Combining bar adsorptive microextraction with capillary electrophoresis—Application for the determination of phenolic acids in food matrices

In this contribution, bar adsorptive microextraction coated with a mixed‐mode anion exchange/RP followed by liquid desorption was combined for the first time with a capillary electrophoresis‐diode array detection system (BAμE(MAX)‐LD/CE‐DAD), for the determination of phenolic acids in food matrices, using chlorogenic, ferulic, cumaric, and caffeic acids as model compounds. Assays performed in aqueous media spiked at the 0.8 mg/L level yielded average recoveries up to 40% for all four phenolic acids, under optimized experimental conditions. The analytical performance showed also good precision (RSD < 15%), convenient LODs (18.0–85.0 μg/L) and linear dynamic ranges (0.8–8.0 mg/L) with convenient determination coefficients (r² > 0.9900). By using the standard addition method, the application to food matrices such as green tea, red fruit juice, and honey allowed very good performances for the determination of minor amounts of phenolic acids. The proposed methodology proved to be a suitable alternative for the analysis of polar to ionic compounds, showing to be easy to implement, reliable, sensitive, and requiring a low sample volume to determine phenolic acids in food samples.     

Integrated Use of Residues from Olive Mill and Winery for Lipase Production by Solid State Fermentation with Aspergillus sp.

Two-phase olive mill waste (TPOMW) is presently the major waste produced by the olive mill industry. This waste has potential to be used as substrate for solid state fermentation (SSF) despite of its high concentration of phenolic compounds and low nitrogen content. In this work, it is demonstrated that mixtures of TPOMW with winery wastes support the production of lipase by Aspergillus spp. By agar plate screening, Aspergillus niger MUM 03.58, Aspergillus ibericus MUM 03.49, and Aspergillus uvarum MUM 08.01 were chosen for lipase production by SSF. Plackett–Burman experimental design was employed to evaluate the effect of substrate composition and time on lipase production. The highest amounts of lipase were produced by A. ibericus on a mixture of TPOMW, urea, and exhausted grape mark (EGM). Urea was found to be the most influent factor for the lipase production. Further optimization of lipase production by A. ibericus using a full factorial design (3²) conducted to optimal conditions of substrate composition (0.073 g urea/g and 25 % of EGM) achieve 18.67 U/g of lipolytic activity.     

99mTc-labeled bombesin analog for breast cancer identification

Bombesin is a tetradecapeptide that binds specifically to gastrin releasing peptide receptors in humans. Several forms of cancer, including lung, prostate, breast, and colon express receptors for bombesin-like peptides. Radiolabeled bombesin analogs with a high affinity for these receptors might therefore be used for scintigraphic imaging of these tumor types. A truncated bombesin derivative (HYNIC-βAla-Bombesin_(7–14)) was radiolabeled with technetium-99m using EDDA and tricine as coligands. In vitro stability was evaluated in presence of plasma and excess of cysteine. The receptor-binding affinity assays was evaluated in MDA-MB-231 cancer cell line. In addition, in vivo biodistribution was performed in nude mice bearing breast tumor. In vitro assay showed a good affinity for the MDA-MB-231 cell line, showing 20.0 % of internalization at 4 h post-administration. ^99mTc-HYNIC-βAla-Bombesin_(7–14) biodistribution revealed a rapid clearance and a significant renal excretion. In addition, tumor uptake was higher than non-excretory organs, such as the spleen, the liver, and muscles. Tumor-to-muscle and tumor-to-blood ratios for ^99mTc-HYNIC-βAla-Bombesin_(7–14) showed high values at 4 h post-injection (5.34 and 4.55, respectively). Furthermore, blocked studies using cold bombesin peptide were performed, which demonstrated an important decrease in tumor uptake, indicating a tumor specificity for ^99mTc-HYNIC-βAla-Bombesin_(7–14). The ^99mTc-HYNIC-βAla-Bombesin_(7–14) displayed suitable radiochemical characteristics, and adequate affinity to breast tumor cells (MDA-MB-231). Therefore, this analog can be considered as a candidate for the identification of bombesin-positive tumors.     

Experimental and theoretical studies on glucose hydrogenation to produce sorbitol

Quantum chemical calculations were performed to obtain information on the molecular properties of relevant species involved in catalytic glucose hydrogenation for the production of sorbitol.     

The mixed Hodge–Riemann bilinear relations for compact Kähler manifolds

We prove the Hodge–Riemann bilinear relations, the hard Lefschetz theorem and the Lefschetz decomposition for compact K?hler manifolds in the mixed situation. Dedicated to Professor Henri Skoda on the occasion of his 60th birthday Received: February 2005; Revision: March 2005; Accepted: April 2005     

Kinetic study of the thermal decomposition of TEA<Superscript>+</Superscript>/SAPO-5

A silico alumino phosphate with AFI structure (SAPO-5) was prepared in a two-phase medium and characterized by XRD, followed by the addition of TEA⁺. The kinetics of the TEA⁺/SAPO-5 thermal decomposition reaction was studied by isothermal and dynamic thermogravimetry. Two kinetic models, D₃ and D₄ based on diffusion processes were found as best to fit the isothermal data. On the other hand, the best fit for the dynamic data is the F₁ first order reaction model. According to the apparent activation energy values, the use of the dynamic method indicates a higher temperature dependence than the isothermal method.     

Analysing the isotopic life history of the alpine ungulates Capra ibex and Rupicapra rupicapra rupicapra through their horns

The horn of ungulate grazers offers a valuable isotopic record of their diet and environment. However, there have been no reports of the spatio‐temporal variation of the isotopic composition of horns. We investigated patterns of carbon (δ¹³C) and nitrogen (δ¹⁵N) isotopic composition along and perpendicular to the horn axis in Capra ibex and Rupicapra rupicapra rupicapra to assess the effects of animal age, within‐year (seasonal) and inter‐annual variation, natural contamination and sampling position on horn isotope composition. Horns of male C. ibex (n = 23) and R. r. rupicapra (n = 1) were sampled longitudinally on the front (only R. r. rupicapra) and back side and on the surface and sub‐surface. The sides of the R. r. rupicapra horn did not differ in δ¹³C. In both species, the horn surface had a 0.15‰ lower δ¹³C and a higher carbon‐to‐nitrogen (C/N) ratio than the sub‐surface. Washing the horn with water and organic solvents removed material that caused these differences. With age, the δ¹⁵N of C. ibex horns increased (+0.1‰ year^?1), C/N ratio increased, and ¹³C discrimination relative to atmospheric CO₂ (¹³Δ) increased slightly (+0.03‰ year^?1). Geostatistical analysis of one C. ibex horn revealed systematic patterns of inter‐annual and seasonal ¹³C changes, but ¹⁵N changed only seasonally. The work demonstrates that isotopic signals in horns are influenced by natural contamination (δ¹³C), age effects (¹³Δ and δ¹⁵N), and seasonal (δ¹³C and δ¹⁵N) and inter‐annual variation (δ¹³C). The methods presented allow us to distinguish between these effects and thus allow the use of horns as isotopic archives of the ecology of these species and their habitat. Copyright © 2009 John Wiley & Sons, Ltd.     

The analysis of alkyl-capped alcohol ethoxylates and alcohol ethoxycarboxylates from alcohol ethoxylates by atmospheric pressure chemical ionization mass spectrometry

Alcohol ethoxylates (AEs) are nonionic surfactants. They are industrially important compounds that have historically been difficult to analyze, with the best results to date achieved through derivatization (e.g., silylation) followed by analysis by gas chromatography/mass spectrometry (GC/MS). Recently, mass spectrometric techniques such as field desorption (FD), time-of-flight secondary ion mass spectrometry (TOF-SIMS), fast atom bombardment (FAB), electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI) have been employed to analyze surfynol(R) 4xx. In an effort to produce low-cost alkyl-capped AEs and anionic detergents from AEs, a fast and reliable measure of the product yields and conversions from AEs is required in research. We found that the product yields and conversions from reactions of AEs, obtained by the employment of atmospheric pressure chemical ionization (APCI), were in good agreement with those obtained from proton nuclear magnetic resonance spectroscopy ((1)H-NMR). Therefore, APCI can be used as a validated tool for studying AE reactions. Mixtures that contain either silylated or unsilylated ethoxylates and/or carboxylates yield the same APCI mass spectra. Copyright -Copyright 1999 John Wiley & Sons, Ltd.