Evaluation of tea tree oil quality and ascaridole: A deep study by means of chiral and multi heart-cuts multidimensional gas chromatography system coupled to mass spectrometry detection

The natural-like assessment of essential oils is a demanding task due to the growing trend toward adulterations. Usually chiral chromatography was used for this purpose due to the capability of assessing stereospecificity which is directly related to the enzymatic pathways of each plant species. On the other hand, the quality of an essential oil involves also the evaluation of its oxidative state, mainly connected with the age and storage conditions. In fact, some modifications in the chemical profile of the oil can occur if not properly preserved. Alterations of the components due to oxidative reactions lead to the formation of peroxides, endoperoxides and epoxides, such as ascaridole and 1,2,4-trihydroxymenthane, usually present in very low amount, formed by the oxidation of terpinen-4-ol and α-terpinene, respectively. Therefore, in the present research, the quality of Australian Tea Tree oil (Melaleuca alternifolia (Maiden & Betche) Cheel, Myrtaceae) was investigated by means of a multi heart-cut multidimensional gas chromatographic system coupled to a mass spectrometer detector and by conventional enantio-GC. The MDGC system allowed the complete separation of the compounds of interest transferred from the first column to a second dimension based on a different separation mechanism. The MS detector at the end of the second column provided the identification of the peaks with high similarity values because of their high purities after the multidimensional separation. Method validation was carried out, in order to use this procedure for routine application, monitoring the repeatability of 1D retention times and 2D peak areas, LoD and LoQ. Finally, enantiomeric ratios for chiral compounds were established to support quality data obtained.     

Screening Brazilian commercial gasoline quality by hydrogen nuclear magnetic resonance spectroscopic fingerprintings and pattern-recognition multivariate chemometric analysis

The identification of gasoline adulteration by organic solvents is not an easy task, because compounds that constitute the solvents are already in gasoline composition. In this work, the combination of Hydrogen Nuclear Magnetic Resonance (¹H NMR) spectroscopic fingerprintings with pattern-recognition multivariate Soft Independent Modeling of Class Analogy (SIMCA) chemometric analysis provides an original and alternative approach to screening Brazilian commercial gasoline quality in a Monitoring Program for Quality Control of Automotive Fuels. SIMCA was performed on spectroscopic fingerprints to classify the quality of representative commercial gasoline samples selected by Hierarchical Cluster Analysis (HCA) and collected over a 6-month period from different gas stations in the São Paulo state, Brazil. Following optimized the ¹H NMR-SIMCA algorithm, it was possible to correctly classify 92.0% of commercial gasoline samples, which is considered acceptable. The chemometric method is recommended for routine applications in Quality-Control Monitoring Programs, since its measurements are fast and can be easily automated. Also, police laboratories could employ this method for rapid screening analysis to discourage adulteration practices.     

Essential oil composition of leaves of Stachys yemenensis obtained by supercritical CO₂

This article reports the composition of the essential oil from the leaves of Stachys yemenensis. The essential oil was extracted by supercritical CO? (90 bar; 40 °C) and its chemical composition was determined by gas chromatography and gas chromatography-mass spectrometry. The major components of the sample were α-phellandrene (13.9%), β-phellandrene (11.7%), elemol (12.0%), spathulenol (6.7%), β-eudesmol (5.0%), α-eudesmol (4.75%) and squalene (4.8%). On the exhausted matrix, deprived of the volatiles, we carried out a high-pressure (250 bar) treatment for the extraction of squalene (49.7%). The antimicrobial activity of the essential oils has been assayed by using the broth dilution method on two American Type Culture Collection (ATCC) strains, Escherichia coli ATCC 35218 and Staphylococcus aureus ATCC 43300, and two clinical strains, Candida albicans and Candida glabrata.     

Quantum Chemical Investigation of Secondary Reactions in Poly(vinyl chloride) Free‐Radical Polymerization

Free‐radical polymerization of vinyl chloride is investigated computationally with special attention to the secondary reactions involving mid‐chain radicals (MCRs). Namely, the rate constants of backbiting, chain scission, chain transfer, and propagation reactions are evaluated using a density functional theory method. The rate coefficients of such reactions are estimated taking into account the position of the radical along the chain as well as its distance from the chain‐end. In particular 1:5, 5:1, and 5:9 backbiting are the most relevant secondary reactions, followed by the slower propagation of MCRs. Finally, a kinetic model of suspension polymerization including the investigated reactions is developed, in order to determine their impact on the quality of the final polymer.

     

Structural and vibrational characterization of medieval like glass samples

Within the framework of a project aimed to develop protective coatings for antique glass windows, three glass varieties of medieval-like composition were prepared using recipes deduced from archaeometric studies and different amounts of potassium for fluxing (15–20–25 K₂O wt.%). Batches were melted in mullite crucibles using an electric furnace at 1350 °C, the glass was fast cooled in air and annealed at temperatures 20 °C higher than the sample glass transition temperatures (726, 702 and 683 °C for V1, V2 and V3, respectively). The chemical composition of the glass was determined by X-Ray Fluorescence Spectroscopy (XRF) and the glass transition temperature was checked by differential thermal analysis (DTA). X-Ray Powder Diffraction (XRPD) data and vibrational spectroscopic experiments (FT-IR and Raman) revealed a direct dependence of glass de-polymerization on potassium content. In particular, the Raman data were interpreted on the basis of SiO₄ structural units Qⁿ and the polymerization index I_p.     

Thin Notched Beams

The three-dimensional elasticity energy for a notched rod under axial loads is shown to converge in a variational sense to a class of one-dimensional models with a localized compliance when the beam becomes very slender and when the ratio between the depth and the width of each notch vanishes in a suitable way. Also the case of notched thermal conductors is considered, in a parallel treatment, because it falls in a similar but simpler framework.     

The delay vector variance method for detecting determinism and nonlinearity in time series

A novel ‘delay vector variance’ (DVV) method for detecting the presence of determinism and nonlinearity in a time series is introduced. The method is based upon the examination of local predictability of a signal. Additionally, it spans the complete range of local linear models due to the standardisation to the distribution of pairwise distances between delay vectors. This provides consistent and easy-to-interpret diagrams, which convey information about the nature of a time series. In order to gain further insight into the technique, a DVV scatter diagram is introduced, which plots the DVV curve against that for a globally linear model (surrogate data). This way, the deviation from the bisector line represents a qualitative measure of nonlinearity, which can be used additionally for constructing a quantitative measure for statistical testing. The proposed method is compared to existing methods on synthetic, as well as standard real-world signals, and is shown to provide more consistent results overall, compared to other, established nonlinearity analysis methods.     

Digital image processing algorithms for diagnosis in arterial diseases

Computed Tomography images (C.T.) are currently part of the routine procedure in medical diagnostic techniques and can be used for the evaluation of occlusion rate of arterial vessels in presence of many diseases. The correct individuation of the morphology of these arterial anomalies allows specialists to diagnose the risk rate for the health of patients and to decide for surgical stent implants. Multivariate sampling Kantorovich operators are suitable for studying not necessarily continuos signals/images as the ones involved in the medical field. Convergent results for such a family of discrete operators translate into reconstruction and even enhancement of a given signal/image increasing the sampling rate. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

A comparison between ab initio calculated and measured Raman spectrum of triclinic albite (NaAlSi3O8)

Albite is one of the most common minerals in the Earth's crust, and its polymorphs can be found in rocks with different cooling histories. The characteristic spectrum of vibration of the albite mineral reflects its structural Si/Al ordering. In this study, we report on the comparison between the Raman spectra measured on a natural and fully ordered (as deduced on the basis of single‐crystal X‐ray diffraction data) ‘low albite’, NaAlSi₃O₈, and those calculated at the hybrid Hartree–Fock/density functional theory level by employing the WC1LYP Hamiltonian, which has proven to give excellent agreement between calculated and experimentally measured vibrational wavenumbers in silicate minerals. All the 39 expected A_g modes are identified in the Raman spectra, and their wavenumbers and intensities, in different scattering configurations, correspond well to the calculated ones. The average absolute discrepancy is ~3.4 cm⁻¹, being the maximum discrepancy |Δv|_max ~ 10.3 cm⁻¹. The very good quality of the WC1LYP results allows for reliable assignments of the Raman features to specific patterns of atomic vibrational motion. Copyright © 2015 John Wiley & Sons, Ltd.