Easy mass spectrometry for metabolomics and quality control of vegetable and animal fats

Easy ambient sonic spray ionization (EASI), a novel desorption/ionization technique for ambient mass spectrometry analysis, is shown to permit the characterization of different types of vegetable and animal fats. The taxonomic markers of the oils, mainly fatty acids and phenols, are extracted with methanol/water (1:1) solution and made alkaline with NH₄OH, then placed and dried on the surface of a glass tip and directly analyzed by EASI‐MS in the negative‐ion mode. EASI provides a supersonic cloud of charged droplets that causes efficient desorption and ionization of the oil markers directly from the surface of the glass tip. As proof‐of‐principle cases, EASI(?)‐MS was applied to genuine samples of olive oil, hazelnut oil, soybean oil, grape seed oil, canola oil, butter, and lard. Characteristic metabolomics EASI(?)‐MS profiles of fatty acids and eventually phenols were obtained.     

Asymmetric bihomologous crosslinkers for bicomponent gels—The way to strongly increased elastic moduli

2‐Hydroxyethylmethacrylate (HEMA) and acrylamide (AA) have been copolymerized via free radical mechanism, in the presence of 5 mol % of four different crosslinker systems, the symmetric ethylenglycoldimethacrylate (EGDMA), bisacrylamide (BIS), a mixture of EGDMA and BIS, and the asymmetric acrylamideethylenmethacrylate (METAA). The polymerizations have been monitored with a rheometer, exhibiting the gel obtained with the asymmetric METAA, an elastic modulus that is dramatically increased compared with those of the gels prepared with the other three crosslinker systems. A kinetic analysis using the terminal model has been used to build probabilistic surfaces that give information about how the crosslinker is incorporated into the network. This analysis shows a high dissimilarity between the reactions using the asymmetric and the mixture of symmetric crosslinkers, what has been correlated to the difference in modulus. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Characterization of Apo-Form Selective Inhibition of Indoleamine 2,3-Dioxygenase**

Indoleamine-2,3-dioxygenase 1 (IDO1) is a heme-containing enzyme that catalyzes the rate-limiting step in the kynurenine pathway of tryptophan (TRP) metabolism. As it is an inflammation-induced immunoregulatory enzyme, pharmacological inhibition of IDO1 activity is currently being pursued as a potential therapeutic tool for the treatment of cancer and other disease states. As such, a detailed understanding of the mechanism of action of IDO1 inhibitors with various mechanisms of inhibition is of great interest. Comparison of an apo-form-binding IDO1 inhibitor (GSK5628) to the heme-coordinating compound, epacadostat (Incyte), allows us to explore the details of the apo-binding inhibition of IDO1. Herein, we demonstrate that GSK5628 inhibits IDO1 by competing with heme for binding to a heme-free conformation of the enzyme (apo-IDO1), whereas epacadostat coordinates its binding with the iron atom of the IDO1 heme cofactor. Comparison of these two compounds in cellular systems reveals a long-lasting inhibitory effect of GSK5628, previously undescribed for other known IDO1 inhibitors. Detailed characterization of this apo-binding mechanism for IDO1 inhibition might help design superior inhibitors or could confer a unique competitive advantage over other IDO1 inhibitors vis-à-vis specificity and pharmacokinetic parameters.     

Bi-layer gelatin active films with “Pitanga” leaf hydroethanolic extract and/or natamycin in the second layer

Research on biopolymers-based active films produced with natural antioxidants and/or antimicrobials has gained attention over the last few years; however, anti-mold activity has been less studied than those of anti-bacteria. The aim of this work was the development and characterization of bi-layer films based on gelatin with natamycin and/or “Pitanga” leaf hydroethanolic extract in the second thin layer in order to determine the effects of these bioactive compounds on bi-layered film properties. The films were characterized regarding their moisture content and solubility in water, optical properties, microstructure, mechanical and thermal properties, water contact angle, water vapor permeability, UV/visible light transmission, X-ray diffraction, Fourier transform infrared (FTIR) spectroscopy, and antioxidant and anti-mold activities. Active films presented activity against Penicillium spp and Aspergillus niger and demonstrated antioxidant activity, as measured by ABTS ^•+ and DPPH ^• methods. Neither additive used in the films' second layer significantly affected the films' moisture content, thermal properties or the molecular interactions of the polymer matrix, assessed by FTIR, although some mechanical properties were affected, and the water contact angle. In conclusion, bi-layer films have reduced the quantity of additives required to maintain the antioxidant and anti-mold activities, as compared to similar monolayer films of the same thickness.     

Excited States of Bromopyrimidines Probed by VUV Photoabsorption Spectroscopy and Theoretical Calculations

We report absolute photoabsorption cross sections for gas-phase 2- and 5-bromopyrimidine in the 3.7–10.8 eV energy range, in a joint theoretical and experimental study. The measurements were carried out using high-resolution vacuum ultraviolet synchrotron radiation, with quantum chemical calculations performed through the nuclear ensemble approach in combination with time-dependent density functional theory, along with additional Franck–Condon Herzberg–Teller calculations for the first absorption band (3.7–4.6 eV). The cross sections of both bromopyrimidines are very similar below 7.3 eV, deviating more substantially from each other at higher energies. In the 7.3–9.0 eV range where the maximum cross-section is found, a single and broad band is observed for 5-bromopyrimidine, while more discernible features appear in the case of 2-bromopyrimidine. Several π* ← π transitions account for the most intense bands, while weaker ones are assigned to transitions involving the nitrogen and bromine lone pairs, the antibonding σ*_Br orbital, and the lower-lying Rydberg states. A detailed comparison with the available photo-absorption data of bromobenzene is also reported. We have found significant differences regarding the main absorption band, which is more peaked in bromobenzene, becoming broader and shifting to higher energies in both bromopyrimidines. In addition, there is a significant suppression of vibrational structures and of Rydberg states in the pair of isomers, most noticeably for 2-bromopyrimidine.     

Water Resources Assessment at Piracicaba,Capivari and Jundiaí River Basins: A Dynamic Systems Approach

The Piracicaba, Capivari, and Jundiaí River Basins (RB-PCJ) are mainly located in the State of São Paulo, Brazil. Using a dynamics systems simulation model (WRM-PCJ) to assess water resources sustainability, five 50-year simulations were run. WRM-PCJ was developed as a tool to aid decision and policy makers on the RB-PCJ Watershed Committee. The model has 254 variables. The model was calibrated and validated using available information from the 80s. Falkenmark Water Stress Index went from 1,403 m³ person^???1 year^???1 in 2004 to 734 m³ P^???1 year^???1 in 2054, and Xu Sustainability Index from 0.44 to 0.20. In 2004, the Keller River Basin Development Phase was Conservation, and by 2054 was Augmentation. The three criteria used to evaluate water resources showed that the watershed is at crucial water resources management turning point. The WRM-PCJ performed well, and it proved to be an excellent tool for decision and policy makers at RB-PCJ.     

Determination of avermectin and milbemycin residues in bovine muscle by liquid chromatography-tandem mass spectrometry and fluorescence detection using solvent extraction and low temperature cleanup

A simple and inexpensive sample preparation method based on solvent extraction, followed by low temperature cleanup, was demonstrated to be applicable for the determination of avermectin and milbemycin residues in bovine muscle by liquid chromatography-tandem mass spectrometry (LC-MS/MS) and liquid chromatography with fluorescence (LC-FL) detection. The analytical methodology was validated according to the Commission Decision 2002/657/EC, using LC-MS/MS for confirmatory and LC-FL for quantitative purposes. Mean recovery was between 88.9 and 100.7% in three distinct concentrations. The coefficient of variation for repeatability and within-laboratory reproducibility ranged from 0.78 to 5.1% and from 0.28 to 9.0%, respectively. Method precision led to satisfactory values of decision limits (CCα) and detection capabilities (CCβ). The proposed method has been applied in the Brazilian National Residue Control Plan since 2010 for the determination of avermectins and milbemycin residues in bovine muscle samples. A total of 760 samples were analyzed and none of them presented residues at concentrations above the permitted levels established by the more recently applied directives.     

Mapping woody-biomass supply costs using forest inventory and competing industry data

The goals of energy independence and sustainability have motivated many countries to consider biomass-based energy sources. The United States has substantial and increasing forest resources that could be used to produce both electricity and liquid fuel. However, these forest resources are highly heterogeneous in terms of the wood’s properties, the logging cost, the spatial distribution, and the value to other industries. These factors make predicting costs and selecting plant locations particularly challenging. When dealing with forest biomass, feedstock cost and location have frequently been highly simplified in previous studies. This paper presents a methodology for combining highly resolved forest inventory and price data with records of competing industries to develop detailed maps of feedstock availability. The feedstock sourcing strategy of the proposed bioenergy plants is modeled by a cost-minimizing linear program, as is the feedstock selection of the competing mills. A case study is performed on the southeast United States.     

Screening,optimization and kinetics of Jatropha curcas oil transesterification with heterogeneous catalysts

This work investigates the production of fatty acid methyl esters (FAME) from Jatropha curcas oil using a variety of heterogeneous catalysts: resins, zeolites, clays, hydrotalcites, aluminas and niobium oxide. For this purpose, a catalyst screening was first conducted in a batch reactor at the following operating conditions: oil to methanol molar ratio of 1:9, 6 h of reaction, 5 wt% catalyst, at 333 and 393 K. From the screening step, KSF clay and Amberlyst 15 catalysts were selected to carry out a 2³ full factorial central composite rotatable design so as to elucidate the effects of process variables on FAME yield. The optimum reaction conditions for both catalysts were found to be oil to methanol molar ratio of 1:12, 5 wt% of catalyst, 433 K and 6 h of reaction with a FAME yield of about 70 wt%. A kinetic study was then experimentally performed and a semi-empirical model was built to represent the experimental data. Finally, catalyst re-utilization in five successive batch experiments was evaluated at the optimized conditions.     

A Weibull model to describe antimicrobial kinetics of oregano and lemongrass essential oils against Salmonella Enteritidis in ground beef during refrigerated storage

The antimicrobial effect of oregano (Origanum vulgare L.) and lemongrass (Cymbopogon citratus (DC.) Stapf.) essential oils (EOs) against Salmonella enterica serotype Enteritidis in in vitro experiments, and inoculated in ground bovine meat during refrigerated storage (4 ± 2 °C) for 6 days was evaluated. The Weibull model was tested to fit survival/inactivation bacterial curves (estimating of p and δ parameters). The minimum inhibitory concentration (MIC) value for both EOs on S. Enteritidis was 3.90 μl/ml. The EO concentrations applied in the ground beef were 3.90, 7.80 and 15.60 μl/g, based on MIC levels and possible activity reduction by food constituents. Both evaluated EOs in all tested levels, showed antimicrobial effects, with microbial populations reducing (p ≤ 0.05) along time storage. Evaluating fit-quality parameters (RSS and RSE) Weibull models are able to describe the inactivation curves of EOs against S. Enteritidis. The application of EOs in processed meats can be used to control pathogens during refrigerated shelf-life.