Nanostructured CaWO4, CaWO4 : Pb2+ and CaWO4 : Tb3+ particles: Polyol-mediated synthesis and luminescent properties

Nano-submicrostructured CaWO4, CaWO4 : Pb2+ and CaWO4 : Tb3+ particles were prepared by polyol method and characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier transform infrared spectra (FT-IR), thermogravimetry-differential thermal analysis (TG-DTA), photoluminescence (PL), cathodo-luminescence (CL) spectra and PL lifetimes. The results of XRD indicate that the as-prepared samples are well crystallized with the scheelite structure of CaWO4. The FE-SEM images illustrate that CaWO4 and CaWO4 : Pb2+ and CaWO4 : Tb3+ powders are composed of spherical particles with sizes around 260, 290, and 190 nm respectively, which are the aggregates of smaller nanoparticles around 10-20 nm. Under the UV light or electron beam excitation, the CaWO4 powders exhibits a blue emission band with a maximum at about 440 nm. When the CaWO4 particles are doped with Pb2+, the intensity of luminescence is enhanced to some extent and the luminescence band maximum is red shifted to 460 nm. Tb3+-doped CaWO4 particles show the characteristic emission of Tb3+ D-5(4)-F-7(J) (J=6-3) transitions due to an energy transfer from WO42- groups to Tb3+.

Synthesis and characterization of monodisperse spherical core-shell structured SiO2@Y3Al5O12 : Ce3+/Tb3+ phosphors for field emission displays

Nanocrystalline Y3Al5O12: Ce3+/Tb3+ ( average crystalline size 30 nm) phosphor layers were coated on non-aggregated, monodisperse and spherical SiO2 particles by the sol-gel method, resulting in the formation of core-shell structured SiO2@Y3Al5O12:Ce3+/Tb3+ particles. X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, photoluminescence, cathodoluminescence spectra, as well as lifetimes were utilized to characterize the core-shell structured SiO2@Y3Al5O12: Ce3+/Tb3+ phosphor particles. The obtained core-shell structured phosphors consist of well-dispersed submicron spherical particles with a narrow size distribution. The thickness of the Y3Al5O12:Ce3+/Tb3+ shells on the SiO2 cores ( average size about 500 nm, crystalline size about 30 nm) could be easily tailored by varying the number of deposition cycles (100 nm for four deposition cycles). Under the excitation of ultraviolet and low-voltage electron beams (1-3 kV), the core-shell SiO2@Y3Al5O12:Ce3+/ Tb3+ particles show strong yellow-green and green emission corresponding to the 5d-4f emission of Ce3+ and D-5(4)-F-7(J) ( J = 6, 5, 4, 3) emission of Tb3+, respectively.

Monodisperse spherical core-shell structured SiO2-CaTiO3 : Pr3+ phosphors for field emission displays

Nanocrystalline CaTiO3:Pr3+ phosphor layers were coated on nonaggregated, monodisperse, and spherical SiO2 particles by the sol-gel method, resulting in the formation of core-shell structured SiO2-CaTiO3:Pr3+ particles. X-ray diffraction, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, photoluminescence, cathodoluminescence spectra, as well as lifetimes were utilized to characterize the core-shell structured SiO2-CaTiO3:Pr3+ phosphor particles. The obtained core-shell structured phosphors consist of well dispersed submicron spherical particles with a narrow size distribution. The thickness of the CaTiO3:Pr3+ shell could be easily controlled by changing the number of deposition cycles (about 70 nm for four deposition cycles). The core-shell SiO2-CaTiO3:Pr3+ particles show a strong red emission corresponding to D-1(2)-H-3(4) (612 nm) of Pr3+ under the excitation of ultraviolet (326 nm) and low voltage electron beams (1-5 kV). These particles may be used in field emission displays.

Unbiased Linear Property Estimation For Spheres From Sections Exhibiting Overprojection And Truncation

In the biological sciences, stereological techniques are frequently used to infer changes in structural parameters (volume fraction, for example) between samples from different populations or subject to differing treatment regimes. Non-homogeneity of these parameters is virtually guaranteed, both between experimental animals and within the organ under consideration. A two-stage strategy is then desirable, the first stage involving unbiased estimation of the required parameter, separately for each experimental unit, the latter being defined as a subset of the organ for which homogeneity can reasonably be assumed. In the second stage, these point estimates are used as data inputs to a hierarchical analysis of variance, to distinguish treatment effects from variability between animals, for example. Techniques are therefore required for unbiased estimation of parameters from potentially small numbers of sample profiles. This paper derives unbiased estimates of linear properties in one special case—the sampling of spherical particles by transmission microscopy, when the section thickness is not negligible and the resulting circular profiles are subject to lower truncation. The derivation uses the general integral equation formulation of Nicholson (1970); the resulting formulae are simplified, algebraically, and their efficient computation discussed. Bias arising from variability in slice thickness is shown to be negligible in typical cases. The strategy is illustrated for data examining the effects, on the secondary lysosomes in the digestive cells, of exposure of the common mussel to hydrocarbons. Prolonged exposure, at 30 μg 1−1 total oil-derived hydrocarbons, is seen to increase the average volume of a lysosome, and the volume fraction that lysosomes occupy, but to reduce their number.

Influence of Angle of Air Injection and Particles in Bed Hydrodynamics of Swirling Fluidized Bed

The thesis presented here unveils an experimental study of the hydrodynamic characteristics of swirling fluidized bed viz. pressure drop across the distributor and the bed, minimum fluidizing velocity, bed behaviour and angle of air injection. In swirling fluidized bed the air is admitted to the bed at an angle 'Ѳ' to the horizontal. The vertical component of the velocity v sin Ѳ causes fluidization and the horizontal component v cos Ѳ contributes to swirl motion of the bed material.The study was conducted using spherical particles having sizes 3.2 mm, 5.5 mm & 7.4 mm as the bed materials. Each of these particles was made from high density polyethylene, nylon and acetal having relative densities of 0.93, 1.05 and 1.47 respectively.The experiments were conducted using conidour type distributors having four rows of slits. Altogether four distributors having angles of air injection (Φ)- 0°, 5°, 10° & 15° were designed and fabricated for the study. The total number of slits in each distributor was 144. The area of opening was 6220 mm2 making the percentage area of opening to 9.17. But the percentage useful area of opening of the distributor was 96.The experiments on the variation of distributor pressure drop with superficial velocity revealed that the distributor pressure drop decreases with angle of air injection. Investigations related to bed hydrodynamics were conducted using 2.5 kg of bed material. The bed pressure drop measurements were made along the radial direction of the distributor at distances of 60 mm, 90 mm, 120 mm & 150 mm from the centre of the distributor. It was noticed that after attaining minimum fluidizing velocity, the bed pressure drop increases along the radial direction of the distributor. But at a radial distance of 90 mm from the distributor centre, after attaining minimum fluidizing velocity the bed pressure drop remains almost constant. It was also observed that the bed pressure drop varies inversely with particle size as well as particle density.An attempt was made to determine the effect of various parameters on minimum fluidizing velocity. It was noticed that the minimum fluidizing velocity varies directly with angle of air injection (Φ), particle size and particle density.The study on the bed behaviour showed that the superficial velocity required for initiating various bed phenomena (such as swirl motion and separation of particles from the cone at the centre) increase with increase in particle size as well as particle density. It was also observed that the particle size and particle density directly influence the superficial velocity required for various regimes of bed behaviour such as linear variation of bed pressure drop, constant bed pressure drop and sudden increase or decrease in bed pressure drop.Experiments were also performed to study the effect of angle of air injection (Φ). It was noticed that the bed pressure drop decreases with angle of air injection. It was also noticed that the angle of air injection directly influence the superficial velocity required for initiating various bed phenomena as well as the various regimes of bed behaviour.

Design and study of self-assembled functional organic and hybrid systems for biological applications

The focus of self-assembly as a strategy for the synthesis has been confined largely to molecules, because of the importance of manipulating the structure of matter at the molecular scale. We have investigated the influence of temperature and pH, in addition to the concentration of the capping agent used for the formation of the nano-bio conjugates. For example, the formation of the narrower size distribution of the nanoparticles was observed with the increase in the concentration of the protein, which supports the fact that γ-globulin acts both as a controller of nucleation as well as stabiliser. As analyzed through various photophysical, biophysical and microscopic techniques such as TEM, AFM, C-AFM, SEM, DLS, OPM, CD and FTIR, we observed that the initial photoactivation of γ-globulin at pH 12 for 3 h resulted in small protein fibres of ca. Further irradiation for 24 h, led to the formation of selfassembled long fibres of the protein of ca. 5-6 nm and observation of surface plasmon resonance band at around 520 nm with the concomitant quenching of luminescence intensity at 680 nm. The observation of light triggered self-assembly of the protein and its effect on controlling the fate of the anchored nanoparticles can be compared with the naturally occurring process such as photomorphogenesis.Furthermore,our approach offers a way to understand the role played by the self-assembly of the protein in ordering and knock out of the metal nanoparticles and also in the design of nano-biohybrid materials for medicinal and optoelectronic applications. Investigation of the potential applications of NIR absorbing and water soluble squaraine dyes 1-3 for protein labeling and anti-amyloid agents forms the subject matter of the third chapter of the thesis. The study of their interactions with various proteins revealed that 1-3 showed unique interactions towards serum albumins as well as lysozyme. 69%, 71% and 49% in the absorption spectra as well as significant quenching in the fluorescence intensity of the dyes 1-3, respectively. Half-reciprocal analysis of the absorption data and isothermal titration calorimetric (ITC) analysis of the titration experiments gave a 1:1 stoichiometry for the complexes formed between the lysozyme and squaraine dyes with association constants (Kass) in the range 104-105 M-1. We have determined the changes in the free energy (ΔG) for the complex formation and the values are found to be -30.78, -32.31 and -28.58 kJmol-1, respectively for the dyes 1, 2 and 3. Furthermore, we have observed a strong induced CD (ICD) signal corresponding to the squaraine chromophore in the case of the halogenated squaraine dyes 2 and 3 at 636 and 637 nm confirming the complex formation in these cases. To understand the nature of interaction of the squaraine dyes 1-3 with lysozyme, we have investigated the interaction of dyes 1-3 with different amino acids. These results indicated that the dyes 1-3 showed significant interactions with cysteine and glutamic acid which are present in the side chains of lysozyme. In addition the temperature dependent studies have revealed that the interaction of the dye and the lysozyme are irreversible. Furthermore, we have investigated the interactions of these NIR dyes 1-3 with β- amyloid fibres derived from lysozyme to evaluate their potential as inhibitors of this biologically important protein aggregation. These β-amyloid fibrils were insoluble protein aggregates that have been associated with a range of neurodegenerative diseases, including Huntington, Alzheimer’s, Parkinson’s, and Creutzfeldt-Jakob diseases. We have synthesized amyloid fibres from lysozyme through its incubation in acidic solution below pH 4 and by allowing to form amyloid fibres at elevated temperature. To quantify the binding affinities of the squaraine dyes 1-3 with β-amyloids, we have carried out the isothermal titration calorimetric (ITC) measurements. The association constants were determined and are found to be 1.2 × 105, 3.6× 105 and 3.2 × 105 M-1 for the dyes, 1-3, respectively. To gain more insights into the amyloid inhibiting nature of the squaraine dyes under investigations, we have carried out thioflavin assay, CD, isothermal titration calorimetry and microscopic analysis. The addition of the dyes 1-3 (5μM) led to the complete quenching in the apparent thioflavin fluorescence, thereby indicating the destabilization of β-amyloid fibres in the presence of the squaraine dyes. Further, the inhibition of the amyloid fibres by the squaraine dyes 1-3, has been evidenced though the DLS, TEM AFM and SAED, wherein we observed the complete destabilization of the amyloid fibre and transformation of the fibre into spherical particles of ca. These results demonstrate the fact that the squaraine dyes 1-3 can act as protein labeling agents as well as the inhibitors of the protein amyloidogenesis. The last chapter of the thesis describes the synthesis and investigation of selfassembly as well as bio-imaging aspects of a few novel tetraphenylethene conjugates 4-6.Expectedly, these conjugates showed significant solvatochromism and exhibited a hypsochromic shift (negative solvatochromism) as the solvent polarity increased, and these observations were justified though theoretical studies employing the B3LYP/6-31g method. We have investigated the self-assembly properties of these D-A conjugates though variation in the percentage of water in acetonitrile solution due to the formation of nanoaggregates. Further the contour map of the observed fluorescence intensity as a function of the fluorescence excitation and emission wavelength confirmed the formation of J-type aggregates in these cases. To have a better understanding of the type of self-assemblies formed from the TPE conjugates 4-6, we have carried out the morphological analysis through various microscopic techniques such as DLS, SEM and TEM. 70%, we observed rod shape architectures having ~ 780 nm in diameter and ~ 12 μM in length as evidenced through TEM and SEM analysis. We have made similar observations with the dodecyl conjugate 5 at ca. 70% and 50% water/acetonitrile mixtures, the aggregates formed from 4 and 5 were found to be highly crystalline and such structures were transformed to amorphous nature as the water fraction was increased to 99%. To evaluate the potential of the conjugate as bio-imaging agents, we have carried out their in vitro cytotoxicity and cellular uptake studies though MTT assay, flow cytometric and confocal laser scanning microscopic techniques. Thus nanoparticle of these conjugates which exhibited efficient emission, large stoke shift, good stability, biocompatibility and excellent cellular imaging properties can have potential applications for tracking cells as well as in cell-based therapies. In summary we have synthesized novel functional organic chromophores and have studied systematic investigation of self-assembly of these synthetic and biological building blocks under a variety of conditions. The investigation of interaction of water soluble NIR squaraine dyes with lysozyme indicates that these dyes can act as the protein labeling agents and the efficiency of inhibition of β-amyloid indicate, thereby their potential as anti-amyloid agents.

Bubble Behavior in a Taylor Vortex

We present an experimental study on the behavior of bubbles captured in a Taylor vortex. The gap between a rotating inner cylinder and a stationary outer cylinder is filled with a Newtonian mineral oil. Beyond a critical rotation speed (ω[subscript c]), Taylor vortices appear in this system. Small air bubbles are introduced into the gap through a needle connected to a syringe pump. These are then captured in the cores of the vortices (core bubble) and in the outflow regions along the inner cylinder (wall bubble). The flow field is measured with a two-dimensional particle imaging velocimetry (PIV) system. The motion of the bubbles is monitored by using a high speed video camera. It has been found that, if the core bubbles are all of the same size, a bubble ring forms at the center of the vortex such that bubbles are azimuthally uniformly distributed. There is a saturation number (N[subscript s]) of bubbles in the ring, such that the addition of one more bubble leads eventually to a coalescence and a subsequent complicated evolution. Ns increases with increasing rotation speed and decreasing bubble size. For bubbles of non-uniform size, small bubbles and large bubbles in nearly the same orbit can be observed to cross due to their different circulating speeds. The wall bubbles, however, do not become uniformly distributed, but instead form short bubble-chains which might eventually evolve into large bubbles. The motion of droplets and particles in a Taylor vortex was also investigated. As with bubbles, droplets and particles align into a ring structure at low rotation speeds, but the saturation number is much smaller. Moreover, at high rotation speeds, droplets and particles exhibit a characteristic periodic oscillation in the axial, radial and tangential directions due to their inertia. In addition, experiments with non-spherical particles show that they behave rather similarly. This study provides a better understanding of particulate behavior in vortex flow structures.

The role of gypsum in the reactions of phosphate with soils

The aim of this study was to examine the mechanisms by which gypsum increases the sorption of fertilizer-P in soils of and and semi-arid regions. Either gypsum or soil (Usher from the UK; pH 7.8, 7% organic matter, 21% CaCO3: Yasouj from Iran; pH 8.2, 1.4% OM, 18% CaCO3: Ghanimeh from Saudi Arabia; pH 7.8, 1% OM, 26% CaCO3, 13% gypsum) was shaken for 24 It with KH2PO4 solutions in 10 mM CaCl2. With gypsum, grinding increased sorption by a factor of about 3, and increase in pH from 5.6 to 7.5 greatly increased sorption. Scanning electron micrographs (SEM) and EDX quantitative analysis showed that small crystals of gypsum disappeared and roughly spherical particles of dicalcium phosphate (DCPD) were formed. Analysis of equilibrium Solutions showed, using GEOCHEM, that octa-calcium phosphate (OCP) coated the DCPD. For the soils, sorption was in the order Ghanimeh > Yasouj > Usher. Removal of gypsum from Ghanimeh reduced sorption, with precipitated gypsum having a greater effect than gypsum mixed physically with the soil. Addition to Usher had no effect. SEM and EDX could not be used in the soil matrix, but solubility analysis again showed that solutions were close to equilibrium with OCP. Usher was unresponsive to added gypsum, presumably because of its small sorption capacity and high organic matter content. In Ghanimeh and Yasouj soils, gypsum increased sorption by being a source of readily available Ca2+ (c) 2005 Elsevier B.V. All rights reserved.

Rheology of magmas with bimodal crystal size and shape distributions: insights from analog experiments

Magmas in volcanic conduits commonly contain microlites in association with preexisting phenocrysts, as often indicated by volcanic rock textures. In this study, we present two different experiments that inves- tigate the flow behavior of these bidisperse systems. In the first experiments, rotational rheometric methods are used to determine the rheology of monodisperse and polydisperse suspensions consisting of smaller, prolate particles (microlites) and larger, equant particles (phenocrysts) in a bubble‐free Newtonian liquid (silicate melt). Our data show that increasing the relative proportion of prolate microlites to equant pheno- crysts in a magma at constant total particle content can increase the relative viscosity by up to three orders of magnitude. Consequently, the rheological effect of particles in magmas cannot be modeled by assuming a monodisperse population of particles. We propose a new model that uses interpolated parameters based on the relative proportions of small and large particles and produces a considerably improved fit to the data than earlier models. In a second series of experiments we investigate the textures produced by shearing bimodal suspensions in gradually solidifying epoxy resin in a concentric cylinder setup. The resulting textures show the prolate particles are aligned with the flow lines and spherical particles are found in well‐organized strings, with sphere‐depleted shear bands in high‐shear regions. These observations may explain the measured variation in the shear thinning and yield stress behavior with increasing solid fraction and particle aspect ratio. The implications for magma flow are discussed, and rheological results and tex- tural observations are compared with observations on natural samples.

Viruses in soils: morphological diversity and abundance in the rhizosphere

Soil viruses are potentially of great importance as they may influence the ecology and evolution of soil biological communities through both an ability to transfer genes from host to host and as a potential cause of microbial mortality. Despite this importance, the area of soil virology is understudied. Here, we report the isolation and preliminary characterisation of viruses from soils in the Dundee area of Scotland. Different virus morphotypes including tailed, polyhedral (spherical), rod shaped, filamentous and bacilliform particles were detected in the soil samples. An apparent predominance of small spherical and filamentous bacteriophages was observed, whereas tailed bacteriophages were significantly less abundant. In this report, we also present observations and characterisation of viruses from different soil functional domains surrounding wheat roots: rhizosheath, rhizosphere and bulk soil. In spite of the differences in abundance of bacterial communities in these domains, no significant variations in viral population structure in terms of morphology and abundance were found. Typically, there were approximately 1.1–1.2 × 109 virions g−1 dry weight, implicating remarkable differences in virus-to-bacteria ratios in domains close to roots, rhizosphere and rhizosheath (approximately 0.27) and in bulk soil (approximately 4.68).

Antimicrobial Particles from Cationic Lipid and Polyelectrolytes

Hybrid nanoparticles from cationic lipid and polymers were prepared and characterized regarding physical properties and antimicrobial activity. Carboxymethylcellulose (CMC) and polydiallyldimethylammonium chloride (PDDA) were sequentially added to cationic bilayer fragments (BF) prepared from ultrasonic dispersion in water of the synthetic and cationic lipid dioctadecyldimethylammonium bromide (DODAB). Particles thus obtained were characterized by dynamic light-scattering for determination of z-average diameter (Dz) and zeta-potential (zeta). Antimicrobial activity of the DODAB BF/CMC/PDDA particles against Pseudomonas aeruginosa or Staphylococcus aureus was determined by plating and CFU counting over a range of particle compositions. DODAB BF/CMC/PDDA particles exhibited sizes and zeta-potentials strictly dependent on DODAB, CM C, and PDDA concentrations. At 0.1 mM DODAB, 0.1 mg/mL CMC, and 0.1 mg/mL PDDA, small cationic particles with Dz = 100 nm and zeta = 30 mV were obtained. At 0.5 mM DODAB, 0.5 mg/mL CMC and 0.5 mg/mL PDDA, large cationic particles with Dz = 470 nm and zeta= 50 mV were obtained. Both particulates were highly reproducible regarding physical properties and yielded 0% of p. aeruginosa viability (10(7) CFU/mL) at 1 or 2 mu g/mL PDDA dissolved in solution or in form of particles, respectively. 99% of S. aureus cells died at 10 mu g/mL PDDA alone or in small or large DODAB BF/CMC/PDDA particles. The antimicrobial effect was dependent on the amount of positive charge on particles and independent of particle size. A high microbicide potency for PDDA over a range of nanomolar concentrations was disclosed. P. aeruginosa was more sensitive to all cationic assemblies than S. aureus.

Comparative structural analyses of purified glycogen particles from rat liver, human skeletal muscle and commercial preparations

Glycogen is a cellular energy store that is crucial for whole body energy metabolism, metabolic regulation and exercise performance. To understand glycogen structure we have purified glycogen particles from rat liver and human skeletal muscle tissues and compared their biophysical properties with those found in commercial glycogen preparations. Ultrastructural analysis of commercial liver glycogens fails to reveal the classical α-rosette structure but small irregularly shaped particles. In contrast, commercial slipper limpet glycogen consists of β-particles with similar branching and chain lengths to purified rat liver glycogen together with a tendency to form small α-particles, and suggest it should be used as a source of glycogen for all future studies requiring a substitute for mammalian liver glycogen.

Dynamical evolution of Saturn's F ring dust particles

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Challenging the weak cosmic censorship conjecture with charged quantum particles

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Loading of praziquantel in the crystal lattice of solid lipid nanoparticles Studies by DSC and SAXS

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)