The isotropic nuclear magnetic shielding constants of acetone in supercritical water: A sequential Monte Carlo/quantum mechanics study including solute polarization

The nuclear isotropic shielding constants sigma((17)O) and sigma((13)C) of the carbonyl bond of acetone in water at supercritical (P=340.2 atm and T=673 K) and normal water conditions have been studied theoretically using Monte Carlo simulation and quantum mechanics calculations based on the B3LYP/6-311++G(2d,2p) method. Statistically uncorrelated configurations have been obtained from Monte Carlo simulations with unpolarized and in-solution polarized solute. The results show that solvent effects on the shielding constants have a significant contribution of the electrostatic interactions and that quantitative estimates for solvent shifts of shielding constants can be obtained modeling the water molecules by point charges (electrostatic embedding). In supercritical water, there is a decrease in the magnitude of sigma((13)C) but a sizable increase in the magnitude of sigma((17)O) when compared with the results obtained in normal water. It is found that the influence of the solute polarization is mild in the supercritical regime but it is particularly important for sigma((17)O) in normal water and its shielding effect reflects the increase in the average number of hydrogen bonds between acetone and water. Changing the solvent environment from normal to supercritical water condition, the B3LYP/6-311++G(2d,2p) calculations on the statistically uncorrelated configurations sampled from the Monte Carlo simulation give a (13)C chemical shift of 11.7 +/- 0.6 ppm for polarized acetone in good agreement with the experimentally inferred result of 9-11 ppm. (C) 2008 American Institute of Physics.

Nonmonotonic thickness dependence of spin wave energy in ultrathin Fe films: Experiment and theory

High wave-vector spin waves in ultrathin Fe/W(110) films up to 20 monolayers (MLs) thick have been studied using spin-polarized electron energy-loss spectroscopy. An unusual nonmonotonous dependence of the spin wave energies on the film thickness is observed, featuring a pronounced maximum at 2 ML coverage. First-principles theoretical study reveals the origin of this behavior to be in the localization of the spin waves at the surface of the film, as well as in the properties of the interlayer exchange coupling influenced by the hybridization of the electron states of the film and substrate and by the strain.

Magnons in a Ferromagnetic Monolayer

We report the first observation of high wave vector magnon excitations in a ferromagnetic monolayer. Using spin-polarized electron energy loss spectroscopy, we observed the magnon dispersion in one atomic layer (ML) of Fe on W(110) at 120 K. The magnon energies are small in comparison to the bulk and surface Fe(110) excitations. We find an exchange parameter and magnetic anisotropy similar to that from static measurements. Our results are in sharp contrast to theoretical calculations, indicating that the present understanding of magnetism of the ML Fe requires considerable revision.

Elementary Excitations at Magnetic Surfaces and Their Spin Dependence

The elementary surface excitations are studied by spin-polarized electron energy loss spectroscopy on a prototype oxide surface [an oxygen passivated Fe(001)-p(1 x 1) surface], where the various excitations coexist. For the first time, the surface phonons and magnons are measured simultaneously and are distinguished based on their different spin nature. The dispersion relation of all excitations is probed over the entire Brillouin zone. The different phonon modes observed in our experiment are described by means of ab initio calculations.

Comparison of multispectral wide-field optical imaging modalities to maximize image contrast for objective discrimination of oral neoplasia

Multispectral widefield optical imaging has the potential to improve early detection of oral cancer. The appropriate selection of illumination and collection conditions is required to maximize diagnostic ability. The goals of this study were to (i) evaluate image contrast between oral cancer/precancer and non-neoplastic mucosa for a variety of imaging modalities and illumination/collection conditions, and (ii) use classification algorithms to evaluate and compare the diagnostic utility of these modalities to discriminate cancers and precancers from normal tissue. Narrowband reflectance, autofluorescence, and polarized reflectance images were obtained from 61 patients and 11 normal volunteers. Image contrast was compared to identify modalities and conditions yielding greatest contrast. Image features were extracted and used to train and evaluate classification algorithms to discriminate tissue as non-neoplastic, dysplastic, or cancer; results were compared to histologic diagnosis. Autofluorescence imaging at 405-nm excitation provided the greatest image contrast, and the ratio of red-to-green fluorescence intensity computed from these images provided the best classification of dysplasia/cancer versus non-neoplastic tissue. A sensitivity of 100% and a specificity of 85% were achieved in the validation set. Multispectral widefield images can accurately distinguish neoplastic and non-neoplastic tissue; however, the ability to separate precancerous lesions from cancers with this technique was limited. (C) 2010 Society of Photo-Optical Instrumentation Engineers. [DOI: 10.1117/1.3516593]

NMR analog of Bell's inequalities violation test

In this paper, we present an analog of Bell's inequalities violation test for N qubits to be performed in a nuclear magnetic resonance (NMR) quantum computer. This can be used to simulate or predict the results for different Bell's inequality tests, with distinct configurations and a larger number of qubits. To demonstrate our scheme, we implemented a simulation of the violation of the Clauser, Horne, Shimony and Holt (CHSH) inequality using a two-qubit NMR system and compared the results to those of a photon experiment. The experimental results are well described by the quantum mechanics theory and a local realistic hidden variables model (LRHVM) that was specifically developed for NMR. That is why we refer to this experiment as a simulation of Bell's inequality violation. Our result shows explicitly how the two theories can be compatible with each other due to the detection loophole. In the last part of this work, we discuss the possibility of testing some fundamental features of quantum mechanics using NMR with highly polarized spins, where a strong discrepancy between quantum mechanics and hidden variables models can be expected.

Scanning tunneling microscope operating as a spin diode

We theoretically investigate spin-polarized transport in a system composed of a ferromagnetic scanning-tunneling-microscope (STM) tip coupled to an adsorbed atom (adatom) on a host surface. Electrons can tunnel directly from the tip to the surface or via the adatom. Since the tip is ferromagnetic and the host surface (metal or semiconductor) is nonmagnetic we obtain a spin-diode effect when the adatom is in the regime of single occupancy. This effect leads to an unpolarized current for direct bias (V > 0) and polarized current for reverse (V < 0) bias voltages, if the tip is nearby the adatom. Within the nonequilibrium Keldysh technique we analyze the interplay between the lateral displacement of the tip and the intra adatom Coulomb interaction on the spin-diode effect. As the tip moves away from the adatom the spin-diode effect vanishes and the currents become polarized for both V > 0 and V < 0. We also find an imbalance between the up and down spin populations in the adatom, which can be tuned by the tip position and the bias. Finally, due to the presence of the adsorbate on the surface, we observe spin-resolved Friedel oscillations in the current, which reflects the oscillations in the calculated local density of states (LDOS) of the subsystem surface + adatom.

INFERENCE FOR EIGENVALUES AND EIGENVECTORS OF GAUSSIAN SYMMETRIC MATRICES

This article presents maximum likelihood estimators (MLEs) and log-likelihood ratio (LLR) tests for the eigenvalues and eigenvectors of Gaussian random symmetric matrices of arbitrary dimension, where the observations are independent repeated samples from one or two populations. These inference problems are relevant in the analysis of diffusion tensor imaging data and polarized cosmic background radiation data, where the observations are, respectively, 3 x 3 and 2 x 2 symmetric positive definite matrices. The parameter sets involved in the inference problems for eigenvalues and eigenvectors are subsets of Euclidean space that are either affine subspaces, embedded submanifolds that are invariant under orthogonal transformations or polyhedral convex cones. We show that for a class of sets that includes the ones considered in this paper, the MLEs of the mean parameter do not depend on the covariance parameters if and only if the covariance structure is orthogonally invariant. Closed-form expressions for the MLEs and the associated LLRs are derived for this covariance structure.

Dodigen 213-N as corrosion inhibitor for ASTM 1010 mild steel in 10% HCL

This article describes a study of the behavior of a mixture of amines and amides, commercially known as Dodigen 213-N (D-213 N), as a corrosion inhibitor for ASTM 1010 mild steel in 10% w/w HCl solution. The concentration range used was 1 x 10(-5) M to 8 x 10(-4) M. The weight loss and electrochemical techniques used were corrosion potential measurement, anodic and cathodic polarization curves, and electrochemical impedance spectroscopy (EIS). The solution temperature was 50 +/- A 1 A degrees C and it was naturally aerated. The corrosion potential values shifted to slightly more positive values, thus indicating mixed inhibitor behavior. The anodic and cathodic polarization curves showed that D-213 N is an effective corrosion inhibitor, since both the anodic and the cathodic reactions were polarized in comparison with those obtained without inhibitor. For all concentrations the cathodic polarization curves were more polarized than the anodic ones. The inhibition efficiency was in the range 75-98%, calculated from values of weight loss and corrosion current density, i (corr), obtained by extrapolation of Tafel cathodic linear region.

Denisiuk-type reflection holography display with sillenite crystals for imaging and interferometry of small objects

A novel setup for imaging and interferometry through reflection holography with Bi12TiPO20(BTO) sillenite photorefractive crystals is proposed. A variation of the lensless Denisiuk arrangement was developed resulting in a compact, robust and simple interferometer. A red He-Ne laser was used as light source and the holographic recording occurred by diffusion with the grating vector parallel to the crystal [0 0 1]-axis. In order to enhance the holographic image quality and reduce noise a polarizing beam splitter (PBS) was positioned at the BTO input and the crystal was tilted around the [0 0 1]-axis. This enabled the orthogonally polarized transmission and diffracted beams to be separated by the PBS, providing the holographic image only. The possibility of performing deformation and strain analysis as well as vibration measurement of small objects was demonstrated. (C) 2007 Elsevier B.V. All rights reserved.

Comparative physical-chemical characterization of encapsulated lipid-based isotretinoin products assessed by particle size distribution and thermal behavior analyses

Isotretinoin is the drug of choice for the management of severe recalcitrant nodular acne. Nevertheless, some of its physical-chemical properties are still poorly known. Hence, the aim of our study consisted to comparatively evaluate the particle size distribution (PSD) and characterize the thermal behavior of the three encapsulated isotretinoin products in oil suspension (one reference and two generics) commercialized in Brazil. Here, we show that the PSD, estimated by laser diffraction and by polarized light microscopy, differed between the generics and the reference product. However, the thermal behavior of the three products, determined by thermogravimetry (TGA), differential thermal (DTA) analyses and differential scanning calorimetry (DSC), displayed no significant changes and were more thermostable than the isotretinoin standard used as internal control. Thus, our study suggests that PSD analyses in isotretinoin lipid-based formulations should be routinely performed in order to improve their quality and bioavailability. (C) 2010 Elsevier B.V. All rights reserved.

Electron beam induced second-harmonic generation in Er(3+) doped PbO-GeO(2) glasses containing silver nanoparticles

Electron beam induced second harmonic generation (SHG) is studied in Er(3+) doped PbO-GeO(2) glasses containing silver nanoparticles with concentrations that are controlled by the heat-treatment of the samples. The SHG is observed at T = 4.2 K using a p-polarized laser beam at 1064 nm. Enhancement of the SHG is observed in the samples that are submitted to electron beam incidence. The highest value of the nonlinear susceptibility, 2.08 pm/V, is achieved for the sample heat-treated during 72 h and submitted to an electron beam current of 15 nA. The samples that were not exposed to the electron beam present a susceptibility of a parts per thousand 0.5 pm/V.

In situ gelling hexagonal phases for sustained release of an anti-addiction drug

In this study, fluid precursor formulations for subcutaneous injection and in situ formation of hexagonal phase gels upon water absorption were developed as a strategy to sustain the release of naltrexone, a drug used for treatment of drug addiction. Precursor formulations were obtained by combining BRIJ 97 with propylene glycol (PG, 5-70%, w/w). To study the phase behavior of these formulations, water was added at 10-90% (w/w), and the resulting systems were characterized by polarized light microscopy. Two precursor formulations containing BRIJ:PG at 95:5 (w/w, referred to as BRIJ-95) and at 80:20 (w/w, referred to as BRIJ-80) were chosen. Naltrexone was dissolved at 1% or suspended at 5% (w/w). Precursor formulations were transformed into hexagonal phases when water content exceeded 20%. Water uptake followed second-order kinetics, and after 2-4 h all precursor formulations were transformed into hexagonal phases. Drug release was prolonged by the precursor formulations (compared to a drug solution in PBS), and followed pseudo-first order kinetics regardless of naltrexone concentration. The release from BRIJ-80 was significantly higher than that from BRIJ-95 after 48 h. The relative safety of the precursor formulations was assessed in cultured fibroblasts. Even though BRIJ-95 was more cytotoxic than BRIJ-80, both precursor formulations were significantly less cytotoxic than sodium lauryl sulfate (considered moderate-to-severe irritant) at the same concentration (up to 50 mu g/mL). These results suggest the potential of BRIJ-based precursor formulations for sustained naltrexone release. (C) 2011 Elsevier By. All rights reserved.

Role of phospholipase C and protein kinase C in Aspergillus nidulans during growth on pectin or glucose: Effects on germination and duplication cycle

The effects of PLC and Pkc inhibitors on Aspergillus nidulans depend on the carbon source. PLC inhibitors Spm and C48/80 delayed the first nuclear division in cultures growing on glucose, but stimulated it in media supplemented with pectin. Less intense were these effects on the mutant transformed with PLC-A gene rupture (AP27). Neomycin also delayed the germination in cultures growing on glucose or pectin; however, on glucose, the nuclear division was inhibited whereas in pectin it was stimulated. These effects were minor in AP27. The effects of Ro-31-8425 and BIM (both Pkc inhibitors) were also opposite for cultures growing on glucose or pectin. On glucose cultures of both strains BIM delayed germination and the first nuclear division, whereas on pectin both parameters were stimulated. Opposite effects were also detected when the cultures were growing on glucose or pectin in the presence of Ro-31-8425.

Cdc42p controls yeast-cell shape and virulence of Paracoccidioides brasiliensis

Paracoccidioides brasiliensis is characterized by a multiple budding phenotype and a polymorphic cell growth, leading to the formation of cells with extreme variations in shape and size. Since Cdc42 is a pivotal molecule in establishing and maintaining polarized growth for diverse cell types, as well as during pathogenesis of certain fungi, we evaluated its role during cell growth and virulence of the yeast-form of P. brasiliensis. We used antisense technology to knock-down PbCDC42`s expression in P. brasiliensis yeast cells, promoting a decrease in cell size and more homogenous cell growth, altering the typical polymorphism of wild-type cells. Reduced expression levels also lead to increased phagocytosis and decreased virulence in a mouse model of infection. We provide genetic evidences underlying Pbcdc42p as an important protein during host-pathogen interaction and the relevance of the polymorphic nature and cell size in the pathogenesis of P. brasiliensis. (C) 2009 Elsevier Inc. All rights reserved.