization of astaxanthin accumulation in the green alga, Haematococcus pluvialis. Polarization-in, polarization-out (PIPO) second harmonic generation (SHG) and third harmonic generation (THG) microscopy was applied to study the crystalline organization of astaxanthin molecules in light-stressed H. pluvialis in vivo. Since astaxanthin readily forms H- and J-aggregates in aqueous solutions, PIPO THG studies of astaxanthin aggregates contained in red aplanospores were compared to PIPO THG of in vitro self-assembled H- and J-aggregates of astaxanthin. The PIPO THG data clearly showed an isotropic organization of astaxanthin in red aplanospores of H. pluvialis. This is in contrast to the highly anisotropic organization of astaxanthin in synthetic H- and J-aggregates, which showed to be uniaxial. Since carotenoids in vitro preferentially form H- and J-aggregates, but in vivo form a randomly organized structure, this implies that astaxanthin undergoes a different way of packing in biological organisms, which is either due to the unique physical environment of the alga or is controlled enzymatically.

Organization of Astaxanthin within Oil Bodies of Haematococcus pluvialis Studied with Polarization-Dependent Harmonic Generation Microscopy

PubMed Central

Tokarz, Danielle; Cisek, Richard; El-Ansari, Omar; Espie, George S.; Fekl, Ulrich; Barzda, Virginijus

2014-01-01

Nonlinear optical microscopy was used to image the localization of astaxanthin accumulation in the green alga, Haematococcus pluvialis. Polarization-in, polarization-out (PIPO) second harmonic generation (SHG) and third harmonic generation (THG) microscopy was applied to study the crystalline organization of astaxanthin molecules in light-stressed H. pluvialis in vivo. Since astaxanthin readily forms H- and J-aggregates in aqueous solutions, PIPO THG studies of astaxanthin aggregates contained in red aplanospores were compared to PIPO THG of in vitro self-assembled H- and J-aggregates of astaxanthin. The PIPO THG data clearly showed an isotropic organization of astaxanthin in red aplanospores of H. pluvialis. This is in contrast to the highly anisotropic organization of astaxanthin in synthetic H- and J-aggregates, which showed to be uniaxial. Since carotenoids in vitro preferentially form H- and J-aggregates, but in vivo form a randomly organized structure, this implies that astaxanthin undergoes a different way of packing in biological organisms, which is either due to the unique physical environment of the alga or is controlled enzymatically. PMID:25215522

Spherical and cylindrical particle resonator as a cloak system

NASA Astrophysics Data System (ADS)

Minin, I. V.; Minin, O. V.; Eremeev, A. I.; Tseplyaev, I. S.

2018-05-01

The concept of dielectric spherical or cylindrical particle in resonant mode as a cloak system is offered. In fundamental modes (modes with the smallest volume correspond to |m| = l, and s = 1) the field is concentrated mostly in the equatorial plane and at the surface of the sphere. Thus under resonance modes, such perturbation due to cuboid particle inserted in the spherical or cylindrical particle has almost no effect on the field forming resonance regardless of the value of internal particle material (defect) as long as this material does not cover the region where resonance takes place.

Three-dimensional spherical models of convection in the earth's mantle

NASA Technical Reports Server (NTRS)

Bercovici, Dave; Schubert, Gerald; Glatzmaier, Gary A.

1989-01-01

Three-dimensional spherical models of mantle convection in the earth reveal that upwelling cylindrical plumes and downwelling planar sheets are the primary features of mantle circulation. Thus subduction zones and descending sheetlike slabs in the mantle are fundamental characteristics of thermal convection in a spherical shell and are not merely the consequences of the rigidity of the slabs, which are cooler than the surrounding mantle. Cylindrical mantle plumes that cause hot spots such as Hawaii are probably the only form of active upwelling and are therefore not just secondary convective currents separate from the large-scale mantle circulation.

On the Interaction and Coalescence if Spherical Blast Waves

NASA Technical Reports Server (NTRS)

Kandula, Max; Freeman, Robert J.

2005-01-01

The scaling and similarity laws concerning the propagation of isolated spherical blast waves are briefly reviewed. Both point source explosions and high pressure gas explosions are considered. Test data on blast overpressure from the interaction and coalescence of spherical blast waves emanating from explosives in the form of shaped charges of different strength placed in the vicinity of a solid propellant stack are presented. These data are discussed with regard to the scaling laws concerning the decay of blast overpressure. The results point out the possibility of detecting source explosions from far-field pressure measurements.

Effect of degassing on the aggregation of carbon nanotubes dispersed in water

NASA Astrophysics Data System (ADS)

Chen, C.-J.; Huang, J.-R.; Hwang, I.-S.; Choi, H. J.; Lai, P.-Y.; Chan, C. K.

2017-10-01

Dynamic light scattering (DLS) along with centrifugation and shaking tests reveal that dissolved gases can significantly affect the aggregation behavior of carbon nanotubes (CNTs) dispersed in water. The CNTs in non-degassed samples form loose, stable networks having the DLS result reminiscent of semidilute polymer solutions, whereas the CNTs in degassed samples aggregate to form Brownian colloids that sediment quickly. Interestingly, the CNTs dispersed in acetone, with or without degassing, also behave like semidilute polymers in DLS experiments. We propose a surface nanobubble-assisted mechanism to explain the observed aggregation behaviors. Our work signifies that dissolved gases may play an important role in determining hydrophobicity and biomolecular functions in aqueous environments.

Dynamic light-scattering study of gelatin and aggregation of gastric mucin

NASA Astrophysics Data System (ADS)

Bansil, Rama; Cao, Xingxiang; Bhaskar, K. Ramakrishnan; LaMont, Jeffrey T.

1997-05-01

Dynamic light scattering studies show that concentration and pH play important roles in determining pig gastric mucin's (PGM) ability to aggregate and gel. At low concentrations, PGM macromolecules exist in solution predominantly in the form of monomers. At high concentrations, PGM macromolecules aggregate to form supra-macromolecular clusters. When the pH of the high concentration PGM solution is changed from 7.0 to 2.0, the system undergoes a sol-gel transition: from a solution of polydisperse aggregates to a gel. This pH and concentration dependent sol-gel transition of PGM solution may provide a mechanism for the mammalian stomach to protect itself against being digested by the gastric juice.

Inherent toxicity of aggregates implies a common mechanism for protein misfolding diseases

NASA Astrophysics Data System (ADS)

Bucciantini, Monica; Giannoni, Elisa; Chiti, Fabrizio; Baroni, Fabiana; Formigli, Lucia; Zurdo, Jesús; Taddei, Niccolò; Ramponi, Giampietro; Dobson, Christopher M.; Stefani, Massimo

2002-04-01

A range of human degenerative conditions, including Alzheimer's disease, light-chain amyloidosis and the spongiform encephalopathies, is associated with the deposition in tissue of proteinaceous aggregates known as amyloid fibrils or plaques. It has been shown previously that fibrillar aggregates that are closely similar to those associated with clinical amyloidoses can be formed in vitro from proteins not connected with these diseases, including the SH3 domain from bovine phosphatidyl-inositol-3'-kinase and the amino-terminal domain of the Escherichia coli HypF protein. Here we show that species formed early in the aggregation of these non-disease-associated proteins can be inherently highly cytotoxic. This finding provides added evidence that avoidance of protein aggregation is crucial for the preservation of biological function and suggests common features in the origins of this family of protein deposition diseases.

Laser desorption vs. electrospray of polyyne-threaded rotaxanes: Preventing covalent cross-linking and promoting noncovalent aggregation

NASA Astrophysics Data System (ADS)

Neugebauer, Thomas S.; Franz, Michael; Frankenberger, Stephanie; Tykwinski, Rik R.; Drewello, Thomas

2018-02-01

Laser-induced cross-linking of polyynes is successfully hindered when the polyyne is encapsulated as part of a rotaxane and therefore protected by a surrounding macrocycle. When the rotaxane is electrosprayed, however, noncovalent aggregate ions are efficiently formed. Aggregates of considerable size (including more than 50 rotaxane molecules with masses beyond 100k Da) and charge states (up to 13 charges and beyond) have been observed. Either protons or sodium cations act as the charge carriers. These aggregates are not formed when the individual components of the rotaxane, i.e., the macrocycle or the polyyne, are separately electrosprayed. This underlines the structural importance of the rotaxane for the aggregate formation. Straightforward force field calculations indicate that the polyyne thread hinders the folding of the macrocycles, which facilitates the bonding interaction between the two components.

Scattering properties of soot-containing particles and their impact by humidity in 1.6 μm

NASA Astrophysics Data System (ADS)

Fan, M.; Chen, L.; Xiong, X.; Li, S.; Tao, J.; Su, L.; Zou, M.; Zhang, Y.

2014-02-01

Short-wave infrared (SWIR) band in wavelength near 1.6 μm is one of the key bands used for satellite observation of Carbon Dioxide (CO2). However, one major uncertainty to use this band for the CO2 retrieval is the scattering by cloud and aerosol particles. To better understand the scattering properties of soot-containing particles in this band, this paper studied the scattering properties for three typical types of soot-containing particles in China: (I) internal mixture, (II) pure soot aggregate, and (III) semi-external mixture. Assumed as single non-spherical particle for type I, its scattering property is computed using the T-matrix method combined with the Maxwell-Garnett effective medium theory and the hygroscopic growth theory. For types II and III, a particle-cluster aggregation algorithm is employed to generate fractal-like aggregates, and their scattering properties are computed using the Core-Mantle Generalized Multi-sphere Mie-solution method combined with the hygroscopic growth theory of both monomers and aggregated particles. The simulated results demonstrate that their scattering properties are quite different and strongly impacted by the levels of relative humidity (RH). For type I, the RH plays a much more important role than the morphology in impacting the scattering properties, and the scattering phase functions among different shaped particles have a larger difference for larger particles and higher RH. For type II, both the RH and morphology significantly affect its scattering properties. The single scattering albedo (ω) can be underestimated up to ~50% without considering the effects of RH and morphological changes. For type III, its scattering properties mainly depend on the RH and the size of the large water-soluble particle. Although the enlarged soot aggregate, which is attached to a water-soluble particle, almost does not change the light direction, it can result in a significant reduction in ω (~0.15) at low RH for small particles. By comparing the scattering parameters of wet particles at a certain RH level with the dry ones, the impact by the heterogeneity of aerosols generally becomes larger with the increase of RH, but becomes smaller with the increase of particle size. These results suggest that, although the water vapor absorption itself is small in 1.6 μm CO2 band, it can significantly impact the scattering properties of these particles through its effect on the hygroscopic growth of the non-spherical and heterogeneous aerosols. This impact should be taken into account in the retrieval of CO2 using 1.6 μm as well as other related remote sensing applications.

Molecules of the quinoline family block tau self-aggregation: implications toward a therapeutic approach for Alzheimer's disease.

PubMed

Navarrete, Leonardo P; Guzmán, Leonardo; San Martín, Aurelio; Astudillo-Saavedra, Luis; Maccioni, Ricardo B

2012-01-01

The neurofibrillary tangles (NFTs) generated by self-aggregation of anomalous forms of tau represent a neuropathological hallmark of Alzheimer's disease (AD). These lesions begin to form long before the clinical manifestation of AD, and its severity is correlated with cognitive impairment in patients. We focused on the search for molecules that interact with aggregated tau of the Alzheimer's type and that may block its aggregation before the formation of NFTs. We show that molecules from a family of quinolines interact specifically with oligomeric forms of tau, inhibiting their assembly into AD filaments. The quinolines 2-(4-methylphenyl)-6-methyl quinoline (THQ-4S) and 2-(4-aminophenyl)-6-methylquinoline (THQ-55) inhibited in vitro aggregation of heparin-induced polymers of purified brain tau and aggregates of human recombinant tau. They also interact with paired helical filaments (PHFs) purified from AD postmortem brains. In vitro studies indicated a significantly lower inhibitory effect of amyloid-β42 on the aggregation, suggesting that tau aggregates are specific targets for quinoline interactions. These compounds showed highly lipophilic properties as corroborated with the analysis of total polar surface areas, and evaluation of their molecular properties. Moreover, these quinolines exhibit physical chemical properties similar to drugs able to penetrate the human brain blood barrier. Docking studies based on tau modeling, as a structural approach to the analysis of the interaction of tau-binding ligands, indicated that a C-terminal tau moiety, involved in the formation of PHFs, seems to be a site for binding of quinolines. Studies suggest the potential clinical use of these quinolines and of their derivatives to inhibit tau aggregation and possible therapeutic routes for AD.

A discrete three-layer stack aggregate of a linear porphyrin tetramer: solution-phase structure elucidation by NMR and X-ray scattering.

PubMed

Hutin, Marie; Sprafke, Johannes K; Odell, Barbara; Anderson, Harry L; Claridge, Tim D W

2013-08-28

Formation of stacked aggregates can dramatically alter the properties of aromatic π-systems, yet the solution-phase structure elucidation of these aggregates is often impossible because broad distributions of species are formed, giving uninformative spectroscopic data. Here, we show that a butadiyne-linked zinc porphyrin tetramer forms a remarkably well-defined aggregate, consisting of exactly three molecules, in a parallel stacked arrangement (in chloroform at room temperature; concentration 1 mM-0.1 μM). The aggregate has a mass of 14.7 kDa. Unlike most previously reported aggregates, it gives sharp NMR resonances and aggregation is in slow exchange on the NMR time scale. The structure was elucidated using a range of NMR techniques, including diffusion-editing, (1)H-(29)Si HMBC, (1)H-(1)H COSY, TOCSY and NOESY, and (1)H-(13)C edited HSQC spectroscopy. Surprisingly, the (1)H-(1)H COSY spectrum revealed many long-range residual dipolar couplings (RDCs), and detailed analysis of magnetic field-induced (1)H-(13)C RDCs provided further evidence for the structural model. The size and shape of the aggregate is supported by small-angle X-ray scattering (SAXS) data. It adopts a geometry that maximizes van der Waals contact between the porphyrins, while avoiding clashes between side chains. The need for interdigitation of the side chains prevents formation of stacks consisting of more than three layers. Although a detailed analysis has only been carried out for one compound (the tetramer), comparison with the NMR spectra of other oligomers indicates that they form similar three-layer stacks. In all cases, aggregation can be prevented by addition of pyridine, although at low pyridine concentrations, disaggregation takes many hours to reach equilibrium.

Bacterial and iron oxide aggregates mediate secondary iron mineral formation: green rust versus magnetite.

PubMed

Zegeye, A; Mustin, C; Jorand, F

2010-06-01

In the presence of methanoate as electron donor, Shewanella putrefaciens, a Gram-negative, facultative anaerobe, is able to transform lepidocrocite (gamma-FeOOH) to secondary Fe (II-III) minerals such as carbonated green rust (GR1) and magnetite. When bacterial cells were added to a gamma-FeOOH suspension, aggregates were produced consisting of both bacteria and gamma-FeOOH particles. Recently, we showed that the production of secondary minerals (GR1 vs. magnetite) was dependent on bacterial cell density and not only on iron reduction rates. Thus, gamma-FeOOH and S. putrefaciens aggregation pattern was suggested as the main mechanism driving mineralization. In this study, lepidocrocite bioreduction experiments, in the presence of anthraquinone disulfonate, were conducted by varying the [cell]/[lepidocrocite] ratio in order to determine whether different types of aggregate are formed, which may facilitate precipitation of GR1 as opposed to magnetite. Confocal laser scanning microscopy was used to analyze the relative cell surface area and lepidocrocite concentration within the aggregates and captured images were characterized by statistical methods for spatial data (i.e. variograms). These results suggest that the [cell]/[lepidocrocite] ratio influenced both the aggregate structure and the nature of the secondary iron mineral formed. Subsequently, a [cell]/[lepidocrocite] ratio above 1 x 10(7) cells mmol(-1) leads to densely packed aggregates and to the formation of GR1. Below this ratio, looser aggregates are formed and magnetite was systematically produced. The data presented in this study bring us closer to a more comprehensive understanding of the parameters governing the formation of minerals in dense bacterial suspensions and suggest that screening mineral-bacteria aggregate structure is critical to understanding (bio)mineralization pathways.

Effect of cobalt ions on the interaction between macrophages and titanium.

PubMed

Pettersson, Mattias; Pettersson, Jean; Thorén, Margareta Molin; Johansson, Anders

2018-04-30

Inflammation and bone reduction around dental implants are described as peri-implantitis and can be caused by an inflammatory response against bacterial products and toxins. Titanium (Ti) forms aggregates with serum proteins, which activate and cause release of the cytokine interleukin (IL-1β) from human macrophages. It was hypothesized that cobalt (Co) ions can interact in the formation of pro-inflammatory aggregates, formed by titanium. To test this hypothesis, we differentiated THP-1 cells into macrophages and exposed them to Ti ions alone or in combination with Co ions to investigate if IL-1β release and cytotoxicity were affected. We also investigated aggregate formation, cell uptake and human biopsies with inductively coupled plasma atomic emission spectroscopy (ICP-AES) and electron microscopy. Co at a concentration of 100 µM neutralized the IL-1β release from human macrophages and affected the aggregate formation. The aggregates formed by Ti could be detected in the cytosol of macrophages. In the presence of Co, the Ti-induced aggregates were located in the cytosol of the cultured macrophages, but outside the lysosomal structures. It is concluded that Co can neutralize the Ti-induced activation and release of active IL-1β from human macrophages in vitro. Also, serum proteins are needed for the formation of metal-protein aggregates in cell medium. Furthermore, the structures of the aggregates as well as the localisation after cellular uptake differ if Co is present in a Ti solution. Phagocytized aggregates with a similar appearance seen in vitro with Ti present, were also visible in a sample from human peri-implant tissue. This article is protected by copyright. All rights reserved. © 2018 Wiley Periodicals, Inc.

Aeolian bedforms, yardangs, and indurated surfaces in the Tharsis Montes as seen by the HiRISE Camera: Evidence for dust aggregates

USGS Publications Warehouse

Bridges, N.T.; Banks, M.E.; Beyer, R.A.; Chuang, F.C.; Noe Dobrea, E.Z.; Herkenhoff, K. E.; Keszthelyi, L.P.; Fishbaugh, K.E.; McEwen, A.S.; Michaels, T.I.; Thomson, B.J.; Wray, J.J.

2010-01-01

HiRISE images of Mars with ground sampling down to 25 cm/pixel show that the dust-rich mantle covering the surfaces of the Tharsis Montes is organized into ridges whose form and distribution are consistent with formation by aeolian saltation. Other dusty areas near the volcanoes and elsewhere on the planet exhibit a similar morphology. The material composing these "reticulate" bedforms is constrained by their remote sensing properties and the threshold curve combined with the saltation/suspension boundary, both of which vary as a function of elevation (atmospheric pressure), particle size, and particle composition. Considering all of these factors, dust aggregates are the most likely material composing these bedforms. We propose that airfall dust on and near the volcanoes aggregates in situ over time, maybe due to electrostatic charging followed by cementation by salts. The aggregates eventually reach a particle size at which saltation is possible. Aggregates on the flanks are transported downslope by katabatic winds and form linear and "accordion" morphologies. Materials within the calderas and other depressions remain trapped and are subjected to multidirectional winds, forming an interlinked "honeycomb" texture. In many places on and near the volcanoes, light-toned, low thermal inertia yardangs and indurated surfaces are present. These may represent "duststone" formed when aggregates reach a particle size below the threshold curve, such that they become stabilized and subsequently undergo cementation. ?? 2009 Elsevier Inc.

Kinetic Model for 1D aggregation of yeast ``prions''

NASA Astrophysics Data System (ADS)

Kunes, Kay; Cox, Daniel; Singh, Rajiv

2004-03-01

Mammalian prion proteins (PrP) are of public health interest because of mad cow and chronic wasting diseases. Yeast have proteins which can undergo similar reconformation and aggregation processes to PrP; yeast forms are simpler to experimentally study and model. Recent in vitro studies of the SUP35 protein(1), showed long aggregates and pure exponential growth of the misfolded form. To explain this data, we have extended a previous model of aggregation kinetics(2). The model assumes reconformation only upon aggregation, and includes aggregate fissioning and an initial nucleation barrier. We find for sufficiently small nucleation rates or seeding by small dimer concentrations that we can achieve the requisite exponential growth and long aggregates. We will compare to a more realistic stochastic kinetics model and present prelimary attempts to describe recent experiments on SUP35 strains. *-Supported by U.S. Army Congressionally Mandated Research Fund. 1) P. Chien and J.S. Weissman, Nature 410, 223 (2001); http://online.kitp.ucsb.edu/online/bionet03/collins/. 2) J. Masel, V.A.> Jansen, M.A. Nowak, Biophys. Chem. 77, 139 (1999).

Division of labour and the evolution of multicellularity

PubMed Central

Ispolatov, Iaroslav; Ackermann, Martin; Doebeli, Michael

2012-01-01

Understanding the emergence and evolution of multicellularity and cellular differentiation is a core problem in biology. We develop a quantitative model that shows that a multicellular form emerges from genetically identical unicellular ancestors when the compartmentalization of poorly compatible physiological processes into component cells of an aggregate produces a fitness advantage. This division of labour between the cells in the aggregate occurs spontaneously at the regulatory level owing to mechanisms present in unicellular ancestors and does not require any genetic predisposition for a particular role in the aggregate or any orchestrated cooperative behaviour of aggregate cells. Mathematically, aggregation implies an increase in the dimensionality of phenotype space that generates a fitness landscape with new fitness maxima, in which the unicellular states of optimized metabolism become fitness saddle points. Evolution of multicellularity is modelled as evolution of a hereditary parameter: the propensity of cells to stick together, which determines the fraction of time a cell spends in the aggregate form. Stickiness can increase evolutionarily owing to the fitness advantage generated by the division of labour between cells in an aggregate. PMID:22158952

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

Peteanu, Linda A.; Chowdhury, Sanchari; Wildeman, Jurjen

One measure of exciton mobility in an aggregate is the efficiency of exciton–exciton annihilation (EEA). Both exciton mobilities and EEA are enhanced for aggregate morphologies in which the distances between chromophores and their relative orientations are favorable for Förster energy transfer. Here this principle is applied to gauge the strength of interchain interactions in aggregates of two substituted PPV oligomers of 7 (OPPV7) and 13 (OPPV13) phenylene rings. These are models of the semiconducting conjugated polymer MEH–PPV. The aggregates were formed by adding a poor solvent (methanol or water) to the oligomers dissolved in a good solvent. Aggregates formed frommore » the longer-chain oligomer and/or by addition of the more polar solvent showed the largest contribution of EEA in their emission decay dynamics. This was found to correlate with the degree to which the steady-state emission spectrum of the monomer is altered by aggregation. Furthermore, the wavelength dependence of the EEA signal was also shown to be useful in differentiating emission features due to monomeric and aggregated chains when their spectra overlap significantly.« less

Dual Effect of (LK)nL Peptides on the Onset of Insulin Amyloid Fiber Formation at Hydrophobic Surfaces.

PubMed

Chouchane, Karim; Vendrely, Charlotte; Amari, Myriam; Moreaux, Katie; Bruckert, Franz; Weidenhaupt, Marianne

2015-08-20

Soluble proteins are constantly in contact with material or cellular surfaces, which can trigger their aggregation and therefore have a serious impact on the development of stable therapeutic proteins. In contact with hydrophobic material surfaces, human insulin aggregates readily into amyloid fibers. The kinetics of this aggregation can be accelerated by small peptides, forming stable beta-sheets on hydrophobic surfaces. Using a series of (LK)nL peptides with varying length, we show that these peptides, at low, substoichiometric concentrations, have a positive, cooperative effect on insulin aggregation. This effect is based on a cooperative adsorption of (LK)nL peptides at hydrophobic surfaces, where they form complexes that help the formation of aggregation nuclei. At higher concentrations, they interfere with the formation of an aggregative nucleus. These effects are strictly dependent on the their adsorption on hydrophobic material surfaces and highlight the importance of the impact of materials on protein stability. (LK)nL peptides prove to be valuable tools to investigate the mechanism of HI aggregation nuclei formation on hydrophobic surfaces.

Characterization of Nanoparticles and Colloids in Aquatic Systems 1. Small Angle Neutron Scattering Investigations of Suwannee River Fulvic Acid Aggregates in Aqueous Solutions

NASA Astrophysics Data System (ADS)

Diallo, Mamadou S.; Glinka, Charles J.; Goddard, William A.; Johnson, James H.

2005-10-01

Fulvic acids (FA) and humic acids (HA) constitute 30-50% of dissolved organic matter in natural aquatic systems. In aqueous solutions, a commonly accepted view is that FA and HA exist as soluble macroligands at low concentration and as supramolecular aggregates at higher concentration. The size, shape and structure of these aggregates are still the subject of ongoing debate in the environmental chemistry literature. In this article, we use small angle neutron scattering (SANS) to assess the effects of solute concentration, solution pH and background electrolyte (NaCl) concentration on the structures of Suwannee River FA (SRFA) aggregates in D2O. The qualitative features of the SANS curves and data analysis are not consistent with the view point that SRFA forms micelle-like aggregates as its concentration in aqueous solution increases. We find that SRFA forms fractal aggregates in D20 with size greater than 242 nm. The SRFA aggregates undergo a significant degree of restructuring in compactness as solution pH, solute concentration and NaCl concentration increase.

An Enzyme from Aristolochia indica Destabilizes Fibrin-β Amyloid Co-Aggregate: Implication in Cerebrovascular Diseases

PubMed Central

Bhattacharjee, Payel; Bhattacharyya, Debasish

2015-01-01

Fibrinogen and β-amyloid (Aβ) peptide independently form ordered aggregates but in combination, they form disordered structures which are resistant to fibrinolytic enzymes like plasmin and cause severity in cerebral amyloid angiopathy (CAA). A novel enzyme of 31.3 kDa has been isolated from the root of the medicinal plant Aristolochia indica that showed fibrinolytic as well as fibrin-Aβ co-aggregate destabilizing properties. This enzyme is functionally distinct from plasmin. Thrombolytic action of the enzyme was demonstrated in rat model. The potency of the plant enzyme in degrading fibrin and fibrin-plasma protein (Aβ, human serum albumin, lysozyme, transthyretin and fibronectin) co-aggregates was demonstrated by atomic force microscopy, scanning electron microscopy and confocal microscopy that showed better potency of the plant enzyme as compared to plasmin. Moreover, the plant enzyme inhibited localization of the co-aggregate inside SH-SY5Y human neuroblastoma cells and also co-aggregate induced cytotoxicity. Plasmin was inefficient in this respect. In the background of limited options for fragmentation of these co-aggregates, the plant enzyme may appear as a potential proteolytic enzyme. PMID:26545113

Fullerene-Based Symmetry in Hibiscus rosa-sinensis Pollen

PubMed Central

Andrade, Kleber; Guerra, Sara; Debut, Alexis

2014-01-01

The fullerene molecule belongs to the so-called super materials. The compound is interesting due to its spherical configuration where atoms occupy positions forming a mechanically stable structure. We first demonstrate that pollen of Hibiscus rosa-sinensis has a strong symmetry regarding the distribution of its spines over the spherical grain. These spines form spherical hexagons and pentagons. The distance between atoms in fullerene is explained applying principles of flat, spherical, and spatial geometry, based on Euclid’s “Elements” book, as well as logic algorithms. Measurements of the pollen grain take into account that the true spine lengths, and consequently the real distances between them, are measured to the periphery of each grain. Algorithms are developed to recover the spatial effects lost in 2D photos. There is a clear correspondence between the position of atoms in the fullerene molecule and the position of spines in the pollen grain. In the fullerene the separation gives the idea of equal length bonds which implies perfectly distributed electron clouds while in the pollen grain we suggest that the spines being equally spaced carry an electrical charge originating in forces involved in the pollination process. PMID:25003375

Proteins with Intrinsically Disordered Domains Are Preferentially Recruited to Polyglutamine Aggregates

PubMed Central

O’Meally, Robert; Sonnenberg, Jason L.; Cole, Robert N.; Shewmaker, Frank P.

2015-01-01

Intracellular protein aggregation is the hallmark of several neurodegenerative diseases. Aggregates formed by polyglutamine (polyQ)-expanded proteins, such as Huntingtin, adopt amyloid-like structures that are resistant to denaturation. We used a novel purification strategy to isolate aggregates formed by human Huntingtin N-terminal fragments with expanded polyQ tracts from both yeast and mammalian (PC-12) cells. Using mass spectrometry we identified the protein species that are trapped within these polyQ aggregates. We found that proteins with very long intrinsically-disordered (ID) domains (≥100 amino acids) and RNA-binding proteins were disproportionately recruited into aggregates. The removal of the ID domains from selected proteins was sufficient to eliminate their recruitment into polyQ aggregates. We also observed that several neurodegenerative disease-linked proteins were reproducibly trapped within the polyQ aggregates purified from mammalian cells. Many of these proteins have large ID domains and are found in neuronal inclusions in their respective diseases. Our study indicates that neurodegenerative disease-associated proteins are particularly vulnerable to recruitment into polyQ aggregates via their ID domains. Also, the high frequency of ID domains in RNA-binding proteins may explain why RNA-binding proteins are frequently found in pathological inclusions in various neurodegenerative diseases. PMID:26317359

Structural formation of huntingtin-like aggregates probed by small-angle neutron scattering

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

Stanley, Christopher B; Perevozchikova, Tatiana; Berthelier-Jung, Valerie M

2011-01-01

In several neurodegenerative disorders, including Huntington s disease (HD), aspects concerning the earliest of protein structures that form along the aggregation pathway have increasingly gained attention since these particular species are likely to be neurotoxic. We used time-resolved small-angle neutron scattering (SANS) to probe in solution these transient structures formed by peptides having the N-terminal sequence context of mutant huntingtin (Htt) exon 1. We obtained snapshots of the formed aggregates as the kinetic reaction ensued to yield quantitative information on their size and mass. At the early stage, small precursor species with an initial radius of gyration (Rg) of 16.1more » 5.9 and average mass of a dimer to trimer were monitored. Structural growth was treated as two modes with a transition from three-dimensional early aggregate formation to two-dimensional fibril growth and association. Our SANS results on the internal structure of the mature fibrils demonstrate loose packing with about 1 peptide per 4.75 -sheet repeat distance, which is shown to be quantitatively consistent with a -helix model. This research provides new insights into the structures forming along the pathway of Htt exon 1 aggregation and should assist in determining the role that precursors play in neuronal toxicity.« less

Simple method for forming thin-wall pressure vessels

NASA Technical Reports Server (NTRS)

Erickson, A. L.; Guist, L. R.

1972-01-01

Application of internal hydrostatic pressure to seam-welded circular cylindrical tanks having corner-welded, flat, circular ends forms large thin-walled high quality tanks. Form limits expansion of cylindrical portion of final tank while hemispherical ends develop freely; no external form or restraint is required to fabricate spherical tanks.

Impact of Supramolecular Aggregation on the Crystallization Kinetics of Organic Compounds from the Supercooled Liquid State.

PubMed

Kalra, Arjun; Tishmack, Patrick; Lubach, Joseph W; Munson, Eric J; Taylor, Lynne S; Byrn, Stephen R; Li, Tonglei

2017-06-05

Despite numerous challenges in their theoretical description and practical implementation, amorphous drugs are of growing importance to the pharmaceutical industry. One such challenge is to gain molecular level understanding of the propensity of a molecule to form and remain as a glassy solid. In this study, a series of structurally similar diarylamine compounds was examined to elucidate the role of supramolecular aggregation on crystallization kinetics from supercooled liquid state. The structural similarity of the compounds makes it easier to isolate the molecular features that affect crystallization kinetics and glass forming ability of these compounds. To examine the role of hydrogen-bonded aggregation and motifs on crystallization kinetics, a combination of thermal and spectroscopic techniques was employed. Using variable temperature FTIR, Raman, and solid-state NMR spectroscopies, the presence of hydrogen bonding in the melt and glassy state was examined and correlated with observed phase transition behaviors. Spectroscopic results revealed that the formation of hydrogen-bonded aggregates involving carboxylic acid and pyridine nitrogen (acid-pyridine aggregates) between neighboring molecules in the melt state impedes crystallization, while the presence of carboxylic acid dimers (acid-acid dimers) in the melt favors crystallization. This study suggests that glass formation of small molecules is influenced by the type of intermolecular interactions present in the melt state and the kinetics associated with the molecules to assemble into a crystalline lattice. For the compounds that form acid-pyridine aggregates, the formation of energy degenerate chains, produced due to conformational flexibility of the molecules, presents a kinetic barrier to crystallization. The poor crystallization tendency of these aggregates stems from the highly directional hydrogen-bonding interactions needed to form the acid-pyridine chains. Conversely, for the compounds that form acid-acid dimers, the nondirectional van der Waals forces needed to construct a nucleus promote rapid assembly and crystallization.

Structural organization of surfactant aggregates in vacuo: a molecular dynamics and well-tempered metadynamics study.

PubMed

Longhi, Giovanna; Fornili, Sandro L; Turco Liveri, Vincenzo

2015-07-07

Experimental investigations using mass spectrometry have established that surfactant molecules are able to form aggregates in the gas phase. However, there is no general consensus on the organization of these aggregates and how it depends on the aggregation number and surfactant molecular structure. In the present paper we investigate the structural organization of some surfactants in vacuo by molecular dynamics and well-tempered metadynamics simulations to widely explore the space of their possible conformations in vacuo. To study how the specific molecular features of such compounds affect their organization, we have considered as paradigmatic surfactants, the anionic single-chain sodium dodecyl sulfate (SDS), the anionic double-chain sodium bis(2-ethylhexyl) sulfosuccinate (AOT) and the zwitterionic single-chain dodecyl phosphatidyl choline (DPC) within a wide aggregation number range (from 5 to 100). We observe that for low aggregation numbers the aggregates show in vacuo the typical structure of reverse micelles, while for large aggregation numbers a variety of globular aggregates occur that are characterized by the coexistence of interlaced domains formed by the polar or ionic heads and by the alkyl chains of the surfactants. Well-tempered metadynamics simulations allows us to confirm that the structural organizations obtained after 50 ns of molecular dynamics simulations are practically the equilibrium ones. Similarities and differences of surfactant aggregates in vacuo and in apolar media are also discussed.

Spherical shock waves in general relativity

NASA Astrophysics Data System (ADS)

Nutku, Y.

1991-11-01

We present the metric appropriate to a spherical shock wave in the framework of general relativity. This is a Petrov type-N vacuum solution of the Einstein field equations where the metric is continuous across the shock and the Riemann tensor suffers a step-function discontinuity. Spherical gravitational waves are described by type-N Robinson-Trautman metrics. However, for shock waves the Robinson-Trautman solutions are unacceptable because the metric becomes discontinuous in the Robinson-Trautman coordinate system. Other coordinate systems that have so far been introduced for describing Robinson-Trautman solutions also suffer from the same defect. We shall present the C0-form of the metric appropriate to spherical shock waves using Penrose's approach of identification with warp. Further extensions of Penrose's method yield accelerating, as well as coupled electromagnetic-gravitational shock-wave solutions.

Real-time imaging of Huntingtin aggregates diverting target search and gene transcription

PubMed Central

Li, Li; Liu, Hui; Dong, Peng; Li, Dong; Legant, Wesley R; Grimm, Jonathan B; Lavis, Luke D; Betzig, Eric; Tjian, Robert; Liu, Zhe

2016-01-01

The presumptive altered dynamics of transient molecular interactions in vivo contributing to neurodegenerative diseases have remained elusive. Here, using single-molecule localization microscopy, we show that disease-inducing Huntingtin (mHtt) protein fragments display three distinct dynamic states in living cells – 1) fast diffusion, 2) dynamic clustering and 3) stable aggregation. Large, stable aggregates of mHtt exclude chromatin and form 'sticky' decoy traps that impede target search processes of key regulators involved in neurological disorders. Functional domain mapping based on super-resolution imaging reveals an unexpected role of aromatic amino acids in promoting protein-mHtt aggregate interactions. Genome-wide expression analysis and numerical simulation experiments suggest mHtt aggregates reduce transcription factor target site sampling frequency and impair critical gene expression programs in striatal neurons. Together, our results provide insights into how mHtt dynamically forms aggregates and disrupts the finely-balanced gene control mechanisms in neuronal cells. DOI: http://dx.doi.org/10.7554/eLife.17056.001 PMID:27484239

NMR study on the network structure of a mixed gel of kappa and iota carrageenans.

PubMed

Hu, Bingjie; Du, Lei; Matsukawa, Shingo

2016-10-05

The temperature dependencies of the (1)H T2 and diffusion coefficient (D) of a mixed solution of kappa-carrageenan and iota-carrageenan were measured by NMR. Rheological and NMR measurements suggested an exponential formation of rigid aggregates of kappa-carrageenan and a gradual formation of fine aggregates of iota-carrageenan during two step increases of G'. The results also suggested that longer carrageenan chains are preferentially involved in aggregation, thus resulting in a decrease in the average Mw of solute carrageenans. The results of diffusion measurements for poly(ethylene oxide) (PEO) suggested that kappa-carrageenan formed thick aggregates that decreased hindrance to PEO diffusion by decreasing the solute kappa-carrageenan concentration in the voids of the aggregated chains, and that iota-carrageenan formed fine aggregates that decreased the solute iota-carrageenan concentration less. DPEO in a mixed solution of kappa-carrageenan and iota-carrageenan suggested two possibilities for the microscopic network structure: an interpenetrating network structure, or micro-phase separation. Copyright © 2016. Published by Elsevier Ltd.

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

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

Shapiro, B I; Tyshkunova, E S; Kondorskiy, A D

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 themore » 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)« less

Protein aggregation induced during glass bead lysis of yeast

PubMed Central

Papanayotou, Irene; Sun, Beimeng; Roth, Amy F.; Davis, Nicholas G.

2013-01-01

Yeast cell lysates produced by mechanical glass bead disruption are widely used in a variety of applications, including for the analysis of native function, e.g. protein–protein interaction, enzyme assays and membrane fractionations. Below, we report a striking case of protein denaturation and aggregation that is induced by this lysis protocol. Most of this analysis focuses on the type 1 casein kinase Yck2, which normally tethers to the plasma membrane through C-terminal palmitoylation. Surprisingly, when cells are subjected to glass bead disruption, non-palmitoylated, cytosolic forms of the kinase denature and aggregate, while membrane-associated forms, whether attached through their native palmitoyl tethers or through a variety of artificial membrane-tethering sequences, are wholly protected from denaturation and aggregation. A wider look at the yeast proteome finds that, while the majority of proteins resist glass bead-induced aggregation, a significant subset does, in fact, succumb to such denaturation. Thus, yeast researchers should be aware of this potential artifact when embarking on biochemical analyses that employ glass bead lysates to look at native protein function. Finally, we demonstrate an experimental utility for glass bead-induced aggregation, using its fine discrimination of membrane-associated from non-associated Yck2 forms to discern fractional palmitoylation states of Yck2 mutants that are partially defective for palmitoylation. PMID:20641011

Ethanol-perturbed amyloidogenic self-assembly of insulin: looking for origins of amyloid strains.

PubMed

Dzwolak, Wojciech; Grudzielanek, Stefan; Smirnovas, Vytautas; Ravindra, Revanur; Nicolini, Chiara; Jansen, Ralf; Loksztejn, Anna; Porowski, Sylwester; Winter, Roland

2005-06-28

A model cosolvent, ethanol, has profound and diversified effects on the amyloidogenic self-assembly of insulin, yielding spectroscopically and morphologically distinguishable forms of beta-aggregates. The alcohol reduces hydrodynamic radii of insulin molecules, decreases enthalpic costs associated with aggregation-prone intermediate states, and accelerates the aggregation itself. Increasing the concentration of the cosolvent promotes curved, amorphous, and finally donut-shaped forms. According to FT-IR data, inter-beta-strand hydrogen bonding is stronger in fibrils formed in the presence of ethanol. Mechanisms underlying the polymorphism of insulin aggregates were investigated by spectroscopic (CD, FT-IR, and fluorescence anisotropy) and calorimetric (DSC and PPC) methods. The nonmonotonic character of the influence of ethanol on insulin aggregation suggests that both preferential exclusion (predominant at the low concentrations) and direct alcohol-protein interactions are involved. The perturbed hydration of aggregation nuclei appears to be a decisive factor in selection of a dominant mode of beta-strand alignment. It may override unfavorable structural consequences of an alternative strand-to-strand stacking, such as strained hydrogen bonding. A hypothetical mechanism of inducing different amyloid "strains" has been put forward. The cooperative character of fibril assembly creates enormous energy barriers for any interstrain transition, which renders the energy landscape comblike-shaped.

ROCKY PLANETESIMAL FORMATION VIA FLUFFY AGGREGATES OF NANOGRAINS

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

Arakawa, Sota; Nakamoto, Taishi, E-mail: arakawa.s.ac@m.titech.ac.jp

2016-12-01

Several pieces of evidence suggest that silicate grains in primitive meteorites are not interstellar grains but condensates formed in the early solar system. Moreover, the size distribution of matrix grains in chondrites implies that these condensates might be formed as nanometer-sized grains. Therefore, we propose a novel scenario for rocky planetesimal formation in which nanometer-sized silicate grains are produced by evaporation and recondensation events in early solar nebula, and rocky planetesimals are formed via aggregation of these nanograins. We reveal that silicate nanograins can grow into rocky planetesimals via direct aggregation without catastrophic fragmentation and serious radial drift, and ourmore » results provide a suitable condition for protoplanet formation in our solar system.« less

Determination of critical nucleation number for a single nucleation amyloid-β aggregation model.

PubMed

Ghosh, Preetam; Vaidya, Ashwin; Kumar, Amit; Rangachari, Vijayaraghavan

2016-03-01

Aggregates of amyloid-β (Aβ) peptide are known to be the key pathological agents in Alzheimer disease (AD). Aβ aggregates to form large, insoluble fibrils that deposit as senile plaques in AD brains. The process of aggregation is nucleation-dependent in which the formation of a nucleus is the rate-limiting step, and controls the physiochemical fate of the aggregates formed. Therefore, understanding the properties of nucleus and pre-nucleation events will be significant in reducing the existing knowledge-gap in AD pathogenesis. In this report, we have determined the plausible range of critical nucleation number (n(*)), the number of monomers associated within the nucleus for a homogenous aggregation model with single unique nucleation event, by two independent methods: A reduced-order stability analysis and ordinary differential equation based numerical analysis, supported by experimental biophysics. The results establish that the most likely range of n(*) is between 7 and 14 and within, this range, n(*) = 12 closely supports the experimental data. These numbers are in agreement with those previously reported, and importantly, the report establishes a new modeling framework using two independent approaches towards a convergent solution in modeling complex aggregation reactions. Our model also suggests that the formation of large protofibrils is dependent on the nature of n(*), further supporting the idea that pre-nucleation events are significant in controlling the fate of larger aggregates formed. This report has re-opened an old problem with a new perspective and holds promise towards revealing the molecular events in amyloid pathologies in the future. Copyright © 2015 Elsevier Inc. All rights reserved.

Continuous form-dependent focusing of non-spherical microparticles in a highly diluted suspension with the help of microfluidic spirals

NASA Astrophysics Data System (ADS)

Roth, Tanja; Sprenger, Lisa; Odenbach, Stefan; Häfeli, Urs O.

2018-04-01

Microfluidic spirals are able to focus non-spherical microparticles in diluted suspension due to the Dean effect. A secondary flow establishes in a curved channel, consisting of two counter-rotating vortices, which transport particles to an equilibrium position near the inner wall of the channel. The relevant size parameter, which is responsible for successful focusing, is the ratio between the particle diameter of a sphere and the hydraulic diameter, which is a characteristic of the microfluidic spiral. A non-spherical particle has not one but several different size parameters. This study investigated the minor and major axes, the equivalent spherical diameter, and the maximal rotational diameter as an equivalent to the spherical diameter. Using a polydimethylsiloxane (PDMS)-based microfluidic device with spirals, experiments were conducted with artificial peanut-shaped and ellipsoidal particles sized between 3 and 9 μm as well as with the bacteria Bacillus subtilis. Our investigations show that the equivalent spherical diameter, the major axis, and the maximal rotational diameter of a non-spherical particle can predict successful focusing. The minor axis is not suitable for this purpose. Non-spherical particles focused when the ratio of their equivalent spherical diameter to the hydraulic diameter of the channel was larger than 0.07. The particles also focused when the ratio between the maximal rotational diameter or the major axis and the hydraulic diameter was larger than 0.01. These results may help us to separate non-spherical biological particles, such as circulating tumor cells or pathogenic bacteria, from blood in future experimental studies.

Monitoring aggregate disintegration with laser diffraction: A tool for studying soils as sediments

NASA Astrophysics Data System (ADS)

Mason, Joseph; Kasmerchak, Chase; Liang, Mengyu

2016-04-01

One of the more important characteristics of soil that becomes hillslope, fluvial, or aeolian sediment is the presences of aggregates, which disintegrate at varying rates and to varying degrees during transport. Laser diffraction particle size analyzers allow monitoring of aggregate disintegration as a sample of soil or sediment suspended in water is circulated continuously through the measurement cell (Bieganowski et al., 2010, Clay Minerals 45-23-34; Mason et al., Catena 87:107-118). Mason et al. (2011) applied this approach to aeolian sedimentary aggregates (e.g. clay pellets eroded from dry lakebeds), immersing dry samples in DI water and circulating them through a Malvern Mastersizer 2000 particle size analyzer for three hours while repeated size distribution (SD) measurements were made. A final measurement was made after sonication and treatment with Na-metaphosphate. In that study, most samples approached a steady SD within three hours, which included both primary mineral grains and persistent aggregates. The disintegration process could be modeled with a first-order rate law representing the disintegration of a single population of aggregates. A wide range of model parameters were observed among the samples studied, and it was suggested that they could be useful in predicting the behavior of these aggregates, under rainfall impact and during slopewash or fluvial transport. Addition of Ca++ to the suspension altered aggregate behavior in some but not all cases. We applied the same method to dry, unground material from upper horizons of soils sampled along a bioclimatic gradient in northern Minnesota, USA, all formed in lithologically similar glacigenic sediment. These ranged from Alfisols (Luvisols) formed under forest since the last deglaciation, to Alfisols under forest that more recently replaced grassland, and Mollisols (Chernozems) that formed entirely under grassland vegetation. Few of these soil samples approached a steady SD within three hours, and modeling aggregate disintegration required the assumption of at least two aggregate populations. Upper horizons of soils formed under grassland displayed relatively slow disintegration throughout the procedure, with a large proportion of aggregates remaining after three hours. E horizons from forest soils, with low organic matter (OM) and clay content, displayed rapid early distintegration of a large portion of the aggregates, followed by much slower breakdown of the remainder (i.e. the two populations modeled had very different rate constants). OM content is clearly the overriding control on aggregate behavior, but we are also exploring effects of clay content and mineralogy, cation chemistry, and other factors. The differences in aggregate behavior are likely to be relevant to transport and deposition of sediment eroded from these soils, and possibly to the transport of OM or nutrients with eroded soil. We hope to incorporate this method into ongoing field studies of soil erosion with colleagues at UW-Madison.

Aggregate complexes of HIV-1 induced by multimeric antibodies.

PubMed

Stieh, Daniel J; King, Deborah F; Klein, Katja; Liu, Pinghuang; Shen, Xiaoying; Hwang, Kwan Ki; Ferrari, Guido; Montefiori, David C; Haynes, Barton; Pitisuttithum, Punnee; Kaewkungwal, Jaranit; Nitayaphan, Sorachai; Rerks-Ngarm, Supachai; Michael, Nelson L; Robb, Merlin L; Kim, Jerome H; Denny, Thomas N; Tomaras, Georgia D; Shattock, Robin J

2014-10-02

Antibody mediated viral aggregation may impede viral transfer across mucosal surfaces by hindering viral movement in mucus, preventing transcytosis, or reducing inter-cellular penetration of epithelia thereby limiting access to susceptible mucosal CD4 T cells and dendritic cells. These functions may work together to provide effective immune exclusion of virus from mucosal tissue; however little is known about the antibody characteristics required to induce HIV aggregation. Such knowledge may be critical to the design of successful immunization strategies to facilitate viral immune exclusion at the mucosal portals of entry. The potential of neutralizing and non-neutralizing IgG and IgA monoclonals (mAbs) to induce HIV-1 aggregation was assessed by Dynamic light scattering (DLS). Although neutralizing and non-neutralizing IgG mAbs and polyclonal HIV-Ig efficiently aggregated soluble Env trimers, they were not capable of forming viral aggregates. In contrast, dimeric (but not monomeric) IgA mAbs induced stable viral aggregate populations that could be separated from uncomplexed virions. Epitope specificity influenced both the degree of aggregation and formation of higher order complexes by dIgA. IgA purified from serum of uninfected RV144 vaccine trial responders were able to efficiently opsonize viral particles in the absence of significant aggregation, reflective of monomeric IgA. These results collectively demonstrate that dIgA is capable of forming stable viral aggregates providing a plausible basis for testing the effectiveness of aggregation as a potential protection mechanism at the mucosal portals of viral entry.

The spherical-harmonics representation for the interaction between diatomic molecules: The general case and applications to COsbnd CO and COsbnd HF

NASA Astrophysics Data System (ADS)

Barreto, Patricia R. P.; Cruz, Ana Claudia P. S.; Barreto, Rodrigo L. P.; Palazzetti, Federico; Albernaz, Alessandra F.; Lombardi, Andrea; Maciel, Glauciete S.; Aquilanti, Vincenzo

2017-07-01

The spherical-harmonics expansion is a mathematically rigorous procedure and a powerful tool for the representation of potential energy surfaces of interacting molecular systems, determining their spectroscopic and dynamical properties, specifically in van der Waals clusters, with applications also to classical and quantum molecular dynamics simulations. The technique consists in the construction (by ab initio or semiempirical methods) of the expanded potential interaction up to terms that provide the generation of a number of leading configurations sufficient to account for faithful geometrical representations. This paper reports the full general description of the method of the spherical-harmonics expansion as applied to diatomic-molecule - diatomic-molecule systems of increasing complexity: the presentation of the mathematical background is given for providing both the application to the prototypical cases considered previously (O2sbnd O2, N2sbnd N2, and N2sbnd O2 systems) and the generalization to: (i) the COsbnd CO system, where a characteristic feature is the lower symmetry order with respect to the cases studied before, requiring a larger number of expansion terms necessary to adequately represent the potential energy surface; and (ii) the COsbnd HF system, which exhibits the lowest order of symmetry among this class of aggregates and therefore the highest number of leading configurations.

Evaluation of size, morphology, concentration, and surface effect of gold nanoparticles on X-ray attenuation in computed tomography.

PubMed

Khademi, Sara; Sarkar, Saeed; Kharrazi, Sharmin; Amini, Seyed Mohammad; Shakeri-Zadeh, Ali; Ay, Mohammad Reza; Ghadiri, Hossein

2018-01-01

Increasing attention has been focused on the use of nanostructures as contrast enhancement agents in medical imaging, especially in computed tomography (CT). To date, gold nanoparticles (GNPs) have been demonstrated to have great potential as contrast agents for CT imaging. This study was designed to evaluate any effect on X-ray attenuation that might result from employing GNPs with a variety of shapes, sizes, surface chemistries, and concentrations. Gold nanorods (GNRs) and spherical GNPs were synthesized for this application. X-ray attenuation was quantified by Hounsfield unit (HU) in CT. Our findings indicated that smaller spherical GNPs (13 nm) had higher X-ray attenuation than larger ones (60 nm) and GNRs with larger aspect ratio exhibited great effect on X-ray attenuation. Moreover, poly ethylene glycol (PEG) coating on GNRs declined X-ray attenuation as a result of limiting the aggregation of GNRs. We observed X-ray attenuation increased when mass concentration of GNPs was elevated. Overall, smaller spherical GNPs can be suggested as a better alternative to Omnipaque, a good contrast agent for CT imaging. This data can be also considered for the application of gold nanostructures in radiation dose enhancement where nanoparticles with high X-ray attenuation are applied. Copyright © 2017 Associazione Italiana di Fisica Medica. Published by Elsevier Ltd. All rights reserved.

Studies on the preparation and plasma spherodization of yttrium aluminosilicate glass microspheres for their potential application in liver brachytherapy

NASA Astrophysics Data System (ADS)

Sreekumar, K. P.; Saxena, S. K.; Kumar, Yogendra; Thiyagarajan, T. K.; Dash, Ashutosh; Ananthapadmanabhan, P. V.; Venkatesh, Meera

2010-02-01

Plasma spheroidization exploits the high temperature and high enthalpy available in the thermal plasma jet to melt irregularly shaped powder particles and quench them to get dense spherical particles. Plasma spheroidization is a versatile process and can be applied to metals, ceramics, alloys and composites to obtain fine spherical powders. Radioactive microspheres incorporated with high energetic beta emitting radioisotopes have been reported to be useful in the palliative treatment of liver cancer. These powders are to be prepared in closer range of near spherical morphology in the size range 20-35 microns. Inactive glass samples were prepared by heating the pre-calculated amount of glass forming ingredients in a recrystallized alumina crucible. The glass was formed by keeping the glass forming ingredients at 1700°C for a period of three hours to form a homogeneous melt. After cooling, the glass was recovered from the crucible by crushing and was subsequently powdered mechanically with the help of mortar and pestle. This powder was used as the feed stock for plasma spheroidization using an indigenously developed 40 kW plasma spray system. Experiments were carried out at various operating parameters. The operating parameters were optimised to get spheroidised particles. The powder was sieved to get the required size range before irradiation.

Application of mesoscale simulation to explore the aggregate morphology of pH-sensitive nanoparticles used as the oral drug delivery carriers under different conditions.

PubMed

Wang, Yan; Chen, Bo Zhi; Liu, Yue Jin; Wu, Zhi Min; Guo, Xin Dong

2017-03-01

The pH-sensitive nanoparticles are selected as the potentially promising oral protein and peptide drug carriers due to their excellent performance. With the poly (lactic-co-glycolic acid)/hydroxypropyl methylcellulose phthalate (PLGA/HP55) nanoparticle as a model nanoparticle, the structure-property relationship of nanoparticles with different conditions is investigated by dissipative particle dynamics (DPD) simulations in our work. In the oral drug delivery system, the poly (lactic-co-glycolic acid) (PLGA) is hydrophobic polymer, hydroxypropyl methylcellulose phthalate (HP55) is pH-sensitive enteric polymer which used to protect the nanoparticles through the stomach and polyvinyl alcohol (PVA) is hydrophilic polymer as the stabilizer. It can be seen from DPD simulations that all polymer molecules form spherical core-shell nanoparticles with stabilizer PVA molecules adsorbed on the outer surface of the PLGA/HP55 matrix at certain compositions. The DPD simulation study can provide microscopic insight into the formation and morphological changes of pH-sensitive nanoparticles which is useful for the design of new materials for high-efficacy oral drug delivery. Copyright © 2016 Elsevier B.V. All rights reserved.

Precipitation of nitrate-cancrinite in Hanford Tank Sludge.

PubMed

Buck, E C; McNamara, B K

2004-08-15

The chemistry of underground storage tanks containing high-level waste at the Hanford Site in Washington State is an area of continued research interest. Thermodynamic models have predicted the formation of analcime and clinoptilolite in Hanford tanks, rather than cancrinite; however, these predictions were based on carbonate-cancrinite. We report the first observation of a nitrate-cancrinite [possibly Na8(K,Cs)(AlSiO4)6(NO3)2 x nH2O] extracted from a Hanford tank 241-AP-101 sample that was evaporated to 6, 8, and 10 M NaOH concentrations. The nitrate-cancrinite phase formed spherical aggregates (4 microm in diameter) that consisted of platy hexagonal crystals (approximately 0.2 microm thick). Cesium-137 was concentrated in these aluminosilicate structures. These phases possessed a morphology identical to that of nitrate-cancrinite synthesized using simulant tests of nonradioactive tank waste, supporting the contention that it is possible to develop nonradioactive artificial sludges. This investigation points to the continued importance of understanding the solubility of NO3-cancrinite and related phases. Knowledge of the detailed structure of actual phases in the tank waste helps with thermodynamic modeling of tank conditions and waste processing.

The nitrogen cycle in cryoconites: naturally occurring nitrification-denitrification granules on a glacier.

PubMed

Segawa, Takahiro; Ishii, Satoshi; Ohte, Nobuhito; Akiyoshi, Ayumi; Yamada, Akinori; Maruyama, Fumito; Li, Zhongqin; Hongoh, Yuichi; Takeuchi, Nozomu

2014-10-01

Cryoconites are microbial aggregates commonly found on glacier surfaces where they tend to take spherical, granular forms. While it has been postulated that the microbes in cryoconite granules play an important role in glacier ecosystems, information on their community structure is still limited, and their functions remain unclear. Here, we present evidence for the occurrence of nitrogen cycling in cryoconite granules on a glacier in Central Asia. We detected marker genes for nitrogen fixation, nitrification and denitrification in cryoconite granules by digital polymerase chain reaction (PCR), while digital reverse transcription PCR analysis revealed that only marker genes for nitrification and denitrification were abundantly transcribed. Analysis of isotope ratios also indicated the occurrence of nitrification; nitrate in the meltwater on the glacier surface was of biological origin, while nitrate in the snow was of atmospheric origin. The predominant nitrifiers on this glacier belonged to the order Nitrosomonadales, as suggested by amoA sequences and 16S ribosomal RNA pyrosequencing analysis. Our results suggest that the intense carbon and nitrogen cycles by nitrifiers, denitrifiers and cyanobacteria support abundant and active microbes on the Asian glacier. © 2014 Society for Applied Microbiology and John Wiley & Sons Ltd.

Application of dynamic light scattering for studying the evolution of micro- and nano-droplets

NASA Astrophysics Data System (ADS)

Derkachov, G.; Jakubczyk, D.; Kolwas, K.; Shopa, Y.; Woźniak, M.; Wojciechowski, T.

2018-01-01

The dynamic light scattering (DLS) technique was used for studying the processes of aggregation of spherical SiO2 particles in various diethylene glycol (DEG) suspensions. The suspensions were studied in a cuvette, in a millimeter-sized droplet and in a micrometer-sized droplet. For the first time DLS signals for droplets of picolitre volume, levitated in an electrodynamic quadrupole trap, were obtained. It is shown that the correlation analysis of light scattered from a micro-droplet allows monitoring the changes of its internal structure, as well as its motions: trap-constricted Brownian motions and random rotations.

Cluster analysis in systems of magnetic spheres and cubes

NASA Astrophysics Data System (ADS)

Pyanzina, E. S.; Gudkova, A. V.; Donaldson, J. G.; Kantorovich, S. S.

2017-06-01

In the present work we use molecular dynamics simulations and graph-theory based cluster analysis to compare self-assembly in systems of magnetic spheres, and cubes where the dipole moment is oriented along the side of the cube in the [001] crystallographic direction. We show that under the same conditions cubes aggregate far less than their spherical counterparts. This difference can be explained in terms of the volume of phase space in which the formation of the bond is thermodynamically advantageous. It follows that this volume is much larger for a dipolar sphere than for a dipolar cube.

Characteristics and origin of coarse gold in Late Pleistocene sediments of the Cariboo placer mining district, British Columbia, Canada

NASA Astrophysics Data System (ADS)

Eyles, N.

1995-02-01

The Cariboo placer mining district (1000 km 2) sited in the Interior Plateau of central British Columbia, Canada, is the premier placer gold mining district of the Province. Gold is recovered from three Late Pleistocene sedimentary facies: postglacial fluvial gravels (< 10 Ka), Late Wisconsin till (ca. 25-10 Ka), and "older" fluvial gravels (>25 Ka). This study reports the morphology (size, roundness, sphericity) of 1636 gold grains, ranging in size from 0.25 to 17 mm, recovered from 19 placer mines. Older gravels contain the smallest gold grains (mean grani size 1.53 mm), grains of intermediate size occur in till (2.23 mm) and the coarsest gold occurs in postglacial gravels (2.34 mm) with a mean of 1.93 mm for the mining district as a whole. The most common grain shapes are sub-rounded, discoidal (14.73% of the grain population), sub-angular, discoidal (10.88%), and sub-rounded, sub-discoidal (9.59%); the most angular grains occur in postglacial gravels. In-situ growth of coarse, angular grains is indicated by a "composite" grain structure, consisting of aggregates of gold particles welded together by high-grade (Ag = < 2%) filamentous gold; in-situ coarsening may be reliant on organic complexing agents produced below a dense forest cover. An evolutionary sequence of grain form, from angular aggregates to rounded "pumpkin seed" grains, is suggested. Rounded grains commonly show a crystalline structure which may result from the cold hammering of gold during transport; fracturing along crystal boundaries is common. Gold grains may undergo cycles of coarsening, rounding, diagenesis and breakup in response to repeated recycling through Pleistocene sedimentary environments.

Lipid-based nanoparticles for contrast-enhanced MRI and molecular imaging.

PubMed

Mulder, Willem J M; Strijkers, Gustav J; van Tilborg, Geralda A F; Griffioen, Arjan W; Nicolay, Klaas

2006-02-01

In the field of MR imaging and especially in the emerging field of cellular and molecular MR imaging, flexible strategies to synthesize contrast agents that can be manipulated in terms of size and composition and that can be easily conjugated with targeting ligands are required. Furthermore, the relaxivity of the contrast agents, especially for molecular imaging applications, should be very high to deal with the low sensitivity of MRI. Lipid-based nanoparticles, such as liposomes or micelles, have been used extensively in recent decades as drug carrier vehicles. A relatively new and promising application of lipidic nanoparticles is their use as multimodal MR contrast agents. Lipids are amphiphilic molecules with both a hydrophobic and a hydrophilic part, which spontaneously assemble into aggregates in an aqueous environment. In these aggregates, the amphiphiles are arranged such that the hydrophobic parts cluster together and the hydrophilic parts face the water. In the low concentration regime, a wide variety of structures can be formed, ranging from spherical micelles to disks or liposomes. Furthermore, a monolayer of lipids can serve as a shell to enclose a hydrophobic core. Hydrophobic iron oxide particles, quantum dots or perfluorocarbon emulsions can be solubilized using this approach. MR-detectable and fluorescent amphiphilic molecules can easily be incorporated in lipidic nanoparticles. Furthermore, targeting ligands can be conjugated to lipidic particles by incorporating lipids with a functional moiety to allow a specific interaction with molecular markers and to achieve accumulation of the particles at disease sites. In this review, an overview of different lipidic nanoparticles for use in MRI is given, with the main emphasis on Gd-based contrast agents. The mechanisms of particle formation, conjugation strategies and applications in the field of contrast-enhanced, cellular and molecular MRI are discussed. 2006 John Wiley & Sons, Ltd.

Nontemplated Approach to Tuning the Spectral Propertiesof Cyanine-Based Fluorescent NanoGUMBOS

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

Das, Susmita; Bwambok, David; El-Zahab, Bilal

2010-01-01

Template-free controlled aggregation and spectral properties in fluorescent organic nanoparticles (FONs) is highly desirable for various applications.Herein, we report a nontemplated method for controlling the aggregation in near-infrared (NIR) cyanine-based nanoparticles derived from a group of uniformmaterials based on organic salts (GUMBOS). Cationic heptamethine cyanine dye 1,10,3,3,30,30-hexamethylindotricarbocyanine (HMT) was coupled with five different anions, viz., [NTf2 -], [BETI-], [TFPB-], [AOT-], and [TFP4B-], by an ion-exchange method to obtain the respective GUMBOS. The nanoGUMBOS obtained via a reprecipitation method were primarily amorphous and spherical (30-100 nm) as suggested by selected area electron diffraction (SAED) and transmission electron microscopy (TEM). The formationmore » of tunable self-assemblies within the nanoGUMBOS was characterized using absorption and fluorescence spectroscopy in conjunction with molecular dynamics simulations. Counterion-controlled spectral properties observed in the nanoGUMBOS were attributed to variations in J/H ratios with different anions. Association with the [AOT-] anion afforded predominant J aggregation enabling the highest fluorescence intensity, whereas [TFP4B-] disabled the fluorescence due to predominantHaggregation in the nanoparticles. Analyses of the stacking angle of the cations based on molecular dynamic simulation results in [HMT][NTf2], [HMT][BETI], and [HMT][AOT] dispersed in water and a visual analysis of the representative simulation snapshots also imply that the type of aggregation was controlled through the counterion associated with the dye cation.« less

Study of nucleic acid-gold nanorod interactions and detecting nucleic acid hybridization using gold nanorod solutions in the presence of sodium citrate.

PubMed

Kanjanawarut, Roejarek; Su, Xiaodi

2010-09-01

In this study, the authors report that sodium citrate can aggregate hexadecyl-trimethyl-ammonium ion(+)-coated gold nanorods (AuNRs), and nucleic acids of different charge and structure properties, i.e., single-stranded DNA (ssDNA), double-stranded DNA (dsDNA), single-stranded peptide nucleic acid (PNA), and PNA-DNA complex, can bind to the AuNRs and therefore retard the sodium citrate-induced aggregation to different extents. The discovery that hybridized dsDNA (and the PNA-DNA complex) has a more pronounced protection effect than ssDNA (and PNA) allows the authors to develop a homogeneous phase AuNRs-based UV-visible (UV-vis) spectral assay for detecting specific sequences of oligonucleotides (20 mer) with a single-base-mismatch selectivity and a limit of detection of 5 nM. This assay involves no tedious bioconjugation and on-particle hybridization. The simple "set and test" format allows for a highly efficient hybridization in a homogeneous phase and a rapid display of the results in less than a minute. By measuring the degree of reduction in AuNR aggregation in the presence of different nucleic acid samples, one can assess how different nucleic acids interact with the AuNRs to complement the knowledge of spherical gold nanoparticles. Besides UV-vis characterization, transmission electron microscopy and zeta potential measurements were conduced to provide visual evidence of the particle aggregation and to support the discussion of the assay principle.

Characterization, origin and aggregation behavior of colloids in eutrophic shallow lake.

PubMed

Xu, Huacheng; Xu, Mengwen; Li, Yani; Liu, Xin; Guo, Laodong; Jiang, Helong

2018-05-31

Stability of colloidal particles contributes to the turbidity in the water column, which significantly influences water quality and ecological functions in aquatic environments especially shallow lakes. Here we report characterization, origin and aggregation behavior of aquatic colloids, including natural colloidal particles (NCPs) and total inorganic colloidal particles (TICPs), in a highly turbid shallow lake, via field observations, simulation experiments, ultrafiltration, spectral and microscopic, and light scattering techniques. The colloidal particles were characterized with various shapes (spherical, polygonal and elliptical) and aluminum-, silicon-, and ferric-containing mineralogical structures, with a size range of 20-200 nm. The process of sediment re-suspension under environmentally relevant conditions contributed 78-80% of TICPs and 54-55% of NCPs in Lake Taihu, representing an important source of colloids in the water column. Both mono- and divalent electrolytes enhanced colloidal aggregation, while a reverse trend was observed in the presence of natural organic matter (NOM). The influence of NOM on colloidal stability was highly related to molecular weight (MW) properties with the high MW fraction exhibiting higher stability efficiency than the low MW counterparts. However, the MW-dependent aggregation behavior for NCPs was less significant than that for TICPs, implying that previous results on colloidal behavior using model inorganic colloids alone should be reevaluated. Further studies are needed to better understand the mobility/stability and transformation of aquatic colloids and their role in governing the fate and transport of pollutants in natural waters. Copyright © 2018. Published by Elsevier Ltd.

Particles size distribution in diluted magnetic fluids

NASA Astrophysics Data System (ADS)

Yerin, Constantine V.

2017-06-01

Changes in particles and aggregates size distribution in diluted kerosene based magnetic fluids is studied by dynamic light scattering method. It has been found that immediately after dilution in magnetic fluids the system of aggregates with sizes ranging from 100 to 250-1000 nm is formed. In 50-100 h after dilution large aggregates are peptized and in the sample stationary particles and aggregates size distribution is fixed.

Density- and wavefunction-normalized Cartesian spherical harmonics for l ≤ 20.

PubMed

Michael, J Robert; Volkov, Anatoliy

2015-03-01

The widely used pseudoatom formalism [Stewart (1976). Acta Cryst. A32, 565-574; Hansen & Coppens (1978). Acta Cryst. A34, 909-921] in experimental X-ray charge-density studies makes use of real spherical harmonics when describing the angular component of aspherical deformations of the atomic electron density in molecules and crystals. The analytical form of the density-normalized Cartesian spherical harmonic functions for up to l ≤ 7 and the corresponding normalization coefficients were reported previously by Paturle & Coppens [Acta Cryst. (1988), A44, 6-7]. It was shown that the analytical form for normalization coefficients is available primarily for l ≤ 4 [Hansen & Coppens, 1978; Paturle & Coppens, 1988; Coppens (1992). International Tables for Crystallography, Vol. B, Reciprocal space, 1st ed., edited by U. Shmueli, ch. 1.2. Dordrecht: Kluwer Academic Publishers; Coppens (1997). X-ray Charge Densities and Chemical Bonding. New York: Oxford University Press]. Only in very special cases it is possible to derive an analytical representation of the normalization coefficients for 4 < l ≤ 7 (Paturle & Coppens, 1988). In most cases for l > 4 the density normalization coefficients were calculated numerically to within seven significant figures. In this study we review the literature on the density-normalized spherical harmonics, clarify the existing notations, use the Paturle-Coppens (Paturle & Coppens, 1988) method in the Wolfram Mathematica software to derive the Cartesian spherical harmonics for l ≤ 20 and determine the density normalization coefficients to 35 significant figures, and computer-generate a Fortran90 code. The article primarily targets researchers who work in the field of experimental X-ray electron density, but may be of some use to all who are interested in Cartesian spherical harmonics.

Highly curved image sensors: a practical approach for improved optical performance

NASA Astrophysics Data System (ADS)

Guenter, Brian; Joshi, Neel; Stoakley, Richard; Keefe, Andrew; Geary, Kevin; Freeman, Ryan; Hundley, Jake; Patterson, Pamela; Hammon, David; Herrera, Guillermo; Sherman, Elena; Nowak, Andrew; Schubert, Randall; Brewer, Peter; Yang, Louis; Mott, Russell; McKnight, Geoff

2017-06-01

The significant optical and size benefits of using a curved focal surface for imaging systems have been well studied yet never brought to market for lack of a high-quality, mass-producible, curved image sensor. In this work we demonstrate that commercial silicon CMOS image sensors can be thinned and formed into accurate, highly curved optical surfaces with undiminished functionality. Our key development is a pneumatic forming process that avoids rigid mechanical constraints and suppresses wrinkling instabilities. A combination of forming-mold design, pressure membrane elastic properties, and controlled friction forces enables us to gradually contact the die at the corners and smoothly press the sensor into a spherical shape. Allowing the die to slide into the concave target shape enables a threefold increase in the spherical curvature over prior approaches having mechanical constraints that resist deformation, and create a high-stress, stretch-dominated state. Our process creates a bridge between the high precision and low-cost but planar CMOS process, and ideal non-planar component shapes such as spherical imagers for improved optical systems. We demonstrate these curved sensors in prototype cameras with custom lenses, measuring exceptional resolution of 3220 line-widths per picture height at an aperture of f/1.2 and nearly 100% relative illumination across the field. Though we use a 1/2.3" format image sensor in this report, we also show this process is generally compatible with many state of the art imaging sensor formats. By example, we report photogrammetry test data for an APS-C sized silicon die formed to a 30$^\\circ$ subtended spherical angle. These gains in sharpness and relative illumination enable a new generation of ultra-high performance, manufacturable, digital imaging systems for scientific, industrial, and artistic use.

Mutually catalyzed birth of population and assets in exchange-driven growth

NASA Astrophysics Data System (ADS)

Lin, Zhenquan; Ke, Jianhong; Ye, Gaoxiang

2006-10-01

We propose an exchange-driven aggregation growth model of population and assets with mutually catalyzed birth to study the interaction between the population and assets in their exchange-driven processes. In this model, monomer (or equivalently, individual) exchange occurs between any pair of aggregates of the same species (population or assets). The rate kernels of the exchanges of population and assets are K(k,l)=Kkl and L(k,l)=Lkl , respectively, at which one monomer migrates from an aggregate of size k to another of size l . Meanwhile, an aggregate of one species can yield a new monomer by the catalysis of an arbitrary aggregate of the other species. The rate kernel of asset-catalyzed population birth is I(k,l)=Iklμ [and that of population-catalyzed asset birth is J(k,l)=Jklν ], at which an aggregate of size k gains a monomer birth when it meets a catalyst aggregate of size l . The kinetic behaviors of the population and asset aggregates are solved based on the rate equations. The evolution of the aggregate size distributions of population and assets is found to fall into one of three categories for different parameters μ and ν : (i) population (asset) aggregates evolve according to the conventional scaling form in the case of μ⩽0 (ν⩽0) , (ii) population (asset) aggregates evolve according to a modified scaling form in the case of ν=0 and μ>0 ( μ=0 and ν>0 ), and (iii) both population and asset aggregates undergo gelation transitions at a finite time in the case of μ=ν>0 .

Studies by immune electron microscopy of hepatitis B surface antigen in PLC/PRF/5 cells.

PubMed

Shibayama, T; Watanabe, T; Kojima, H; Yoshikawa, A; Watanabe, S; Kamimura, T; Suzuki, S; Ichida, F

1984-01-01

Electron microscopic studies of the morphology of hepatitis B surface antigen (HBsAg) produced by PLC/PRF/5 cells in vitro were carried out. Aggregates of 20-nm spherical particles in 3-day culture supernatants were observed by immune electron microscopy (IEM). Aggregates of tubular structures were found with IEM in the extracts of the cells. Tubular structures 18 to 22 nm in diameter were seen by electron microscopy (EM) in the cisternae of the endoplasmic reticulum in 2-3% of the cells. The tubular structures in the cytoplasm and extracts of PLC/PRF/5 cells resembled those observed in the hepatocytes of human carriers of hepatitis B virus (HBV). Intracellular localization of HBsAg in PLC/PRF/5 cells by direct peroxidase-conjugated antibody staining was observed on the tubular structures and the cisternal wall, which contained these structures. Rotation technique analysis indicated that the tubular structures were composed of 11 or 12 subunits.

Development of a Sono-Assembled, Bifunctional Soy Peptide Nanoparticle for Cellular Delivery of Hydrophobic Active Cargoes.

PubMed

Zhang, Yuanhong; Zhao, Mouming; Ning, Zhengxiang; Yu, Shujuan; Tang, Ning; Zhou, Feibai

2018-04-25

Soy proteins are prone to aggregate upon proteolysis, hindering their sustainable development in food processing. Here, a continuous work on the large insoluble peptide aggregates was carried out, aiming to develop a new type of soy peptide-based nanoparticle (SPN) for active cargo delivery. Sono-assembled SPN in spherical appearance and core-shell structure maintained by noncovalent interactions was successfully fabricated, exhibiting small particle size (103.95 nm) in a homogeneous distribution state (PDI = 0.18). Curcumin as a model cargo was efficiently encapsulated into SPN upon sonication, showing high water dispersity (129.6 mg/L, 10 4 higher than its water solubility) and storage stability. Additionally, the pepsin-resistant SPN contributed to the controlled release of curcumin at the intestinal phase and thus significantly improved the bioaccessibility. Encapsulated curcumin was effective in protecting glutamate-induced toxicity in PC12 cells, where the matrix SPN can simultaneously reduce lipid peroxidation and elevate antioxidant enzymes levels, innovatively demonstrating its bifunctionality during cellular delivery.

Deformation and relaxation of an incompressible viscoelastic body with surface viscoelasticity

NASA Astrophysics Data System (ADS)

Liu, Liping; Yu, Miao; Lin, Hao; Foty, Ramsey

2017-01-01

Measuring mechanical properties of cells or cell aggregates has proven to be an involved process due to their geometrical and structural complexity. Past measurements are based on material models that completely neglect the elasticity of either the surface membrane or the interior bulk. In this work, we consider general material models to account for both surface and bulk viscoelasticity. The boundary value problems are formulated for deformations and relaxations of a closed viscoelastic surface coupled with viscoelastic media inside and outside of the surface. The linearized surface elasticity models are derived for the constant surface tension model and the Helfrich-Canham bending model for coupling with the bulk viscoelasticity. For quasi-spherical surfaces, explicit solutions are obtained for the deformation, stress-strain and relaxation behaviors under a variety of loading conditions. These solutions can be applied to extract the intrinsic surface and bulk viscoelastic properties of biological cells or cell aggregates in the indentation, electro-deformation and relaxation experiments.

Size determination of gold nanoparticles in silicate glasses by UV-Vis spectroscopy

NASA Astrophysics Data System (ADS)

Ali, Shahid; Khan, Younas; Iqbal, Yaseen; Hayat, Khizar; Ali, Muhammad

2017-01-01

A relatively easier and more accurate method for the determination of average size of metal nanoparticles/aggregates in silicate glasses based on ultraviolet visible (UV-Vis) spectra fitted with the Mie and Mie-Gans models was reported. Gold ions were diffused into sodalime silicate and borosilicate glasses by field-assisted solid-state ion-exchange technique using the same experimental parameters for both glasses. Transmission electron microscopy was performed to directly investigate the morphology and distribution of the dopant nanoparticles. UV-Vis spectra of the doped glasses showed broad surface plasmon resonance peaks in their fingerprint regions, i.e., at 525 and 500 nm for sodalime silicate and borosilicate glass matrices, respectively. These spectra were fitted with the Mie model for spherical nanoparticles and the Mie-Gans model for spheroidal nanoparticles. Although both the models were developed for colloidal nanoparticles, the size of the nanoparticles/aggregates calculated was accurate to within ˜10% in both the glass matrices in comparison to the size measured directly from the transmission electron microscope images.

The search for refractory interplanetary dust particles from preindustrial aged Antarctic ice

NASA Technical Reports Server (NTRS)

Zolensky, Michael E.; Webb, Susan J.; Thomas, Kathie

1988-01-01

In a study of refractory interplanetary dust particles, preindustrial-aged Antarctic ice samples have been collected, melted, and filtered to separate the particle load. Particles containing a significant amount of aluminum, titanium, and/or calcium were singled out for detailed SEM and STEM characterization. The majority of these particles are shown to be volcanic tephra from nearby volcanic centers. Six spherical aggregates were encountered that consist of submicron-sized grains of rutile within polycrystalline cristobalite. These particles are probably of terrestrial volcanic origin, but have not been previously reported from any environment. One aggregate particle containing fassaite and hibonite is described as a probable interplanetary dust particle. The constituent grain sizes of this particle vary from 0.1 to 0.3 microns, making it significantly more fine-grained than meteoritic calcium-aluminum-rich inclusions. This particle is mineralogically and morphologically similar to recently reported refractory interplanetary dust particles collected from the stratosphere, and dissimilar to the products of modern spacecraft debris.

A model study of aggregates composed of spherical soot monomers with an acentric carbon shell

NASA Astrophysics Data System (ADS)

Luo, Jie; Zhang, Yongming; Zhang, Qixing

2018-01-01

Influences of morphology on the optical properties of soot particles have gained increasing attentions. However, studies on the effect of the way primary particles are coated on the optical properties is few. Aimed to understand how the primary particles are coated affect the optical properties of soot particles, the coated soot particle was simulated using the acentric core-shell monomers model (ACM), which was generated by randomly moving the cores of concentric core-shell monomers (CCM) model. Single scattering properties of the CCM model with identical fractal parameters were calculated 50 times at first to evaluate the optical diversities of different realizations of fractal aggregates with identical parameters. The results show that optical diversities of different realizations for fractal aggregates with identical parameters cannot be eliminated by averaging over ten random realizations. To preserve the fractal characteristics, 10 realizations of each model were generated based on the identical 10 parent fractal aggregates, and then the results were averaged over each 10 realizations, respectively. The single scattering properties of all models were calculated using the numerically exact multiple-sphere T-matrix (MSTM) method. It is found that the single scattering properties of randomly coated soot particles calculated using the ACM model are extremely close to those using CCM model and homogeneous aggregate (HA) model using Maxwell-Garnett effective medium theory. Our results are different from previous studies. The reason may be that the differences in previous studies were caused by fractal characteristics but not models. Our findings indicate that how the individual primary particles are coated has little effect on the single scattering properties of soot particles with acentric core-shell monomers. This work provides a suggestion for scattering model simplification and model selection.

Controlled release of β-carotene in β-lactoglobulin-dextran-conjugated nanoparticles' in vitro digestion and transport with Caco-2 monolayers.

PubMed

Yi, Jiang; Lam, Tina I; Yokoyama, Wallace; Cheng, Luisa W; Zhong, Fang

2014-09-03

Undesirable aggregation of nanoparticles stabilized by proteins may occur at the protein's isoelectric point when the particle has zero net charge. Stability against aggregation of nanoparticles may be improved by reacting free amino groups with reducing sugars by the Maillard reaction. β-Lactoglobulin (BLG)-dextran conjugates were characterized by SDS-PAGE and CD. Nanoparticles (60-70 nm diameter) of β-carotene (BC) encapsulated by BLG or BLG-dextran were prepared by the homogenization-evaporation method. Both BLG and BLG-dextran nanoparticles appeared to be spherically shaped and uniformly dispersed by TEM. The stability and release of BC from the nanoparticles under simulated gastrointestinal conditions were evaluated. Dextran conjugation prevented the flocculation or aggregation of BLG-dextran particles at pH ∼4-5 compared to very large sized aggregates of BLG nanoparticles. The released contents of BC from BLG and BLG-dextran nanoparticles under acidic gastric conditions were 6.2 ± 0.9 and 5.4 ± 0.3%, respectively. The release of BC from BLG-dextran nanoparticles by trypsin digestion was 51.8 ± 4.3% of total encapsulated BC, and that from BLG nanoparticles was 60.9 ± 2.9%. Neither BLG-BC nanoparticles nor the Maillard-reacted BLG-dextran conjugates were cytotoxic to Caco-2 cells, even at 10 mg/mL. The apparent permeability coefficient (Papp) of Caco-2 cells to BC was improved by nanoencapsulation, compared to free BC suspension. The results indicate that BC-encapsulated β-lactoglobulin-dextran-conjugated nanoparticles are more stable to aggregation under gastric pH conditions with good release and permeability properties.

Temporal and spatial variation of morphological descriptors for atmospheric aerosols collected in Mexico City

NASA Astrophysics Data System (ADS)

China, S.; Mazzoleni, C.; Dubey, M. K.; Chakrabarty, R. K.; Moosmuller, H.; Onasch, T. B.; Herndon, S. C.

2010-12-01

We present an analysis of morphological characteristics of atmospheric aerosol collected during the MILAGRO (Megacity Initiative: Local and Global Research Observations) field campaign that took place in Mexico City in March 2006. The sampler was installed on the Aerodyne mobile laboratory. The aerosol samples were collected on nuclepore clear polycarbonate filters mounted in Costar pop-top membrane holders. More than one hundred filters were collected at different ground sites with different atmospheric and geographical characteristics (urban, sub-urban, mountain-top, industrial, etc.) over a month period. Selected subsets of these filters were analyzed for aerosol morphology using a scanning electron microscope and image analysis techniques. In this study we investigate spatial and temporal variations of aerosol shape descriptors, morphological parameters, and fractal dimension. We also compare the morphological results with other aerosol measurements such as aerosol optical properties(scattering and absorption) and size distribution data. Atmospheric aerosols have different morphological characteristics depending on many parameters such as emission sources, atmospheric formation pathways, aging processes, and aerosol mixing state. The aerosol morphology influences aerosol chemical and mechanical interactions with the environment, physical properties, and radiative effects. In this study, ambient aerosol particles have been classified in different shape groups as spherical, irregularly shaped, and fractal-like aggregates. Different morphological parameters such as aspect ratio, roundness, feret diameter, etc. have been estimated for irregular shaped and spherical particles and for different kinds of soot particles including fresh soot, collapsed and coated soot. Fractal geometry and image processing have been used to obtain morphological characteristics of different soot particles. The number of monomers constituting each aggregate and their diameters were measured and used to estimate an ensemble three-dimensional (3-d) fractal dimension. One-dimensional (1-d) and two-dimensional (2-d) fractal geometries have been measured using a power-law scaling relationship between 1-d and 2-d properties of projected images. Temporal variations in fractal dimension of soot-like aggregates have been observed at the mountaintop site and spatial variation of fractal dimension and other morphological descriptors of different shaped particles have been investigated for the different ground sites.

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

Landreh, Michael; Stukenborg, Jan-Bernd; Willander, Hanna

Highlights: Black-Right-Pointing-Pointer Insulin and C-peptide can interact under insulin fibril forming conditions. Black-Right-Pointing-Pointer C-peptide is incorporated into insulin aggregates and alters aggregation lag time. Black-Right-Pointing-Pointer C-peptide changes insulin fibril morphology and affects backbone accessibility. Black-Right-Pointing-Pointer C-peptide may be a regulator of fibril formation by {beta}-cell granule proteins. -- Abstract: Insulin aggregation can prevent rapid insulin uptake and cause localized amyloidosis in the treatment of type-1 diabetes. In this study, we investigated the effect of C-peptide, the 31-residue peptide cleaved from proinsulin, on insulin fibrillation at optimal conditions for fibrillation. This is at low pH and high concentration, when the fibrilsmore » formed are regular and extended. We report that C-peptide then modulates the insulin aggregation lag time and profoundly changes the fibril appearance, to rounded clumps of short fibrils, which, however, still are Thioflavine T-positive. Electrospray ionization mass spectrometry also indicates that C-peptide interacts with aggregating insulin and is incorporated into the aggregates. Hydrogen/deuterium exchange mass spectrometry further reveals reduced backbone accessibility in insulin aggregates formed in the presence of C-peptide. Combined, these effects are similar to those of C-peptide on islet amyloid polypeptide fibrillation and suggest that C-peptide has a general ability to interact with amyloidogenic proteins from pancreatic {beta}-cell granules. Considering the concentrations, these peptide interactions should be relevant also during physiological secretion, and even so at special sites post-secretory or under insulin treatment conditions in vivo.« less

Monomeric and fibrillar α-synuclein exert opposite effects on the catalytic cycle that promotes the proliferation of Aβ42 aggregates

PubMed Central

Chia, Sean; Habchi, Johnny; Lattanzi, Veronica; Dobson, Christopher M.; Knowles, Tuomas P. J.; Vendruscolo, Michele

2017-01-01

The coaggregation of the amyloid-β peptide (Aβ) and α-synuclein is commonly observed in a range of neurodegenerative disorders, including Alzheimer’s and Parkinson’s diseases. The complex interplay between Aβ and α-synuclein has led to seemingly contradictory results on whether α-synuclein promotes or inhibits Aβ aggregation. Here, we show how these conflicts can be rationalized and resolved by demonstrating that different structural forms of α-synuclein exert different effects on Aβ aggregation. Our results demonstrate that whereas monomeric α-synuclein blocks the autocatalytic proliferation of Aβ42 (the 42-residue form of Aβ) fibrils, fibrillar α-synuclein catalyses the heterogeneous nucleation of Aβ42 aggregates. It is thus the specific balance between the concentrations of monomeric and fibrillar α-synuclein that determines the outcome of the Aβ42 aggregation reaction. PMID:28698377

Externalized decondensed neutrophil chromatin occludes pancreatic ducts and drives pancreatitis

PubMed Central

Leppkes, Moritz; Maueröder, Christian; Hirth, Sebastian; Nowecki, Stefanie; Günther, Claudia; Billmeier, Ulrike; Paulus, Susanne; Biermann, Mona; Munoz, Luis E.; Hoffmann, Markus; Wildner, Dane; Croxford, Andrew L.; Waisman, Ari; Mowen, Kerri; Jenne, Dieter E.; Krenn, Veit; Mayerle, Julia; Lerch, Markus M.; Schett, Georg; Wirtz, Stefan; Neurath, Markus F.; Herrmann, Martin; Becker, Christoph

2016-01-01

Ductal occlusion has been postulated to precipitate focal pancreatic inflammation, while the nature of the primary occluding agents has remained elusive. Neutrophils make use of histone citrullination by peptidyl arginine deiminase-4 (PADI4) in contact to particulate agents to extrude decondensed chromatin as neutrophil extracellular traps (NETs). In high cellular density, NETs form macroscopically visible aggregates. Here we show that such aggregates form inside pancreatic ducts in humans and mice occluding pancreatic ducts and thereby driving pancreatic inflammation. Experimental models indicate that PADI4 is critical for intraductal aggregate formation and that PADI4-deficiency abrogates disease progression. Mechanistically, we identify the pancreatic juice as a strong instigator of neutrophil chromatin extrusion. Characteristic single components of pancreatic juice, such as bicarbonate ions and calcium carbonate crystals, induce aggregated NET formation. Ductal occlusion by aggregated NETs emerges as a pathomechanism with relevance in a plethora of inflammatory conditions involving secretory ducts. PMID:26964500

Spherical crystals of Pb 1 - xSn xTe grown in microgravity

NASA Astrophysics Data System (ADS)

Kinoshita, Kyoichi; Yamada, Tomoaki

1996-07-01

Pb 1- xSn xTe spherical crystals were unintentionally obtained along with a cylindrical Pb 1 - xSn xTe crystal grown during the {SL-J}/{FMPT} mission on board the space shuttle "Endeavor". About 25 spherical crystals ranged from 0.5 to 11 mm in diameter. Melt leaked from the melt reservoir into the spring that plays the role of pushing the melt toward a seed crystal and eliminating free surface areas of the melt. Because of the surface tension of the melt, spherical melt drops formed in the hollow of the spring, then solidified into spherical crystals during the cooling process. Some of the crystals had lower dislocation densities, in the order of 10 4 cm -2, two orders smaller than those of terrestrially grown crystals from a melt. The experiment showed a way of stably positioning a large volume of liquid in microgravity without touching the crucible wall and a way of reducing crystalline defects by such growth.

Solution of an eigenvalue problem for the Laplace operator on a spherical surface. M.S. Thesis - Maryland Univ.

NASA Technical Reports Server (NTRS)

Walden, H.

1974-01-01

Methods for obtaining approximate solutions for the fundamental eigenvalue of the Laplace-Beltrami operator (also referred to as the membrane eigenvalue problem for the vibration equation) on the unit spherical surface are developed. Two specific types of spherical surface domains are considered: (1) the interior of a spherical triangle, i.e., the region bounded by arcs of three great circles, and (2) the exterior of a great circle arc extending for less than pi radians on the sphere (a spherical surface with a slit). In both cases, zero boundary conditions are imposed. In order to solve the resulting second-order elliptic partial differential equations in two independent variables, a finite difference approximation is derived. The symmetric (generally five-point) finite difference equations that develop are written in matrix form and then solved by the iterative method of point successive overrelaxation. Upon convergence of this iterative method, the fundamental eigenvalue is approximated by iteration utilizing the power method as applied to the finite Rayleigh quotient.

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

Antsiferov, P. S., E-mail: Ants@isan.troitsk.ru; Dorokhin, L. A.

The influence of the discharge cavity dimensions on the properties of the spherical plasma formed in a fast discharge was studied experimentally. The passage of a current pulse with an amplitude of 30–40 kA and a rise rate of ~10{sup 12} A/s (a fast discharge) through a spherical ceramic (Al{sub 2}O{sub 3}) cavity with an inner diameter of 11 mm filled with argon at a pressure of 80 Pa results in the formation of a 1- to 2-mm-diameter spherical plasma with an electron temperature of several tens of electronvolts and a density of 10{sup 18}–10{sup 19} cm{sup –3}. It ismore » shown that an increase in the inner diameter of the discharge cavity from 11 to 21 mm leads to the fourfold increase in the formation time of the spherical plasma and a decrease in the average ion charge. A decrease in the cavity diameter to 7 mm makes the spherical plasma unstable.« less

Size analysis of polyglutamine protein aggregates using fluorescence detection in an analytical ultracentrifuge.

PubMed

Polling, Saskia; Hatters, Danny M; Mok, Yee-Foong

2013-01-01

Defining the aggregation process of proteins formed by poly-amino acid repeats in cells remains a challenging task due to a lack of robust techniques for their isolation and quantitation. Sedimentation velocity methodology using fluorescence detected analytical ultracentrifugation is one approach that can offer significant insight into aggregation formation and kinetics. While this technique has traditionally been used with purified proteins, it is now possible for substantial information to be collected with studies using cell lysates expressing a GFP-tagged protein of interest. In this chapter, we describe protocols for sample preparation and setting up the fluorescence detection system in an analytical ultracentrifuge to perform sedimentation velocity experiments on cell lysates containing aggregates formed by poly-amino acid repeat proteins.

Formation and differentiation of three-dimensional rat marrow stromal cell culture on microcarriers in a rotating-wall vessel

NASA Technical Reports Server (NTRS)

Qiu, Q.; Ducheyne, P.; Gao, H.; Ayyaswamy, P.

1998-01-01

Using a high aspect ratio vessel (HARV), this study investigated the formation of 3-D rat marrow stromal cell culture on microcarriers and the expression of bone-related biochemical markers under conditions of simulated microgravity. In addition, it calculated the shear stresses imparted on the surface of microcarriers of different densities by the medium fluid in an HARV. Secondary rat marrow stromal cells were cultured on two types of microcarriers, Cytodex-3 beads and modified bioactive glass particles. Examination of cellular morphology by scanning electron microscopy revealed the presence of three-dimensional multicellular aggregates consisting of multiple cell-covered Cytodex-3 microcarriers bridged together. Mineralization was observed in the aggregates. Spherical cell-bead aggregates were observed in an HARV, while cell-bead assemblies were mostly loosely packed in a chain-like or branched structure in a cell bag. The expressions of alkaline phosphatase activity, collagen type I, and osteopontin were shown via the use of histochemical staining, immunolabeling, and confocal scanning electron microscopy. Using a numerical approach, it was found that at a given rotational speed and for a given culture medium, a larger density difference between the microcarrier and the culture medium (e.g., a modified bioactive glass particle) imparted a higher maximum shear stress on the microcarrier.

Detection of Mutant Huntingtin Aggregation Conformers and Modulation of SDS-Soluble Fibrillar Oligomers by Small Molecules

PubMed Central

Sontag, Emily Mitchell; Lotz, Gregor P.; Yang, Guocheng; Sontag, Christopher J.; Cummings, Brian J.; Glabe, Charles G.; Muchowski, Paul J.; Thompson, Leslie Michels

2012-01-01

The Huntington’s disease (HD) mutation leads to a complex process of Huntingtin (Htt) aggregation into multimeric species that eventually form visible inclusions in cytoplasm, nuclei and neuronal processes. One hypothesis is that smaller, soluble forms of amyloid proteins confer toxic effects and contribute to early cell dysfunction. However, analysis of mutant Htt aggregation intermediates to identify conformers that may represent toxic forms of the protein and represent potential drug targets remains difficult. We performed a detailed analysis of aggregation conformers in multiple in vitro, cell and ex vivo models of HD. Conformation-specific antibodies were used to identify and characterize aggregation species, allowing assessment of multiple conformers present during the aggregation process. Using a series of assays together with these antibodies, several forms could be identified. Fibrillar oligomers, defined as having a β-sheet rich conformation, are observed in vitro using recombinant protein and in protein extracts from cells in culture or mouse brain and shown to be globular, soluble and non-sedimentable structures. Compounds previously described to modulate visible inclusion body formation and reduce toxicity in HD models were also tested and consistently found to alter the formation of fibrillar oligomers. Interestingly, these compounds did not alter the rate of visible inclusion formation, indicating that fibrillar oligomers are not necessarily the rate limiting step of inclusion body formation. Taken together, we provide insights into the structure and formation of mutant Htt fibrillar oligomers that are modulated by small molecules with protective potential in HD models. PMID:24086178

Cytoskeleton in gravisensing and signal transductionof lower plants

NASA Astrophysics Data System (ADS)

Braun, M.

Characean rhizoids and protonemata are favourable cell types for studying tip growth and gravisensing. Both processes are highly dependent on the actin cytoskeleton. The multiple functions and different arrangements of actin in both cell types are regulated by the concerted action of actin-binding proteins. Monomer- binding profilin is distributed evenly throughout the cytoplasm and is likely to be involved in the regulation of the polymerization state of actin. Actin-severing ADF, spectrin- and actinin-like epitopes concentrate in a central prominent spot in the apex of both cell types, where they colocalize with a dense, spherical actin array and a unique aggregation of endoplasmic reticulum (ER), the structural center of the tip - growth organizing Spitzenkörper. The ER aggregate disintegrates and immuno- localization of the actin-binding proteins fails when tip growth is arrested; the epitopes reappear when tip growth resumes. Actin filaments form a meshwork of axially oriented filaments in the subapical zone and focus in this central apical area which seems to represent their apical polymerization site. The rapid turn-over and rearrangement of actin might be under control of ADF and profilin. Spectrin- and actinin-like proteins are candidates for establishing the actin-mediated anchoring and maintaining of the ER aggregate. They could also provide a mechanism for recruiting specific membrane proteins that create the particular physiological environment for gravity-oriented tip growth. The positioning and sedimentation of statoliths in the subapical region (crucial for gravisensing) is highly coordinated by actomyosin. Non-invasive infrared laser micromanipulation techniques, centri- fugation and experiments in microgravity revealed that reorientation of the growth direction was initiated when at least 2-3 statoliths were directed to specific areas of the plasma membrane by actomyosin and gravitational forces. The statolith-sensitive area is confined to the statolith region (10-35 μm) in positively gravitropic rhizoids, whereas in negatively gravitropic protonemata, it is limited to the apical plasma membrane (0-10 μm). The statolith-sensitive plasma-membrane areas represent the primary sites for graviperception, where the information derived from statolith sedimentation is transformed into physiological signals which trigger the molecular mechanisms of the opposite graviresponses in characean rhizoids and protonemata

Cytosolic Proteostasis via Importing of Misfolded Proteins into Mitochondria

PubMed Central

Ruan, Linhao; Zhou, Chuankai; Jin, Erli; Kucharavy, Andrei; Zhang, Ying; Wen, Zhihui; Florens, Laurence; Li, Rong

2017-01-01

Loss of proteostasis underlies aging and neurodegeneration characterized by the accumulation of protein aggregates and mitochondrial dysfunction1–5. Although many neurodegenerative-disease proteins can be found in mitochondria4,6, it remains unclear how these disease manifestations may be related. In yeast, protein aggregates formed under stress or during aging are preferentially retained by the mother cell in part through tethering to mitochondria, while the disaggregase Hsp104 helps dissociate aggregates to enable refolding or degradation of misfolded proteins7–10. Here we show that in yeast cytosolic proteins prone to aggregation are imported into mitochondria for degradation. Protein aggregates formed under heat shock (HS) contain both cytosolic and mitochondrial proteins and interact with mitochondrial import complex. Many aggregation-prone proteins enter mitochondrial intermembrane space and matrix after HS, while some do so even without stress. Timely dissolution of cytosolic aggregates requires mitochondrial import machinery and proteases. Blocking mitochondrial import but not the proteasome activity causes a marked delay in the degradation of aggregated proteins. Defects in cytosolic Hsp70s leads to enhanced entry of misfolded proteins into mitochondria and elevated mitochondrial stress. We term this mitochondria-mediated proteostasis mechanism MAGIC (mitochondria as guardian in cytosol) and provide evidence that it may exist in human cells. PMID:28241148

Long-term Culture of Human iPS Cell-derived Telencephalic Neuron Aggregates on Collagen Gel.

PubMed

Oyama, Hiroshi; Takahashi, Koji; Tanaka, Yoshikazu; Takemoto, Hiroshi; Haga, Hisashi

2018-01-01

It takes several months to form the 3-dimensional morphology of the human embryonic brain. Therefore, establishing a long-term culture method for neuronal tissues derived from human induced pluripotent stem (iPS) cells is very important for studying human brain development. However, it is difficult to keep primary neurons alive for more than 3 weeks in culture. Moreover, long-term adherent culture to maintain the morphology of telencephalic neuron aggregates induced from human iPS cells is also difficult. Although collagen gel has been widely used to support long-term culture of cells, it is not clear whether human iPS cell-derived neuron aggregates can be cultured for long periods on this substrate. In the present study, we differentiated human iPS cells to telencephalic neuron aggregates and examined long-term culture of these aggregates on collagen gel. The results indicated that these aggregates could be cultured for over 3 months by adhering tightly onto collagen gel. Furthermore, telencephalic neuronal precursors within these aggregates matured over time and formed layered structures. Thus, long-term culture of telencephalic neuron aggregates derived from human iPS cells on collagen gel would be useful for studying human cerebral cortex development.Key words: Induced pluripotent stem cell, forebrain neuron, collagen gel, long-term culture.

Measuring the radiation force of megahertz ultrasound acting on a solid spherical scatterer

NASA Astrophysics Data System (ADS)

Nikolaeva, A. V.; Tsysar, S. A.; Sapozhnikov, O. A.

2016-01-01

The paper considers the problem of precise measurement of the acoustic radiation force of an ultrasonic beam on targets in the form of solid spherical scatterers. Using known analytic relations, a numerical model is developed to perform calculations for different sizes of spherical scatterers and arbitrary frequencies of the incident acoustic wave. A novel method is proposed for measuring the radiation force, which is based on the principle of acoustic echolocation. The radiation force is measured experimentally in a wide range of incident wave intensities using two chosen methods differing in the way the location of the target is controlled.

In-situ photopolymerization of monodisperse and discoid oxidized methacrylated alginate microgels in a microfluidic channel

DOE PAGES

Wang, Shuo; Jeon, Oju; Shankles, Peter G.; ...

2016-02-03

Here, we present a simple microfluidic technique to in-situ photopolymerize (by 365 nm ultraviolet) monodisperse oxidized methacrylated alginate (OMA) microgels using a photoinitiator (VA-086). By this technique, we generated monodisperse spherical OMA beads and discoid non-spherical beads with better shape consistency than ionic crosslinking methods do. We found that a high monomer concentration (8 w/v %), a high photoinitiator concentration (1.5 w/v %) and absence of oxygen are critical factors to cure OMA microgels. This photopolymerizing method is an alternative to current methods to form alginate microgels and is a simpler approach to generate non-spherical alginate microgels.

Characterization of aggregates of surface modified fullerenes by asymmetrical flow field-flow fractionation with multi-angle light scattering detection.

PubMed

Astefanei, Alina; Kok, Wim Th; Bäuerlein, Patrick; Núñez, Oscar; Galceran, Maria Teresa; de Voogt, Pim; Schoenmakers, Peter J

2015-08-21

Fullerenes are carbon nanoparticles with widespread biomedical, commercial and industrial applications. Attributes such as their tendency to aggregate and aggregate size and shape impact their ability to be transported into and through the environment and living tissues. Knowledge of these properties is therefore valuable for their human and environmental risk assessment as well as to control their synthesis and manufacture. In this work, asymmetrical flow-field flow fractionation (AF4) coupled to multi-angle light scattering (MALS) was used for the first time to study the size distribution of surface modified fullerenes with both polyhydroxyl and carboxyl functional groups in aqueous solutions having different pH (6.5-11) and ionic strength values (0-200mM) of environmental relevance. Fractionation key parameters such as flow rates, flow programming, and membrane material were optimized for the selected fullerenes. The aggregation of the compounds studied appeared to be indifferent to changes in solution pH, but was affected by changes in the ionic strength. Polyhydroxy-fullerenes were found to be present mostly as 4nm aggregates in water without added salt, but showed more aggregation at high ionic strength, with an up to 10-fold increase in their mean hydrodynamic radii (200mM), due to a decrease in the electrostatic repulsion between the nanoparticles. Carboxy-fullerenes showed a much stronger aggregation degree in water (50-100nm). Their average size and recoveries decreased with the increase in the salt concentration. This behavior can be due to enhanced adsorption of the large particles to the membrane at high ionic strength, because of their higher hydrophobicity and much larger particle sizes compared to polyhydroxy-fullerenes. The method performance was evaluated by calculating the run-to-run precision of the retention time (hydrodynamic radii), and the obtained RSD values were lower than 1%. MALS measurements showed aggregate sizes that were in good agreement with the AF4 data. A comparison of the scattering radii from the MALS with the hydrodynamic radii obtained from the retention times in AF4 indicated that the aggregate shapes are far from spherical. TEM images of the fullerenes in the dry state also showed branched and irregular clusters. Copyright © 2015 Elsevier B.V. All rights reserved.

Characterization of reaction intermediate aggregates in aniline oxidative polymerization at low proton concentration.

PubMed

Ding, Zhongfen; Sanchez, Timothy; Labouriau, Andrea; Iyer, Srinivas; Larson, Toti; Currier, Robert; Zhao, Yusheng; Yang, Dali

2010-08-19

Aggregates of reaction intermediates form during the early stages of aniline oxidative polymerization whenever the initial mole ratio of proton concentration to aniline monomer concentration is low ([H(+)](0)/[An](0)

Cellular Strategies for Regulating Functional and Nonfunctional Protein Aggregation

PubMed Central

Gsponer, Jörg; Babu, M. Madan

2012-01-01

Summary Growing evidence suggests that aggregation-prone proteins are both harmful and functional for a cell. How do cellular systems balance the detrimental and beneficial effect of protein aggregation? We reveal that aggregation-prone proteins are subject to differential transcriptional, translational, and degradation control compared to nonaggregation-prone proteins, which leads to their decreased synthesis, low abundance, and high turnover. Genetic modulators that enhance the aggregation phenotype are enriched in genes that influence expression homeostasis. Moreover, genes encoding aggregation-prone proteins are more likely to be harmful when overexpressed. The trends are evolutionarily conserved and suggest a strategy whereby cellular mechanisms specifically modulate the availability of aggregation-prone proteins to (1) keep concentrations below the critical ones required for aggregation and (2) shift the equilibrium between the monomeric and oligomeric/aggregate form, as explained by Le Chatelier’s principle. This strategy may prevent formation of undesirable aggregates and keep functional assemblies/aggregates under control. PMID:23168257

Formation mechanisms of metal colloids

NASA Astrophysics Data System (ADS)

Halaciuga, Ionel

Highly dispersed uniform metallic particles are widely used in various areas of technology and medicine and are likely to be incorporated into many other applications in the future. It is commonly accepted that size, shape and composition of the particles represent critical factors in most applications. Thus, understanding the mechanisms of formation of metal particles and the ways to control the physical (e.g. shape, size) and chemical (e.g. composition) properties is of great importance. In the current research, the formation of uniform silver spheres is investigated experimentally. The parameters that influence the formation of silver particles when concentrated iso-ascorbic acid and silver-polyamine complex solutions are rapidly mixed were studied in the absence of dispersants. We found that by varying the nature of the amine, temperature, concentration of reactants, silver/amine molar ratio, and the nature of the silver salt, the size of the resulting silver particles can be varied in a wide range (0.08--1.5 microm). The silver particles were formed by aggregation of nanosize subunits as substantiated by both electron microscopy and X-ray diffraction techniques and by the vivid rapid color changes during the chemical precipitation process. From the practical standpoint, the goal of this research was to prepare well dispersed spherical silver particles having a relatively smooth surface and a diameter of about 1 microm to satisfy the demands of the current electronic materials market. A two stage particle growth model previously developed to explain the narrow size distribution occurring in synthesis of gold spheres was applied to the present experimental system, and the parameters that control the size distribution characteristics were identified. The kinetic parameter required to match the final particle size was found to be in agreement with the one used previously in modeling formation of gold spheres, suggesting that similar kinetics governs the aggregation process. Furthermore, the two-stage particle growth model was used to account for the effects of solvent viscosity and temperature on the particle properties, particularly their size. As an application of the above mentioned study, the aggregation process that led to the formation of large silver spheres was used to deposit in a controlled manner layers of silver and other metals (Ni, Au) onto various metallic and non-metallic substrates. In the final section of this thesis methods to form nanosized primary particle strictly through diffusional growth are described. The highly crystalline metallic particles of various sizes and composition prepared provide performance characteristics that are complementary to the polycrystalline metallic particles described in the preceding sections.

Vibrio tapetis, the Causative Agent of Brown Ring Disease, Forms Biofilms with Spherical Components.

PubMed

Rodrigues, Sophie; Paillard, Christine; Le Pennec, Gaël; Dufour, Alain; Bazire, Alexis

2015-01-01

Vibrio tapetis is a marine bacterium causing Brown Ring Disease (BRD) in the Manila clam Ruditapes philippinarum. V. tapetis biofilm formation remains unexplored depite the fact that it might be linked to pathogenicity. Our objectives were to characterize the in vitro biofilm formation of V. tapetis and evaluate the effects of culture conditions. Biofilm structure and its matrix composition were examined by confocal laser scanning microscopy and scanning electron microscopy. V. tapetis was able to form biofilms on a glass substratum within 24 h. Polysaccharides and extracellular DNA of the biofilm matrixes were differently distributed depending on the V. tapetis strains. Spherical components of about 1-2 μm diameter were found at the biofilm surface. They contain DNA, proteins, and seemed to be physically linked to bacteria and of cellular nature. Transmission electron microscopy showed that the spherical components were devoid of internal compartments. Temperatures >21°C inhibit BRD whereas low salinity (2%) favor it, none of the both conditions altered V. tapetis' ability to form biofilms in vitro. We suggest therefore that biofilm formation could play a role in the persistence of the pathogen in clam than in BRD symptoms.

Unveiling One-Dimensional Supramolecular Structures Formed through π-π Stacking of Phenothiazines by Differential Pulse Voltammetry.

PubMed

Carvalho, Fernando R; Zampieri, Eduardo H; Caetano, Wilker; Silva, Rafael

2017-05-19

Organic-based nanomaterials can be self-assembled by strong and directional intermolecular forces such as π-π interactions. Experimental information about the stability, size, and geometry of the formed structures is very limited for species that easily aggregate, even at very low concentrations. Differential pulse voltammetry (DPV) can unveil the formation, growth, and also the stability window of ordered, one-dimensional, lamellar self-aggregates formed by supramolecular π stacking of phenothiazines at micromolar (10 -6  mol L -1 ) concentrations. The self-diffusion features of the species at different concentrations are determined by DPV and used to probe the π staking process through the concept of the frictional resistance. It is observed that toluidine blue and methylene blue start to self-aggregate around 9 μmol L -1 , and that the self-aggregation process occurs by one-dimensional growth as the concentration of the phenothiazines is increased up to around 170 μmol L -1 for toluidine blue and 200 μmol L -1 for methylene blue. At higher concentrations, the aggregation process leads to structures with lower anisometry. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Isolation, characterization, and aggregation of a structured bacterial matrix precursor.

PubMed

Chai, Liraz; Romero, Diego; Kayatekin, Can; Akabayov, Barak; Vlamakis, Hera; Losick, Richard; Kolter, Roberto

2013-06-14

Biofilms are surface-associated groups of microbial cells that are embedded in an extracellular matrix (ECM). The ECM is a network of biopolymers, mainly polysaccharides, proteins, and nucleic acids. ECM proteins serve a variety of structural roles and often form amyloid-like fibers. Despite the extensive study of the formation of amyloid fibers from their constituent subunits in humans, much less is known about the assembly of bacterial functional amyloid-like precursors into fibers. Using dynamic light scattering, atomic force microscopy, circular dichroism, and infrared spectroscopy, we show that our unique purification method of a Bacillus subtilis major matrix protein component results in stable oligomers that retain their native α-helical structure. The stability of these oligomers enabled us to control the external conditions that triggered their aggregation. In particular, we show that stretched fibers are formed on a hydrophobic surface, whereas plaque-like aggregates are formed in solution under acidic pH conditions. TasA is also shown to change conformation upon aggregation and gain some β-sheet structure. Our studies of the aggregation of a bacterial matrix protein from its subunits shed new light on assembly processes of the ECM within bacterial biofilms.

Amyloid-linked cellular toxicity triggered by bacterial inclusion bodies

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

Gonzalez-Montalban, Nuria; Departament de Genetica i de Microbiologia, Universitat Autonoma de Barcelona, Bellaterra, 08193 Barcelona; Ciber de Bioingenieria, Biomateriales y Nanomedicina

The aggregation of proteins in the form of amyloid fibrils and plaques is the characteristic feature of some pathological conditions ranging from neurodegenerative disorders to systemic amyloidoses. The mechanisms by which the aggregation processes result in cell damage are under intense investigation but recent data indicate that prefibrillar aggregates are the most proximate mediators of toxicity rather than mature fibrils. Since it has been shown that prefibrillar forms of the nondisease-related misfolded proteins are highly toxic to cultured mammalian cells we have studied the cytoxicity associated to bacterial inclusion bodies that have been recently described as protein deposits presenting amyloid-likemore » structures. We have proved that bacterial inclusion bodies composed by a misfolding-prone {beta}-galactosidase fusion protein are clearly toxic for mammalian cells but the {beta}-galactosidase wild type enzyme forming more structured thermal aggregates does not impair cell viability, despite it also binds and enter into the cells. These results are in the line that the most cytotoxic aggregates are early prefibrilar assemblies but discard the hypothesis that the membrane destabilization is Key event to subsequent disruption of cellular processes, such as ion balance, oxidative state and the eventually cell death.« less

Characterization of the oligomeric states of insulin in self-assembly and amyloid fibril formation by mass spectrometry.

PubMed Central

Nettleton, E J; Tito, P; Sunde, M; Bouchard, M; Dobson, C M; Robinson, C V

2000-01-01

The self-assembly and aggregation of insulin molecules has been investigated by means of nanoflow electrospray mass spectrometry. Hexamers of insulin containing predominantly two, but up to four, Zn(2+) ions were observed in the gas phase when solutions at pH 4.0 were examined. At pH 3.3, in the absence of Zn(2+), dimers and tetramers are observed. Spectra obtained from solutions of insulin at millimolar concentrations at pH 2.0, conditions under which insulin is known to aggregate in solution, showed signals from a range of higher oligomers. Clusters containing up to 12 molecules could be detected in the gas phase. Hydrogen exchange measurements show that in solution these higher oligomers are in rapid equilibrium with monomeric insulin. At elevated temperatures, under conditions where insulin rapidly forms amyloid fibrils, the concentration of soluble higher oligomers was found to decrease with time yielding insoluble high molecular weight aggregates and then fibrils. The fibrils formed were examined by electron microscopy and the results show that the amorphous aggregates formed initially are converted to twisted, unbranched fibrils containing several protofilaments. Fourier transform infrared spectroscopy shows that both the soluble form of insulin and the initial aggregates are predominantly helical, but that formation of beta-sheet structure occurs simultaneously with the appearance of well-defined fibrils. PMID:10920035

Mineral trioxide aggregate: part 2 - a review of the material aspects.

PubMed

Malhotra, Neeraj; Agarwal, Antara; Mala, Kundabala

2013-03-01

The purpose of this two-part series is to review the composition, properties, and products of mineral trioxide aggregate (MTA) materials. PubMed and MedLine electronic databases were used to identify scientific papers from January 1991 to May 2010. Based on the selected inclusion criteria, citations were referenced from the scientific peer-reviewed dental literature. Mineral trioxide aggregate is a refined form of the parent compound, Portland cement (PC), and demonstrates a strong biocompatibility due to the high pH level and the material's ability to form hydroxyapatite. Mineral trioxide aggregate materials provide better microleakage protection than traditional endodontic materials as observed in findings from dye-leakage, fluid-filtration, protein-leakage, and bacterial penetration-leakage studies and has been recognized as a bioactive material. Various MTA commercial products are available, including gray mineral trioxide aggregate (GMTA), white mineral trioxide aggregate (WMTA), and mineral trioxide aggregate-Angelus (AMTA). Although these materials are indicated for various dental uses and applications, long-term in-vivo clinical studies are needed. Part 1 of this article highlighted and discussed the composition and characteristics of the material. Part 2 provides an overview of commercially available MTA materials.

Carbon Nanotubes, Nanocrystal Forms, and Complex Nanoparticle Aggregates in common fuel-gas combustion sources and the ambient air

NASA Astrophysics Data System (ADS)

Murr, L. E.; Bang, J. J.; Esquivel, E. V.; Guerrero, P. A.; Lopez, D. A.

2004-06-01

Aggregated multiwall carbon nanotubes (with diameters ranging from ˜3 to 30nm) and related carbon nanocrystal forms ranging in size from 0.4 to 2 μm (average diameter) have been collected in the combustion streams for methane/air, natural gas/air, and propane gas/air flames using a thermal precipitator. Individual particle aggregates were collected on carbon/formvar-coated 3mm nickel grids and examined in a transmission electron microscope, utilizing bright-field imaging, selected-area electron diffraction analysis, and energy-dispersive X-ray spectrometry techniques. The natural gas and propane gas sources were domestic (kitchen) stoves, and similar particle aggregates collected in the outdoor air were correspondingly identified as carbon nanocrystal aggregates and sometimes more complex aggregates of silica nanocrystals intermixed with the carbon nanotubes and other carbon nanocrystals. Finally, and in light of the potential for methane-series gas burning as major sources of carbon nanocrystal aggregates in both the indoor and outdoor air, data for natural gas consumption and corresponding asthma deaths and incidence are examined with a degree of speculation regarding any significance in the correlations.

A hypothetical hierarchical mechanism of the self-assembly of the Escherichia coli RNA polymerase σ(70) subunit.

PubMed

Koroleva, O N; Dubrovin, E V; Tolstova, A P; Kuzmina, N V; Laptinskaya, T V; Yaminsky, I V; Drutsa, V L

2016-02-21

Diverse morphology of aggregates of amyloidogenic proteins has been attracting much attention in the last few years, and there is still no complete understanding of the relationships between various types of aggregates. In this work, we propose the model, which universally explains the formation of morphologically different (wormlike and rodlike) aggregates on the example of a σ(70) subunit of RNA polymerase, which has been recently shown to form amyloid fibrils. Aggregates were studied using AFM in solution and depolarized dynamic light scattering. The obtained results demonstrate comparably low Young's moduli of the wormlike structures (7.8-12.3 MPa) indicating less structured aggregation of monomeric proteins than that typical for β-sheet formation. To shed light on the molecular interaction of the protein during the aggregation, early stages of fibrillization of the σ(70) subunit were modeled using all-atom molecular dynamics. Simulations have shown that the σ(70) subunit is able to form quasi-symmetric extended dimers, which may further interact with each other and grow linearly. The proposed general model explains different pathways of σ(70) subunit aggregation and may be valid for other amyloid proteins.

Marine Synechococcus Aggregation

NASA Astrophysics Data System (ADS)

Neuer, S.; Deng, W.; Cruz, B. N.; Monks, L.

2016-02-01

Cyanobacteria are considered to play an important role in the oceanic biological carbon pump, especially in oligotrophic regions. But as single cells are too small to sink, their carbon export has to be mediated by aggregate formation and possible consumption by zooplankton producing sinking fecal pellets. Here we report results on the aggregation of the ubiquitous marine pico-cyanobacterium Synechococcus as a model organism. We first investigated the mechanism behind such aggregation by studying the potential role of transparent exopolymeric particles (TEP) and the effects of nutrient (nitrogen or phosphorus) limitation on the TEP production and aggregate formation of these pico-cyanobacteria. We further studied the aggregation and subsequent settling in roller tanks and investigated the effects of the clays kaolinite and bentonite in a series of concentrations. Our results show that despite of the lowered growth rates, Synechococcus in nutrient limited cultures had larger cell-normalized TEP production, formed a greater volume of aggregates, and resulted in higher settling velocities compared to results from replete cultures. In addition, we found that despite their small size and lack of natural ballasting minerals, Synechococcus cells could still form aggregates and sink at measureable velocities in seawater. Clay minerals increased the number and reduced the size of aggregates, and their ballasting effects increased the sinking velocity and carbon export potential of aggregates. In comparison with the Synechococcus, we will also present results of the aggregation of the pico-cyanobacterium Prochlorococcus in roller tanks. These results contribute to our understanding in the physiology of marine Synechococcus as well as their role in the ecology and biogeochemistry in oligotrophic oceans.

Scanning electron microscopy study of adhesion in sea urchin blastulae. M.S. Thesis

NASA Technical Reports Server (NTRS)

Crowther, Susan D.

1988-01-01

The dissociation supernatant (DS) isolated by disaggregating Strongylocentrotus purpuratus blastulae in calcium- and magnesium-free seawater specifically promotes reaggregation of S. purpuratus blastula cells. The purpose of this study was to use scanning electron microscopy to examine the gross morphology of aggregates formed in the presence of DS to see if it resembles adhesion in partially dissociated blastulae. A new reaggregation procedure developed here, using large volumes of cell suspension and a large diameter of rotation, was utilized to obtain sufficient quantities of aggregates for scanning electron microscopy. The results indicate that aggregates formed in the presence of DS resemble partially dissociated intact embryos in terms of the direct cell-cell adhesion observed. DS did not cause aggregation to form as a result of the entrapment of cells in masses of extracellular material. These studies provide the groundwork for further studies using transmission electron microscopy to more precisely define the adhesive contacts made by cells in the presence of the putative adhesion molecules present in DS.

Lithium Enolates in the Enantioselective Construction of Tetrasubstituted Carbon Centers with Chiral Lithium Amides as Noncovalent Stereodirecting Auxiliaries.

PubMed

Yu, Kai; Lu, Ping; Jackson, Jeffrey J; Nguyen, Thuy-Ai D; Alvarado, Joseph; Stivala, Craig E; Ma, Yun; Mack, Kyle A; Hayton, Trevor W; Collum, David B; Zakarian, Armen

2017-01-11

Lithium enolates derived from carboxylic acids are ubiquitous intermediates in organic synthesis. Asymmetric transformations with these intermediates, a central goal of organic synthesis, are typically carried out with covalently attached chiral auxiliaries. An alternative approach is to utilize chiral reagents that form discrete, well-defined aggregates with lithium enolates, providing a chiral environment conducive of asymmetric bond formation. These reagents effectively act as noncovalent, or traceless, chiral auxiliaries. Lithium amides are an obvious choice for such reagents as they are known to form mixed aggregates with lithium enolates. We demonstrate here that mixed aggregates can effect highly enantioselective transformations of lithium enolates in several classes of reactions, most notably in transformations forming tetrasubstituted and quaternary carbon centers. Easy recovery of the chiral reagent by aqueous extraction is another practical advantage of this one-step protocol. Crystallographic, spectroscopic, and computational studies of the central reactive aggregate, which provide insight into the origins of selectivity, are also reported.

Dendronization-induced phase-transfer, stabilization and self-assembly of large colloidal Au nanoparticles

NASA Astrophysics Data System (ADS)

Malassis, Ludivine; Jishkariani, Davit; Murray, Christopher B.; Donnio, Bertrand

2016-07-01

The phase-transfer of CTAB-coated aqueous, spherical gold nanoparticles, with metallic core diameters ranging from ca. 27 to 54 nm, into organic solvents by exchanging the primitive polar bilayer with lipophilic, disulfide dendritic ligands is reported. The presence of such a thick nonpolar organic shell around these large nanoparticles enhances their stabilization against aggregation, in addition to enabling their transfer into a variety of solvents such as chloroform, toluene or tetrahydrofuran. Upon the slow evaporation of a chloroform suspension deposited on a solid support, the dendronized hybrids were found to self-assemble into ring structures of various diameters. Moreover, their self-assembly at the liquid-air interface affords the formation of fairly long-range ordered monolayers, over large areas, that can then be entirely transferred onto solid substrates.The phase-transfer of CTAB-coated aqueous, spherical gold nanoparticles, with metallic core diameters ranging from ca. 27 to 54 nm, into organic solvents by exchanging the primitive polar bilayer with lipophilic, disulfide dendritic ligands is reported. The presence of such a thick nonpolar organic shell around these large nanoparticles enhances their stabilization against aggregation, in addition to enabling their transfer into a variety of solvents such as chloroform, toluene or tetrahydrofuran. Upon the slow evaporation of a chloroform suspension deposited on a solid support, the dendronized hybrids were found to self-assemble into ring structures of various diameters. Moreover, their self-assembly at the liquid-air interface affords the formation of fairly long-range ordered monolayers, over large areas, that can then be entirely transferred onto solid substrates. Electronic supplementary information (ESI) available: TEM microscope images. See DOI: 10.1039/c6nr03404g

Primate cathelicidin orthologues display different structures and membrane interactions.

PubMed

Morgera, Francesca; Vaccari, Lisa; Antcheva, Nikolinka; Scaini, Denis; Pacor, Sabrina; Tossi, Alessandro

2009-02-01

The human cathelicidin LL-37 displays both direct antibacterial activities and the capacity to modulate host-cell activities. These depend on structural characteristics that are subject to positive selection for variation, as observed in a previous analysis of the CAMP gene (encoding LL-37) in primates. The altered balance between cationic and anionic residues in different primate orthologues affects intramolecular salt-bridging and influences the stability of the helical conformation and tendency to aggregate in solution of the peptide. In the present study, we have analysed the effects of these structural variations on membrane interactions for human LL-37, rhesus RL-37 and orang-utan LL-37, using several complementary biophysical and biochemical methods. CD and ATR (attenuated total reflection)-FTIR (Fourier-transform IR) spectroscopy on model membranes indicate that RL-37, which is monomeric and unstructured in bulk solution [F-form (free form)], and human LL-37, which is partly structured and probably aggregated [A-form (aggregated form)], bind biological membranes in different manners. RL-37 may insert more deeply into the lipid bilayer than LL-37, which remains aggregated. AFM (atomic force microscopy) performed on the same supported bilayer as used for ATR-FTIR measurements suggests a carpet-like mode of permeabilization for RL37 and formation of more defined worm-holes for LL-37. Comparison of data from the biological activity on bacterial cells with permeabilization of model membranes indicates that the structure/aggregation state also affects the trajectory of the peptides from bulk solution through the outer cell-wall layers to the membrane. The results of the present study suggest that F-form cathelicidin orthologues may have evolved to have primarily a direct antimicrobial defensive capacity, whereas the A-forms have somewhat sacrificed this to gain host-cell modulating functions.

Discontinuous hygroscopic growth of an aqueous surfactant/salt aerosol particle levitated in an electrodynamic balance

NASA Astrophysics Data System (ADS)

Soonsin, V.; Krieger, U. K.; Peter, T.

2010-12-01

Organic compounds are a major fraction of tropospheric aerosol. The organic fraction is usually internally mixed with inorganic salts. Surface-active organic matter or surfactants, enriched in the oceanic surface layer and transferred to the atmosphere by bubble-bursting processes, are the most likely candidates to contribute the observed organic fraction in sea salt aerosol [1, 2]. If the organic substance is a surfactant, it will lower the surface tension. In addition aggregates of the organic monomers, called micelles, will form if the concentration of the organic exceeds a certain limit (critical micelle concentration). These aggregates do have different morphology (spheres or globular or rod like micelles, or spherical bilayer vesicles etc.) and size, depending on the nature of the organic molecule, its concentration and the concentration of inorganic salts [3]. These aggregate may promote solubilisation of organic compounds in aqueous atmospheric aerosol. We performed measurements of ternary aqueous solution particles consisting of tetraethylene glycol monooctyl ether (C8E4) as organic surfactant and sodium chloride (NaCl) as inorganic salt and water (H2O) using single levitated aerosol particles in an electrodynamic balance. The particles can be stored contact-free in a temperature and humidity controlled chamber and optical resonance spectroscopy is used to monitor radius change [4]. Mie resonance spectra of ternary droplets show discontinuous growth with increasing relative humidity (RH) and also discontinuous shrinkage with decreasing relative humidity. We observe this behavior at temperatures and RHs at which the salt is completely deliquesced and the concentration of the organic surfactant is larger than the critical micelle concentration. Independent measurements of particle mass show also discontinuous water uptake. We speculate that this discontinuous, step-like, growth is caused by disaggregation of a micelle needed to conserve the monolayer of surfactant molecules on the aqueous aerosol particle surface upon growing. The number of molecules of the disaggregating micelle can be deduced from the known polar surface area of the C8E4 molecule and the surface area increase of the aerosol particle calculated from the step increase in radius. Our measurements yield a broad distribution of aggregation numbers with a peak aggregation number of 105 molecules. This number agrees reasonably well with aggregate sizes directly observed with Cryo-TEM in a related system [5]. References: [1] Oppo, C., Bellandi, S., Degli Innocenti, N., Stortini, A.M., Loglio, G., Schiavuta, E., & Cini, R., Marine Chemistry, 63, 235-253, 1999. [2] O'Dowd, C.D., Facchini, M.C., Cavalli, F., Ceburnis, D., Mircea, M., Decesari, S., Fuzzi, S., Yoon, Y.J., & Putaud, J.P., Nature, 431, 676-680, 2004. [3] Israelachvili, J.N., Intermolecular and surface forces, Academic press London, 1991. [4] Zardini, A.A., Krieger, U.K., & Marcolli, C., Optics Express, 14, 6951-6962, 2006. [5] Bernheim-Groswasser, A., Wachtel E., & Talmon, Y., Langmuir, 16, 4131-4140, 2000.

Micro-scale heterogeneity of soil phosphorus depends on soil substrate and depth

DOE PAGES

Werner, Florian; Mueller, Carsten W.; Thieme, Jurgen; ...

2017-06-09

Soils comprise various heterogeneously distributed pools of lithogenic, free organic, occluded, adsorbed, and precipitated phosphorus (P) forms, which differ depending on soil forming factors. Small-scale heterogeneity of element distributions recently has received increased attention in soil science due to its influence on soil functions and soil fertility. We investigated the micro-scale distribution of total P and different specific P binding forms in aggregates taken from a high-P clay-rich soil and a low-P sandy soil by combining advanced spectrometric and spectroscopic techniques to introduce new insights on P accessibility and availability in soils. Here we show that soil substrate and soilmore » depth determine micro-scale P heterogeneity in soil aggregates. In P-rich areas of all investigated soil aggregates, P was predominantly co-located with aluminium and iron oxides and hydroxides, which are known to strongly adsorb P. Clay minerals were co-located with P only to a lesser extent. In the low-P topsoil aggregate, the majority of the P was bound organically. Aluminium and iron phosphate predominated in the quartz-rich low-P subsoil aggregate. Sorbed and mineral P phases determined P speciation in the high-P top- and subsoil, and apatite was only detected in the high-P subsoil aggregate. Lastly, our results indicate that micro-scale spatial and chemical heterogeneity of P influences P accessibility and bioavailability.« less

Micro-scale heterogeneity of soil phosphorus depends on soil substrate and depth

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

Werner, Florian; Mueller, Carsten W.; Thieme, Jurgen

Soils comprise various heterogeneously distributed pools of lithogenic, free organic, occluded, adsorbed, and precipitated phosphorus (P) forms, which differ depending on soil forming factors. Small-scale heterogeneity of element distributions recently has received increased attention in soil science due to its influence on soil functions and soil fertility. We investigated the micro-scale distribution of total P and different specific P binding forms in aggregates taken from a high-P clay-rich soil and a low-P sandy soil by combining advanced spectrometric and spectroscopic techniques to introduce new insights on P accessibility and availability in soils. Here we show that soil substrate and soilmore » depth determine micro-scale P heterogeneity in soil aggregates. In P-rich areas of all investigated soil aggregates, P was predominantly co-located with aluminium and iron oxides and hydroxides, which are known to strongly adsorb P. Clay minerals were co-located with P only to a lesser extent. In the low-P topsoil aggregate, the majority of the P was bound organically. Aluminium and iron phosphate predominated in the quartz-rich low-P subsoil aggregate. Sorbed and mineral P phases determined P speciation in the high-P top- and subsoil, and apatite was only detected in the high-P subsoil aggregate. Lastly, our results indicate that micro-scale spatial and chemical heterogeneity of P influences P accessibility and bioavailability.« less

Native aggregation as a cause of origin of temporary cellular structures needed for all forms of cellular activity, signaling and transformations.

PubMed

Matveev, Vladimir V

2010-06-09

According to the hypothesis explored in this paper, native aggregation is genetically controlled (programmed) reversible aggregation that occurs when interacting proteins form new temporary structures through highly specific interactions. It is assumed that Anfinsen's dogma may be extended to protein aggregation: composition and amino acid sequence determine not only the secondary and tertiary structure of single protein, but also the structure of protein aggregates (associates). Cell function is considered as a transition between two states (two states model), the resting state and state of activity (this applies to the cell as a whole and to its individual structures). In the resting state, the key proteins are found in the following inactive forms: natively unfolded and globular. When the cell is activated, secondary structures appear in natively unfolded proteins (including unfolded regions in other proteins), and globular proteins begin to melt and their secondary structures become available for interaction with the secondary structures of other proteins. These temporary secondary structures provide a means for highly specific interactions between proteins. As a result, native aggregation creates temporary structures necessary for cell activity."One of the principal objects of theoretical research in any department of knowledge is to find the point of view from which the subject appears in its greatest simplicity."Josiah Willard Gibbs (1839-1903).