Self-assembling of phenothiazine compounds investigated by small-angle X-ray scattering and electron paramagnetic resonance spectroscopy

Small-angle X-ray scattering (SAXS) and electron paramagnetic resonance (EPR) have been carried out to investigate the structure of the self-aggregates of two phenothiazine drugs, chlorpromazine (CPZ) and trifluoperazine (TFP), in aqueous solution. In the SAXS studies, drug solutions of 20 and 60 mM, at pH 4.0 and 7.0, were investigated and the best data fittings were achieved assuming several different particle form factors with a homogeneous electron density distribution in respect to the water environment. Because of the limitation of scattering intensity in the q range above 0.15 angstrom(-1), precise determination of the aggregate shape was not possible and all of the tested models for ellipsoids, cylinders, or parallelepipeds fitted the experimental data equally well. The SAXS data allows inferring, however, that CPZ molecules might self-assemble in a basis set of an orthorhombic cell, remaining as nanocrystallites in solution. Such nanocrystals are composed of a small number of unit cells (up to 10, in c-direction), with CPZ aggregation numbers of 60-80. EPR spectra of 5- and 16-doxyl stearic acids bound to the aggregates were analyzed through simulation, and the dynamic and magnetic parameters were obtained. The phenothiazine concentration in EPR experiments was in the range of 5-60 mM. Critical aggregation concentration of TFP is lower than that for CPZ, consistent with a higher hydrophobicity of TFP. At acidic pH 4.0 a significant residual motion of the nitroxide relative to the aggregate is observed, and the EPR spectra and corresponding parameters are similar to those reported for aqueous surfactant micelles. However, at pH 6.5 a significant motional restriction is observed, and the nitroxide rotational correlation times correlate very well with those estimated for the whole aggregated particle from SAXS data. This implies that the aggregate is densely packed at this pH and that the nitroxide is tightly bound to it producing a strongly immobilized EPR spectrum. Besides that, at pH 6.5 the differences in motional restriction observed between 5- and 16-DSA are small, which is different from that observed for aqueous surfactant micelles.

Directed self-assembly of quantum structures by nanomechanical stamping using probe tips

We demonstrate that nanomechanically stamped substrates can be used as templates to pattern and direct the self-assembly of epitaxial quantum structures such as quantum dots. Diamond probe tips are used to indent or stamp the surface of GaAs( 100) to create nanoscale volumes of dislocation-mediated deformation, which alter the growth surface strain. These strained sites act to bias nucleation, hence allowing for selective growth of InAs quantum dots. Patterns of quantum dots are observed to form above the underlying nanostamped template. The strain state of the patterned structures is characterized by micro-Raman spectroscopy. The potential of using nanoprobe tips as a quantum dot nanofabrication technology are discussed.

Crystalline particles from self-assembled divinyl oligomers

Ethylene glycol dimethacrylate (EGDMA) and/or triethylene glycol dimethacrylate (TEGDMA) oligomers formation was catalyzed in aqueous medium by horseradish peroxidase (HRP) in the presence of H(2)O(2) at room temperature. EGDMA and/or TEGDMA oligomers were characterized by means of gel permeation chromatography, infrared vibrational spectroscopy and (1)H NMR spectroscopy. Self-assembling of oligomers led to right-angled crystalline particles, as evidenced by scanning electron microscopy and differential scanning calorimetry. EGDMA, TEGDMA and EGDMA-co-TEGDMA oligomers synthesized in the presence of HRP-H(2)O(2) system presented pendant vinyl groups along the chains. good solubility in chloroform, and well-defined melting point. These features evidenced few cross-linking or cyclization and revealed that the catalytic properties of HRP led to oligomeric materials with new characteristics. (C) 2008 Elsevier B.V. All rights reserved.

Conformational stability of peanut agglutinin using small angle X-ray scattering

In this work, quaternary conformational studies of peanut agglutinin (PNA) have been carried out using small-angle X-ray scattering (SAXS). PNA was submitted to three different conditions: pH variation (2.5, 4.0, 7.4 and 9.0), guanidine hydrochloride presence (0.5-2 M) at each pH value, and temperature ranging from 25 to 60 degrees C. All experiments were performed in the absence and presence of T-antigen to evaluate its influence on the lectin stability. At room temperature and pH 4.0,7.4 and 9.0, the SAXS curves are consistent with the PNA scattering in its crystallographic native homotetrameric structure, with monomers in a jelly roll fold, associated by non-covalent bonds resulting in an open structure. At pH 2.5, the results indicate that PNA tends to dissociate into smaller sub-units, as dimers and monomers, followed by a self-assembling into larger aggregates. Furthermore, the conformational stability under thermal denaturation follows the pH sequence 7.4 > 9.0 > 4.0 > 2.5. Such results are consistent with the conformational behavior found upon GndHCl influence. The presence of T-antigen does not affect the protein quaternary structure in all studied systems within the SAXS resolution. (C) 2010 Elsevier B.V. All rights reserved.

Vitellin-binding proteins in the nematode Oscheius tipulae (Nematoda, Rhabditida)

We describe the first application of a non-radioactive ligand-blotting technique to the characterization of proteins interacting with nematode vitellins. Chromatographically purified vitellins from the free-living nematode Oscheius tipulae were labeled with fluorescein in vitro. Ligand-blotting assays with horseradish peroxidase-conjugated anti-fluorescein antibodies showed that labeled vitellins reacted specifically with a polypeptide of approximately 100 kDa, which we named P100. This polypeptide is a specific worm`s vitellin-binding protein that is present only in adult worms. Blots containing purified O. tipulae vitellin preparations showed no detectable signal in the 100 kDa region, ruling out any possibility of yolk polypeptides self-assembling under the conditions used in our assay. Experiments done in the presence of alpha-methyl mannoside ruled out the possibility of vitellins binding to P100 through mannose residues. Triton X-114 fractionation of whole worm extracts showed that P100 is either a membrane protein or has highly hydrophobic regions. (C) 2008 Elsevier Inc. All rights reserved.

Langmuir Films of Petroleum at the Air-Water Interface

Understanding the behavior of petroleum films at the air/water interface is crucial for dealing with oil sticks and reducing the damages to the environment, which has normally been attempted with studies of Langmuir films made of fractions of petroleum. However, the properties of films from whole petroleum samples may differ considerably from those of individual fractions, Using surface pressure and surface potential measurements and Brewster angle and fluorescence microscopy, we show that petroleum forms it nonhomogeneous Langmuir film at the air-water interface. The surface pressure isotherms for petroleum Langmuir films exhibit gas (G), liquid-expanded (LE), and liquid-condensed phases, with almost no hysteresis in the compression-decompression cycles. Domains formed upon compression from the G to the LE phase were accompanied by an increase in fluorescence intensity with excitation at 400-440 nm owing to an increase in the surface density of the chromophores in the petroleum film. The surface pressure and the fluorescence microscopy data pointed to self-assembling domains into a pseudophase in thermo-dynamic equilibrium with other less emitting petroleum components. This hypothesis was supported by Brewster angle microscopy images, whereby the appearance of water domains even at high surface pressures confirms the tendency of petroleum to stabilize emulsion systems. The results presented here suggest that, for understanding the interaction with water, it may be more appropriate to use the whole petroleum samples rather than its fractions.

Engineering of 3D self-directed quantum dot ordering in multilayer InGaAs/GaAs nanostructures by means of flux gas composition

Lateral ordering of InGaAs quantum dots on the GaAs (001) surface has been achieved in earlier reports, resembling an anisotropic pattern. In this work, we present a method of breaking the anisotropy of ordered quantum dots (QDs) by changing the growth environment. We show experimentally that using As(2) molecules instead of As(4) as a background flux is efficient in controlling the diffusion of distant Ga adatoms to make it possible to produce isotropic ordering of InGaAs QDs over GaAs (001). The control of the lateral ordering of QDs under As(2) flux has enabled us to improve their optical properties. Our results are consistent with reported experimental and theoretical data for structure and diffusion on the GaAs surface.

Can previous acid etching increase the bond strength of a self-etching primer adhesive to enamel?

Because a greater research effort has been directed to analyzing the adhesive effectiveness of self etch primers to dentin, the aim of this study was to evaluate, by microtensile testing, the bond strength to enamel of a composite resin combined with a conventional adhesive system or with a self-etching primer adhesive, used according to its original prescription or used with previous acid etching. Thirty bovine teeth were divided into 3 groups with 10 teeth each (n= 10). In one of the groups, a self-etching primer (Clearfil SE Bond - Kuraray) was applied in accordance with the manufacturer's instructions and, in the other, it was applied after previous acid etching. In the third group, a conventional adhesive system (Scotchbond Multipurpose Plus - 3M-ESPE) was applied in accordance with the manufacturer's instructions. The results obtained by analysis of variance revealed significant differences between the adhesive systems (F = 22.31). The self-etching primer (Clearfil SE Bond) presented lower enamel bond strength values than the conventional adhesive system (Scotchbond Multipurpose Plus) (m = 39.70 ± 7.07 MPa) both when used according to the original prescription (m = 27.81 ± 2.64 MPa) and with previous acid etching (m = 25.08 ± 4.92 MPa).

Directed Abelian algebras and their application to stochastic models

With each directed acyclic graph (this includes some D-dimensional lattices) one can associate some Abelian algebras that we call directed Abelian algebras (DAAs). On each site of the graph one attaches a generator of the algebra. These algebras depend on several parameters and are semisimple. Using any DAA, one can define a family of Hamiltonians which give the continuous time evolution of a stochastic process. The calculation of the spectra and ground-state wave functions (stationary state probability distributions) is an easy algebraic exercise. If one considers D-dimensional lattices and chooses Hamiltonians linear in the generators, in finite-size scaling the Hamiltonian spectrum is gapless with a critical dynamic exponent z=D. One possible application of the DAA is to sandpile models. In the paper we present this application, considering one- and two-dimensional lattices. In the one-dimensional case, when the DAA conserves the number of particles, the avalanches belong to the random walker universality class (critical exponent sigma(tau)=3/2). We study the local density of particles inside large avalanches, showing a depletion of particles at the source of the avalanche and an enrichment at its end. In two dimensions we did extensive Monte-Carlo simulations and found sigma(tau)=1.780 +/- 0.005.

The role of electron localization in the atomic structure of transition-metal 13-atom clusters: the example of Co(13), Rh(13), and Hf(13)

The crystalline structure of transition-metals (TM) has been widely known for several decades, however, our knowledge on the atomic structure of TM clusters is still far from satisfactory, which compromises an atomistic understanding of the reactivity of TM clusters. For example, almost all density functional theory (DFT) calculations for TM clusters have been based on local (local density approximation-LDA) and semilocal (generalized gradient approximation-GGA) exchange-correlation functionals, however, it is well known that plain DFT fails to correct the self-interaction error, which affects the properties of several systems. To improve our basic understanding of the atomic and electronic properties of TM clusters, we report a DFT study within two nonlocal functionals, namely, the hybrid HSE (Heyd, Scuseria, and Ernzerhof) and GGA + U functionals, of the structural and electronic properties of the Co(13), Rh(13), and Hf(13) clusters. For Co(13) and Rh(13), we found that improved exchange-correlation functionals decrease the stability of open structures such as the hexagonal bilayer (HBL) and double simple-cubic (DSC) compared with the compact icosahedron (ICO) structure, however, DFT-GGA, DFT-GGA + U, and DFT-HSE yield very similar results for Hf(13). Thus, our results suggest that the DSC structure obtained by several plain DFT calculations for Rh(13) can be improved by the use of improved functionals. Using the sd hybridization analysis, we found that a strong hybridization favors compact structures, and hence, a correct description of the sd hybridization is crucial for the relative energy stability. For example, the sd hybridization decreases for HBL and DSC and increases for ICO in the case of Co(13) and Rh(13), while for Hf(13), the sd hybridization decreases for all configurations, and hence, it does not affect the relative stability among open and compact configurations.

Structural control of gold nanoparticles self-assemblies by layer-by-layer process

This work presents a novel way to introduce gold nanoparticles (Au NPs) in a multilayer polymer produced by the layer-by-layer (LbL) assembling technique. The technique chosen shows that, depending on the pH used, different morphological structures can be obtained from monolayer or bilayer Au NPs. The MEIS and RBS techniques allowed for the modelling of the interface polymer-NPs, as well as the understanding of the interaction of LbL system, when adjusting the pH in weak polyelectrolytes. The process reveals that the optical properties of multilayer systems could be fine-tuned by controlling the addition of metallic nanoparticles, which could also modify specific polarization responses.

Assembling a consistent set of sentences in relational probabilistic logic with stochastic independence

We examine the representation of judgements of stochastic independence in probabilistic logics. We focus on a relational logic where (i) judgements of stochastic independence are encoded by directed acyclic graphs, and (ii) probabilistic assessments are flexible in the sense that they are not required to specify a single probability measure. We discuss issues of knowledge representation and inference that arise from our particular combination of graphs, stochastic independence, logical formulas and probabilistic assessments. (C) 2007 Elsevier B.V. All rights reserved.

High Carbon Ferro-chromium Production by Self-reducing Process: Effects of Fe-Si and Fluxing Agent Additions

The technology of self-reducing pellets for ferro-alloys production is becoming an emerging process due to the lower electric energy consumption and the improvement of metal recovery in comparison with the traditional process. This paper presents the effects of reduction temperature, addition of ferro-silicon and addition of slag forming agents for the production of high carbon ferro-chromium by utilization of self-reducing pellets. These pellets were composed of Brazilian chromium ore (chromite) concentrate, petroleum coke, Portland cement, ferro-silicon and slag forming components (silica and hydrated lime). The pellets were processed at 1 773 K, 1 823 K and 1 873 K using an induction furnace. The products obtained, containing slag and metallic phases, were analyzed by scanning electron microscopy and chemical analyses (XEDS). A large effect on the reduction time was observed by increasing the temperature from 1 773 K to 1 823 K for pellets without Fe-Si addition: around 4 times faster at 1 823 K than at 1 773 K for reaction fraction close to one. However, when the temperature was further increased from 1 823 K to 1 873 K the kinetics improved by double. At 1 773 K, the addition of 2% of ferro-silicon in the pellet resulted in an increasing reaction rate of around 6 times, in comparison with agglomerate without it. The addition of fluxing agents (silica and lime), which form initial slag before the reduction is completed, impaired the full reduction. These pellets became less porous after the reduction process.

High Carbon Ferro-Chromium by Self-Reducing Process

This paper discusses the effects of temperature, addition of ferro-silicon and fluxing agents for the production of high carbon ferro-chromium by self-reducing process. The use of self-reducing agglomerates for ferro-alloys production is becoming an emerging processing technology due to lowering the electric energy consumption and improving the metal recovery in comparison with traditional ones. The self-reducing pellets were composed by chromite, petroleum coke, cement and small (0.1% - 2%) addition of ferro-silicon. The slag composition was adjusted by addition of fluxing agents. The reduction of pellets was carried out at 1773K (1500 degrees C), 1823K (1550 degrees C) and 1873K (1600 degrees C) by using induction furnace. The products obtained, containing slag and metallic phases, were analyzed by scanning electron microscopy and chemical analyses (XEDS). By increasing temperature from 1773K to 1823K large effect on the reduction time was observed. It decreased from 30 minutes to 10 minutes, for reaching around 0.98 reduction fraction. No significant effect on reduction time was observed when the reduction temperature was increased from 1823K to 1873K. At 1773K, the addition of 2% of ferro-silicon in the pellet resulted in an increasing reaction rate of around 6 times, in comparison with agglomerate without this addition. The addition of fluxing agents (silica and hydrated lime) has effect on reduction time (inverse relationship) and the pellets become less porous after reduction.

Ten-year Retrospective Study of Treatment of Malignant Colonic Obstructions with Self-expandable Stents

Purpose: To describe the use of self-expandable metallic stents to manage malignant colorectal obstructions and to compare the radiation dose between fluoroscopic guidance of stent placement and combined endoscopic and fluoroscopic guidance. Materials and Methods: From January 1998 to December 2007, 467 oncology patients undergoing colorectal stent placement in a single center were included in the study. Informed consent was obtained in all cases. All procedures were performed with fluoroscopic or combined fluoroscopic and endoscopic guidance. Inclusion criteria were total or partial colorectal obstruction of neoplastic origin. Exclusion criteria were life expectancy shorter than I month, suspicion of perforation, and/or severe colonic neoplastic bleeding. Procedure time and radiation dose were recorded, and technical and clinical success were evaluated. Follow-up was performed by clinical examination and simple abdominal radiographs at 1 day and at I, 3, 6, and 12 months. Results: Of 467 procedures, technical success was achieved in 432 (92.5%). Thirty-five treatments (7.5%) were technical failures, and the patients were advised to undergo surgery. Significant differences in radiation dose and clinical success were found between the fluoroscopy and combined-technique groups (P < .001). Total decompression was achieved in 372 cases, 29 patients showed remarkable improvement, 11 showed slight improvement, and 20 showed clinical failure. Complications were recorded in 89 patients (19%), the most significant were perforation (2.3%) and stent migration (6.9%). Mean interventional time and radiation dose were 67 minutes and 3,378 dGy.cm(2), respectively. Conclusions: Treatment of colonic obstruction with stents requires a long time in the interventional room and considerable radiation dose. Nevertheless, the clinical benefits and improvement in quality of life justify the radiation risk.