Quantitative determination of sotolon, maltol and free furaneol in wine by solid-phase extraction and gas chromatography-ion-trap mass spectrometry

A method for the analytical determination of sotolon [4,5-dimethyl-3-hydroxy-2(5H)-furanone], maltol [3-hydroxy-2-methyl-4H-pyran-4-one] and free furaneol [2,5-dimethyl-4-hydroxy-3(2H)-furanone] in wine has been developed. The analytes are extracted from 50 ml of wine in a solid-phase extraction cartridge filled with 800 mg of LiChrolut EN resins. Interferences are removed with 15 ml of a pentane-dichloromethane (20:1) solution, and analytes are recovered with 6 ml of dichloromethane. The extract is concentrated up to 0.1 ml and analyzed by GC-ion trap MS. Maltol and sotolon were determined by selected ion storage of ions in the m/z ranges 120-153 and 79-95, using the ions m/z 126 and 83 for quantitation, respectively. Furaneol was determined by non-resonant fragmentation of the m/z 128 mother ion and subsequent analysis of the m/z 81 ion. The detection limits of the method are in all cases between 0.5 and 1 microg l(-1), well below the olfactory thresholds of the compounds. The precision of the method is in the 4-5% range for levels in wine around 20 microg l(-1). Linearity holds at least up to 400 microg l(-1), and is satisfactory in all cases. The recoveries of maltol and sotolon are constant (70 and 64%, respectively) and do not depend on the type of wine. On the contrary, in the case of furaneol, red wines show constant and high recoveries (97%), while the recoveries on white wines range between 30 and 80%. Different experiments showed that this behavior is probably due to the existence of complexes formed between furaneol and sulphur dioxide or catechols. Sensory experiments confirmed that the complexed forms found in white wines are not perceived by orthonasal olfaction, and that the furaneol determined by the method can be considered as the free and odor-active fraction.     

Application of SSA thermal fractionation and X‐ray diffraction to elucidate comonomer inclusion or exclusion from the crystalline phases in poly(butylene succinate‐ran‐butylene azelate) random copolymers

Poly(butylene succinate‐ran‐butylene azelate) random copolyesters were thermally fractionated by successive self‐nucleation and annealing (SSA). The samples before and after SSA were analyzed by differential scanning calorimetry (DSC) and X‐ray diffraction (WAXS and SAXS). WAXS results indicate that a small degree of comonomer inclusion is present in the crystalline phases that are formed in the copolymers depending on composition: a PBS‐like unit cell or/and a PBAz‐like unit cell, thus confirming the isodimorphic behavior of the samples. SSA on the other hand demonstrated that the degree of comonomer exclusion during crystallization is far larger than comonomer inclusion, as judged by the increase in fractionation degree with compositions leading to the pseudo‐eutectic point. Furthermore, WAXS, SAXS, and SSA results show that the isodimorphic behavior is not highly dependent on kinetic factors, as the degree of comonomer inclusion or exclusion in the samples was not significantly altered by SSA thermal fractionation, a thermal treatment that promotes annealing and molecular segregation of defects to the amorphous regions of the material. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2346–2358     

Parareal for index two differential algebraic equations

Numerical Algorithms - This article proposes modifications of the Parareal algorithm for its application to higher index differential algebraic equations (DAEs). It is based on the idea of applying...     

Determination of fuel dialkyl ethers and BTEX in water using headspace solid-phase microextraction and gas chromatography-flame ionization detection

A simple procedure for the determination of methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), ethyl butyl ether (EBE), tert-amyl methyl ether (TAME), benzene, toluene, ethylbenzene, and xylenes (BTEX) in water using headspace (HS) solid-phase microextraction (HS-SPME) was developed. The analysis was carried out by gas chromatography (GC) equipped with flame ionization detector (FID) and 100% dimethylpolysiloxane fused capillary column. A 2 Plackett-Burman design for screening and a central composite design (CCD) for optimizing the significant variables were applied. Fiber type, extraction temperature, sodium chloride concentration, and headspace volume were the significant variables. A 65 microm poly(dimethylsiloxane)-divinylbenzene (PDMS-DVB) SPME fiber, 10 degrees C, 300 g/l, and 20 ml of headspace (in 40 ml vial) were respectively chosen for the best extraction response. An extraction time of 10 min was enough to extract the ethers and BTEX. The relative standard deviation (R.S.D.) for the procedure varied from 2.6 (benzene) to 8.5% (ethylbenzene). The method detection limits (MDLs) found were from 0.02 (toluene, ethylbenzene, and xylenes) to 1.1 microg/l (MTBE). The optimized method was applied to the analysis of the rivers, marinas and fishing harbors surface waters from Gipuzkoa (North Spain). Three sampling were done in 1 year from June 2002 to June 2003. Toluene was the most detected analyte (in 90% of the samples analyzed), with an average concentration of 0.56 microg/l. MTBE was the only dialkyl ether detected (in 15% of the samples) showing two high levels over 400 microg/l that were related to accidental fuel spill.     

Aza-Michael reaction with enone-modified vegetable oils: evidence of the keto–enolic equilibrium by NIR chemical imaging and evolving factor analysis

The existence of an enone–dienol tautomerism in enone-containing triglyceride, obtained from high oleic sunflower oil, was detected in an image set captured at 95 °C by fixed-size image window-evolving factor analysis. A ¹H NMR spectrum and a UV–Visible spectrum of the enone-containing triglyceride at 25 °C and at 95 °C were measured to corroborate the presence of the enol form. The presence of this equilibrium explains the different behaviour of the curing reaction between an enone-containing triglyceride and diaminodiphenylmethane, which was evaluated following the spectral evolution of two pixels that differ in the presence or absence of the enol form. As the enol form acts as a inert species in the reaction, it leads to different degree of advance depending on which growing zone is observed.     

Characterization of an X‐ray mirror mechanical bender for the European XFEL

One of the classical devices used to tune a mirror on an X‐ray optical setup is a mechanical bender. This is often designed in such a way that the mirror is held with clamps on both ends; a motor is then used to put a torque on the clamps, inducing a cylindrical shape of the mirror surface. A mechanical bender with this design was recently characterized, to bend a 950 mm‐long mirror up to a radius of curvature of 10 km. The characterization was performed using a large‐aperture Fizeau interferometer with an angled incidence setup. Some particular and critical effects were investigated, such as calibration, hysteresis, twisting and long‐term stability.     

High pressure phases of different tetraboranes

High pressure phases of boron hydrides B₄H₁₀, B₄H₈ and B₄H₆ and their stability against dissociation into H and smaller B–H units are reported. Structure predictions based on particle swarm optimization reveal that all the boron hydrides studied show a tendency to separate into smaller structural units at low pressure. Under high pressure, the three-dimensional network in all the stoichiometries selected seems to be the most favourable arrangement. A study of the dissociation of B₄H₁₀ reflects an affinity to dissociate into B₄H₈ and H₂ in all the studied pressure range. Nevertheless, B₄H₈ does not seem to segregate in the studied pressure range and B₄H₆ may dissociate at 150 GPa.     

Antibacterial and Antiproliferative Activities of Azadirachta indica Leaf Extract and Its Effect on Oil-in-Water Food Emulsion Stability

The present study aims to identify and quantify the phenolic compounds of Azadirachta indica leaf extract using HPLC-MS and to evaluate the antioxidant, antibacterial (against different Gram-positive and negative bacteria) and in vitro anti-proliferative activities of this extract (against breast, human liver and cervix adenocarcinoma-derived cells). The application of this extract as a natural antioxidant for food preservation was also tested on oil-in-water food emulsions for the first time in the present work in order to determine the use of Azadirachta indica leaves as a natural additive to preserve the food against lipid oxidation and rancidity. The results obtained revealed that 50%-aqueous ethanol leaf extract showed the best extraction yield (25.14%), which was characterized by a high content in phenolic compounds and strong antioxidant activity. Moreover, this leaf extract inhibited the growth of the bacterial strains tested (Staphylococcus aureus, Escherichia coli, Salmonella paratyphi and Micrococcus luteus) and showed better anti-proliferative activity against breast and cervix adenocarcinoma-derived cells than human liver cancer cells after 48 h of treatment. Additionally, Azadirachta indica leaf extract showed almost similar effects as gallic acid solutions (0.25% and 0.5%) in preserving the oxidation of oil-in-water food emulsions and prevented the formation of secondary oxidation products (malondialdehyde) as well. The results obtained suggested that extracts of Azadirachta indica leaves are a potential source of antioxidant and antibacterial compounds and pointed to the potential of these natural extracts as therapeutic agents.     

Phenolic Profile,EPR Determination,and Antiproliferative Activity against Human Cancer Cell Lines of Anthyllis vulneraria Extracts

In the current work, the leaf and flower extracts of Anthyllis vulneraria were evaluated for their chemical characterization using HPLC-MS and for their radical scavenging capacity toward methoxy radicals produced by a Fenton-type reaction using an electron paramagnetic resonance (EPR) spectroscopy assay. The in vitro antiproliferative activity of these extracts against several human-derived cancer cells (breast: MCF-7; cervical: HeLa; hepatocellular: HepG2) was also evaluated. The results showed that the Anthyllis vulneraria leaf extract was characterized by 17 different phenolic compounds, among which phenolic acids were the most abundant, while its flower extract exhibited higher contents of flavonoids. Furthermore, Anthyllis vulneraria extracts demonstrated a potent radical scavenging activity against methoxy radicals. Both extracts also significantly reduced the viability of the different cancer cell lines. The results of the current study suggested that Anthyllis vulneraria extracts are a promising source of antioxidant compounds with health benefits and pointed to their potential use for treating cancer and developing novel therapeutic agents.