Development and Validation of QuEChERS Followed by UHPLC-ToF-MS Method for Determination of Multi-Mycotoxins in Pistachio Nuts

Pistachios are one of the types of tree nut fruits with the highest mycotoxin contamination, especially of aflatoxins, worldwide. This study developed a Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) method that was followed by Ultra-High Performance Liquid Chromatography combined with Time-of-Flight Mass Spectrometry (UHPLC–ToF-MS) for the determination of mycotoxins in pistachios. Different approaches to dispersive solid phase extraction as a clean-up method for high lipid matrices were evaluated. For this, classic sorbents such as C18 (octadecyl-modified silica) and PSA (primary secondary amine), and new classes of sorbents, namely EMR-Lipid (enhanced matrix removal-lipid) and Z-Sep (modified silica gel with zirconium oxide), were used. The QuEChERS method, followed by Z-Sep d-SPE clean-up, provided the best analytical performance for aflatoxins (AFB1, AFB2, AFG1 and AFG2), ochratoxin A (OTA), zearalenone (ZEA), toxin T2 (T2) and toxin HT-2 (HT2) in pistachios. The method was validated in terms of linearity, sensitivity, repeatability, interday precision and recovery; it achieved good results according to criteria imposed by Commission Regulation (EC) no. 401/2006. The method was applied to real samples and the results show that pistachios that are available in Portuguese markets are safe from mycotoxins that are of concern to human health.     

Thermal Stability of Biodegradable Films Based on Soy Protein and Corn Starch

Summary: In this paper, films were prepared from soy protein and corn starch in different proportions and thermal stability and kinetic parameters were determined through degradation reactions in an inert atmosphere. Solid residues and decomposition products were identified by infrared spectroscopy. Films from corn starch were less thermally stable than soy protein films. The films containing both components had lower thermal stabilities when compared to those of the pure biopolymers. The mechanism of starch thermal degradation seems to occur in a single step, which can be confirmed by the constant E-values during the thermal degradation reaction. For the pure protein and its mixtures an increase in the activation energy was observed during the reaction. Solid residues for protein at different temperatures showed mainly bands related to CO stretching, angular deformation of N H and C H groups. For starch, absorptions related to free and bound O H, CO stretching of CO₂, CO and carbonyl compounds were observed. For the 50/50 mixture bands related to soy protein and corn starch were observed. The gaseous products for soy protein showed absorptions related to CO₂, CO, CO, NH₃ and C H stretching. For pure starch absorptions related to O H stretching from alcohol, CO from CO₂, CO and carbonyl compounds. The 50/50 mixture had the same characteristics as pure soy protein and corn starch.     

FTIR Spectroscopy as a Tool to Study Age-Related Changes in Cardiac and Skeletal Muscle of Female C57BL/6J Mice

Studying aging is important to further understand the molecular mechanisms underlying this physiological process and, ideally, to identify a panel of aging biomarkers. Animals, in particular mice, are often used in aging studies, since they mimic important features of human aging, age quickly, and are easy to manipulate. The present work describes the use of Fourier Transform Infrared (FTIR) spectroscopy to identify an age-related spectroscopic profile of the cardiac and skeletal muscle tissues of C57BL/6J female mice. We acquired ATR-FTIR spectra of cardiac and skeletal muscle at four different ages: 6; 12; 17 and 24 months (10 samples at each age) and analyzed the data using multivariate statistical tools (PCA and PLS) and peak intensity analyses. The results suggest deep changes in protein secondary structure in 24-month-old mice compared to both tissues in 6-month-old mice. Oligomeric structures decreased with age in both tissues, while intermolecular β-sheet structures increased with aging in cardiac muscle but not in skeletal muscle. Despite FTIR spectroscopy being unable to identify the proteins responsible for these conformational changes, this study gives insights into the potential of FTIR to monitor the aging process and identify an age-specific spectroscopic signature.     

Evolution of Molecular Weight and Long Chain Branch Distributions in Olefin–Diene Copolymerization

A model for olefin–diene copolymerization and long chain branch formation was developed. The model shows that the number‐average molecular weight and branching density increases linearly with time in a semi‐batch polymerization, while the polydispersity depends on the diene content in the polymer and on the polymerization time. For low diene fractions or low polymerization times, the polydispersity increases linearly with time. For higher diene contents, the polydispersity increases exponentially with polymerization time after a critical polymer concentration is reached. The calculated distributions of branched species indicate that diene content influences the amount of highly branched chains produced in the polymerization, markedly broadening the distribution of molecular weight and leading to gel formation.

Weight distribution of branched species after 30 min of polymerization.     

Synthesis of tailor‐made polyethylene through the control of polymerization conditions using selectively combined metallocene catalysts in a supported system

Tailoring of the molecular weight distribution (MWD) in ethylene polymerization was attempted by selectively combining different types of metallocene catalysts onto a single support. The catalyst produced by supporting Et[Ind]₂ZrCl₂ and Cp₂HfCl₂ onto a single MAO pretreated silica support was able to produce polymers with unimodal or bimodal MWD's. This approach permits the synthesis of polyethylene with different MWD's using the same catalyst as a function of the polymerization conditions. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 331–339, 1999     

Spin-glass energy landscape

We consider a nearest-neighbor-interaction ±J Ising spin glass in a square lattice. Inspired by natural evolution, we design a dynamic rule that includesselection, randomness, andmultibranch exploration. Following this rule, we succeed in walking along the space of states between local energy maxima and minima alternately. During the walk, we store various information about the spin states corresponding to these minima and maxima for later statistical analysis. In particular, we plot a histogram displaying how many times each minimum (or maximum) energy is visited as a function of the corresponding density value. Through finite-size scaling analysis, we conclude that a nonvanishing fraction of bonds remains unsatisfied (satisfied) at these energy minimum (maximum) states in the thermodynamic limit. This fraction measures the degree of unavoidable frustration of the system. Also in this limit, the width of these histograms vanishes, meaning that almost all metastable states occur at the same energy density value, with no dispersion.     

Simultaneous Determination of Nickel and Cobalt Using a Solid Bismuth Vibrating Electrode by Adsorptive Cathodic Stripping Voltammetry

A simple, fast, sensitive and greener voltammetric procedure for simultaneous analysis of nickel (Ni) and cobalt (Co) by square wave adsorptive cathodic stripping voltammetry (SW‐AdCSV) using a solid bismuth vibrating electrode is presented for the first time. The procedure enables to determine Ni together with Co, in ammonia buffer 0.1 M (pH 9.2) and in the presence of oxygen, and involves an adsorptive accumulation of metal‐dimethylglyoxime (Ni‐DMG and Co‐DMG) complexes on the electrode surface. For Ni and Co, the detection limits, obtained with 30 s of accumulation time, were 0.6 and 1.0 µg L^?1, respectively. The method was free of metals (Cd²⁺, Cr³⁺, Cr⁶⁺, Cu²⁺, Fe³⁺ and Pb²⁺ up to 50 µg L^?1, Al³⁺ and Mn²⁺ up to 500 µg L^?1; Zn²⁺ up to 300 µg L^?1) interferences up to the concentrations mentioned in brackets. The proposed method was validated for simultaneous determination of Ni and Co in a certified reference surface and river waters with good results.     

Effect of the pore geometry in the characterization of the pore size distribution of activated carbons

In this work, the characterization of Activated Carbons (AC) by using the independent pore models is discussed, with special emphasis on the issue of how the assumed pore geometry can affect the resulting Pore Size Distribution (rPSD) and on the problem of the unicity of the PSD when different probe molecules are used in adsorption experiments. A theoretical test was performed using virtual solids based in the so-called Mixed Geometry Model (MGM) (Azevedo et al. 2010). The MGM uses a kernel of adsorption isotherms generated by GCMC for different pore sizes and two pore geometries: slit and triangular. The adsorption isotherms of a virtual MGM solid were fitted with both the traditional Slit Geometry Model (SGM) and the Mixed Geometry Model (MGM). It is demonstrated that, by assuming a different pore geometry model from that of the real sample, different PSDs may be obtained by fitting adsorption isotherms of different probe gases. Finally, experimental results are shown which both point toward the MGM as an acceptable extension of the SGM and confirm that the MGM is a closer representation of the actual porous structure of most activated carbons.     

Metal‐Free Synthesis of Functional 1‐Substituted‐1,2,3‐Triazoles from Ethenesulfonyl Fluoride and Organic Azides

The boom in growth of 1,4‐disubstituted triazole products, in particular, since the early 2000’s, can be largely attributed to the birth of click chemistry and the discovery of the Cu^I‐catalyzed azide–alkyne cycloaddition (CuAAC). Yet the synthesis of relatively simple, albeit important, 1‐substituted‐1,2,3‐triazoles has been surprisingly more challenging. Reported here is a straightforward and scalable click‐inspired protocol for the synthesis of 1‐substituted‐1,2,3‐triazoles from organic azides and the bench stable acetylene surrogate ethenesulfonyl fluoride (ESF). The new transformation tolerates a wide selection of substrates and proceeds smoothly under metal‐free conditions to give the products in excellent yield. Under controlled acidic conditions, the 1‐substituted‐1,2,3‐triazole products undergo a Michael addition reaction with a second equivalent of ESF to give the unprecedented 1‐substituted triazolium sulfonyl fluoride salts.