Determination of dimethyltryptamine and beta-carbolines (ayahuasca alkaloids) in plasma samples by LC-MS/MS

Background: Ayahuasca is a psychoactive plant beverage originally used by indigenous people throughout the Amazon Basin, long before its modern use by syncretic religious groups established in Brazil, the USA and European countries. The objective of this study was to develop a method for quantification of dimethyltryptamine and beta-carbolines in human plasma samples. Results: The analytes were extracted by means of C18 cartridges and injected into LC-MS/MS, operated in positive ion mode and multiple reaction monitoring. The LOQs obtained for all analytes were below 0.5 ng/ml. By using the weighted least squares linear regression, the accuracy of the analytical method was improved at the lower end of the calibration curve (from 0.5 to 100 ng/ml; r(2)> 0.98). Conclusion: The method proved to be simple, rapid and useful to estimate administered doses for further pharmacological and toxicological investigations of ayahuasca exposure.

Advanced QSAR Studies on PPAR delta Ligands Related to Metabolic Diseases

PPAR delta is a nuclear receptor that, when activated, regulates the metabolism of carbohydrates and lipids and is related to metabolic syndrome and type 2 diabetes. To understand the main interactions between ligands and PPAR delta, we have constructed 2D and 3D QSAR models and compared them with HOMO, LUMO and electrostatic potential maps of the compounds studied, as well as docking results. All QSAR models showed good statistical parameters and prediction outcomes. The QSAR models were used to predict the biological activity of an external test set, and the predicted values are in good agreement with the experimental results. Furthermore, we employed all maps to evaluate the possible interactions between the ligands and PPAR delta. These predictive QSAR models, along with the HOMO, LUMO and MEP maps, can provide insights into the structural and chemical properties that are needed in the design of new PPAR delta ligands that have improved biological activity and can be employed to treat metabolic diseases.

Comparison of multiple-input single-output single-user ultra-wideband systems with pre-distortion

This paper presents a performance analysis of a baseband multiple-input single-output ultra-wideband system over scenarios CM1 and CM3 of the IEEE 802.15.3a channel model, incorporating four different schemes of pre-distortion: time reversal, zero-forcing pre-equaliser, constrained least squares pre-equaliser, and minimum mean square error pre-equaliser. For the third case, a simple solution based on the steepest-descent (gradient) algorithm is adopted and compared with theoretical results. The channel estimations at the transmitter are assumed to be truncated and noisy. Results show that the constrained least squares algorithm has a good trade-off between intersymbol interference reduction and signal-to-noise ratio preservation, providing a performance comparable to the minimum mean square error method but with lower computational complexity. Copyright (C) 2011 John Wiley & Sons, Ltd.

Strategies in identifying individuals in a segregant population of common bean and implications of genotype x environment interaction in the success of selection

The objective of this study was to compare the BLUP selection method with different selection strategies in F-2:4 and assess the efficiency of this method on the early choice of the best common bean (Phaseolus vulgaris) lines. Fifty-one F-2:4 progenies were produced from a cross between the CVIII8511 x RP-26 lines. A randomized block design was used with 20 replications and one-plant field plots. Character data on plant architecture and grain yield were obtained and then the sum of the standardized variables was estimated for simultaneous selection of both traits. Analysis was carried out by mixed models (BLUP) and the least squares method to compare different selection strategies, like mass selection, stratified mass selection and between and within progeny selection. The progenies selected by BLUP were assessed in advanced generations, always selecting the greatest and smallest sum of the standardized variables. Analyses by the least squares method and BLUP procedure ranked the progenies in the same way. The coincidence of the individuals identified by BLUP and between and within progeny selection was high and of the greatest magnitude when BLUP was compared with mass selection. Although BLUP is the best estimator of genotypic value, its efficiency in the response to long term selection is not different from any of the other methods, because it is also unable to predict the future effect of the progenies x environments interaction. It was inferred that selection success will always depend on the most accurate possible progeny assessment and using alternatives to reduce the progenies x environments interaction effect.

Response plateau models fitting via isotonic regression

Within the nutritional context, the supplementation of microminerals in bird food is often made in quantities exceeding those required in the attempt to ensure the proper performance of the animals. The experiments of type dosage x response are very common in the determination of levels of nutrients in optimal food balance and include the use of regression models to achieve this objective. Nevertheless, the regression analysis routine, generally, uses a priori information about a possible relationship between the response variable. The isotonic regression is a method of estimation by least squares that generates estimates which preserves data ordering. In the theory of isotonic regression this information is essential and it is expected to increase fitting efficiency. The objective of this work was to use an isotonic regression methodology, as an alternative way of analyzing data of Zn deposition in tibia of male birds of Hubbard lineage. We considered the models of plateau response of polynomial quadratic and linear exponential forms. In addition to these models, we also proposed the fitting of a logarithmic model to the data and the efficiency of the methodology was evaluated by Monte Carlo simulations, considering different scenarios for the parametric values. The isotonization of the data yielded an improvement in all the fitting quality parameters evaluated. Among the models used, the logarithmic presented estimates of the parameters more consistent with the values reported in literature.

Electrospray Ionization Mass Spectrometry Fingerprinting of Extracts of the Leaves of Arrabidaea chica

Arrabidaea chica (crajiru) is an important Amazonian plant. Its extracts are used as red pigments, antimicrobial agents and astringents. Three different varieties of this species are cultivated in the Amazon region. In this work, direct infusions of A. chica extracts from these three varieties were analyzed via electrospray ionization mass spectrometry (ESI(+)-MS) fingerprinting. Derived data from the spectra were classified by using a multivariate method (PLS-DA, partial least squares-discriminant analysis). The direct method that is herein presented relies on extraction of dry, powdered leaves with acidified methanol/water solution with no further sample preparation. The resulting supernatants were analyzed by direct infusion ESI(+)-MS, which provides characteristic fingerprints of the sample composition. 3-Deoxyanthocyanidins are important substances in A. chica, their ions were used as markers in the PLS-DA data treatment. PLS-DA was able to differentiate the three varieties. ESI(+)-MS fingerprinting works as a simple and fast method to differentiate varieties of A. chica.

Modeling and Identification of an Open-frame Underwater Vehicle: The Yaw Motion Dynamics

A semi-autonomous unmanned underwater vehicle (UUV), named LAURS, is being developed at the Laboratory of Sensors and Actuators at the University of Sao Paulo. The vehicle has been designed to provide inspection and intervention capabilities in specific missions of deep water oil fields. In this work, a method of modeling and identification of yaw motion dynamic system model of an open-frame underwater vehicle is presented. Using an on-board low cost magnetic compass sensor the method is based on the utilization of an uncoupled 1-DOF (degree of freedom) dynamic system equation and the application of the integral method which is the classical least squares algorithm applied to the integral form of the dynamic system equations. Experimental trials with the actual vehicle have been performed in a test tank and diving pool. During these experiments, thrusters responsible for yaw motion are driven by sinusoidal voltage signal profiles. An assessment of the feasibility of the method reveals that estimated dynamic system models are more reliable when considering slow and small sinusoidal voltage signal profiles, i.e. with larger periods and with relatively small amplitude and offset.

Intervention Based Exclusively on Stage- Matched Printed EducationalMaterials Regarding Healthy Eating Does Not Result in Changes to Adolescents' Dietary Behavior

Purpose. To assess the impact of a six-month stage-based intervention on fruit and vegetable intake, regarding perceived benefits and barriers, and self-efficacy among adolescents. Design. Randomized treatment-control, pre-post design. Subjects/ Setting. Schools were randomized between control and experimental groups. 860 adolescents from ten public schools in Bras ' ilia, Federal District, Brazil were evaluated at baseline; 771 (81%) completed the study. Intervention. Experimental group received monthly magazines and newsletters aimed at promotion of healthy eating. Measures. Self-reported fruit and vegetable intake, stages of change, self-efficacy and decisional balance scores were evaluated at baseline and post-intervention in both groups. Analysis. The effectiveness of the intervention was evaluated using the analysis of covariance model (ANCOVA) and repeated measurement analysis by means of weighted least squares. Comparison between the proportions of adolescents who advanced through the stages during the intervention was performed using the Mantel-Haenszel chi-square test. Results. After adjusting for sex and age, study variables showed no modifications through the proposed intervention. There was no statistical difference in participant mobility in the intervention and control groups between the stages of change, throughout the study. Conclusion. A nutritional intervention based exclusively on distribution of stage-matched printed educational materials was insufficient to change adolescents' dietary behavior.

Lipid fingerprinting in women with early-onset preeclampsia: A first look

Objectives: The aim of this preliminary study was to characterize the plasma lipid profiling of women with preeclampsia. Design and methods: Plasma samples of 8 pregnant women with early-onset preeclampsia and 8 normal pregnant women were evaluated. Lipids were extracted from plasma using the Bligh-Dyer protocol. The extracts were subjected to MALDI-MS. Data matrix was exported for partial least squares discriminant analysis (PLS-DA) and a parameter VIP was employed to reflect the variable importance in the discriminant analysis. The major discriminant variables were selected and underwent to Mann-Whitney U test. Results: A total of 1290 ions were initially identified and twelve m/z signals were highlighted as the most important lipids for the discrimination of patients with preeclampsia. The identification of these differential lipids was carried out through Lipid Database Search. Conclusions: The main classes identified were glycerophosphocholines [GP01], glycerophosphoserines [GP03], glycerophosphoglycerols [GP04], glycosyldiradylglycerols [GL05] and glycerophosphates [GP10]. (C) 2012 The Canadian Society of Clinical Chemists. Published by Elsevier Inc. All rights reserved.

Direct Determination of Sugar Cane Quality Parameters by X-ray Spectrometry and Multivariate Analysis

Current methods for quality control of sugar cane are performed in extracted juice using several methodologies, often requiring appreciable time and chemicals (eventually toxic), making the methods not green and expensive. The present study proposes the use of X-ray spectrometry together with chemometric methods as an innovative and alternative technique for determining sugar cane quality parameters, specifically sucrose concentration, POL, and fiber content. Measurements in stem, leaf, and juice were performed, and those applied directly in stem provided the best results. Prediction models for sugar cane stem determinations with a single 60 s irradiation using portable X-ray fluorescence equipment allows estimating the % sucrose, % fiber, and POL simultaneously. Average relative deviations in the prediction step of around 8% are acceptable if considering that field measurements were done. These results may indicate the best period to cut a particular crop as well as for evaluating the quality of sugar cane for the sugar and alcohol industries.

Gaussian deconvolution: a useful method for a form-free modeling of scattering data from mono- and multilayered planar systems

A new method for analysis of scattering data from lamellar bilayer systems is presented. The method employs a form-free description of the cross-section structure of the bilayer and the fit is performed directly to the scattering data, introducing also a structure factor when required. The cross-section structure (electron density profile in the case of X-ray scattering) is described by a set of Gaussian functions and the technique is termed Gaussian deconvolution. The coefficients of the Gaussians are optimized using a constrained least-squares routine that induces smoothness of the electron density profile. The optimization is coupled with the point-of-inflection method for determining the optimal weight of the smoothness. With the new approach, it is possible to optimize simultaneously the form factor, structure factor and several other parameters in the model. The applicability of this method is demonstrated by using it in a study of a multilamellar system composed of lecithin bilayers, where the form factor and structure factor are obtained simultaneously, and the obtained results provided new insight into this very well known system.

Determination of chlorine in food samples via the AlCl molecule using high-resolution continuum source molecular absorption spectrometry in a graphite furnace

Determination of chlorine using the molecular absorption of aluminum mono-chloride (AlCl) at the 261.418 nm wavelength was accomplished by high-resolution continuum source molecular absorption spectrometry using a transversely heated graphite tube furnace with an integrated platform. For the analysis. 10 mu L of the sample followed by 10 mu L of a solution containing Al-Ag-Sr modifier, (1 g L-1 each), were directly injected onto the platform. A spectral interference due to the use of Al-Ag-Sr as mixed modifier was easily corrected by the least-squares algorithm present in the spectrometer software. The pyrolysis and vaporization temperatures were 500 degrees C and 2200 degrees C, respectively. To evaluate the feasibility of a simple procedure for the determination of chlorine in food samples present in our daily lives, two different digestion methods were applied, namely (A) an acid digestion method using HNO3 only at room temperature, and (B) a digestion method with Ag, HNO3 and H2O2, where chlorine is precipitated as a low-solubility salt (AgCl), which is then dissolved with ammonia solution. The experimental results obtained with method B were in good agreement with the certified values and demonstrated that the proposed method is more accurate than method A. This is because the formation of silver chloride prevented analyte losses by volatilization. The limit of detection (LOD, 3 sigma/s) for Cl in methods A and B was 18 mu g g(-1) and 9 mu g g(-1), respectively, 1.7 and 3.3 times lower compared to published work using inductively coupled plasma optical emission spectrometry, and absolute LODs were 2.4 and 1.2 ng, respectively. (C) 2012 Elsevier B.V. All rights reserved.

Efeito direto e interativo do período de avaliação sobre a orientação temporal dos gestores

O objetivo neste estudo é investigar o efeito direto e interativo do período de avaliação sobre a orientação temporal dos gestores (OTG), isto é, o horizonte de tempo entre o momento de alocação de recursos e o momento do impacto financeiro dessa alocação. Tendo por base a literatura contábil e econômica, são examinadas as seguintes hipóteses: um período de avaliação mais de longo prazo afeta positivamente a OTG e o efeito positivo de um período de avaliação mais de longo prazo sobre a OTG é maior no caso de maior importância atribuída a medidas não financeiras do que a medidas financeiras de desempenho. Aplica-se a técnica estatística de mínimos quadrados parciais (PLS) para testar as hipóteses deste estudo, sendo os dados coletados por meio de um levantamento realizado junto a 66 gestores de nível intermediário que atuam em 11 empresas. Os resultados sugerem que o período de avaliação não possui efeitos diretos sobre a OTG; no entanto, quando considerada sua interação com a medida de desempenho, os resultados indicam que o efeito do período de avaliação sobre a OTG depende da importância relativa de medidas financeiras versus não financeiras. A principal implicação desses resultados é que o uso de um período de avaliação de longo prazo em combinação com um peso maior atribuído a medidas não financeiras de desempenho não afeta positivamente a OTG; ao contrário, esse efeito positivo sobre a OTG está presente quando um período de avaliação de curto prazo está associado a menor importância de medidas não financeiras de desempenho.

Experimental model identification of open-frame underwater vehicles

Most of the works published on hydrodynamic parameter identification of open-frame underwater vehicles focus their attention almost exclusively on good coherence between simulated and measured responses, giving less importance to the determination of “actual values” for hydrodynamic parameters. To gain insight into hydrodynamic parameter experimental identification of open-frame underwater vehicles, an experimental identification procedure is proposed here to determine parameters of uncoupled and coupled models. The identification procedure includes: (i) a prior estimation of actual values of the forces/torques applied to the vehicle, (ii) identification of drag parameters from constant velocity tests and (iii) identification of inertia and coupling parameters from oscillatory tests; at this stage, the estimated values of drag parameter obtained in item (ii) are used. The procedure proposed here was used to identify the hydrodynamic parameters of LAURS—an unmanned underwater vehicle developed at the University of São Paulo. The thruster–thruster and thruster–hull interactions and the advance velocity of the vehicle are shown to have a strong impact on the efficiency of thrusters appended to open-frame underwater vehicles, especially for high advance velocities. Results of tests with excitation in 1-DOF and 3-DOF are reported and discussed, showing the feasibility of the developed procedure.

Multivariate spectroscopic methods for the analysis of solutions

In this thesis some multivariate spectroscopic methods for the analysis of solutions are proposed. Spectroscopy and multivariate data analysis form a powerful combination for obtaining both quantitative and qualitative information and it is shown how spectroscopic techniques in combination with chemometric data evaluation can be used to obtain rapid, simple and efficient analytical methods. These spectroscopic methods consisting of spectroscopic analysis, a high level of automation and chemometric data evaluation can lead to analytical methods with a high analytical capacity, and for these methods, the term high-capacity analysis (HCA) is suggested. It is further shown how chemometric evaluation of the multivariate data in chromatographic analyses decreases the need for baseline separation. The thesis is based on six papers and the chemometric tools used are experimental design, principal component analysis (PCA), soft independent modelling of class analogy (SIMCA), partial least squares regression (PLS) and parallel factor analysis (PARAFAC). The analytical techniques utilised are scanning ultraviolet-visible (UV-Vis) spectroscopy, diode array detection (DAD) used in non-column chromatographic diode array UV spectroscopy, high-performance liquid chromatography with diode array detection (HPLC-DAD) and fluorescence spectroscopy. The methods proposed are exemplified in the analysis of pharmaceutical solutions and serum proteins. In Paper I a method is proposed for the determination of the content and identity of the active compound in pharmaceutical solutions by means of UV-Vis spectroscopy, orthogonal signal correction and multivariate calibration with PLS and SIMCA classification. Paper II proposes a new method for the rapid determination of pharmaceutical solutions by the use of non-column chromatographic diode array UV spectroscopy, i.e. a conventional HPLC-DAD system without any chromatographic column connected. In Paper III an investigation is made of the ability of a control sample, of known content and identity to diagnose and correct errors in multivariate predictions something that together with use of multivariate residuals can make it possible to use the same calibration model over time. In Paper IV a method is proposed for simultaneous determination of serum proteins with fluorescence spectroscopy and multivariate calibration. Paper V proposes a method for the determination of chromatographic peak purity by means of PCA of HPLC-DAD data. In Paper VI PARAFAC is applied for the decomposition of DAD data of some partially separated peaks into the pure chromatographic, spectral and concentration profiles.