Identification of sulfoquinovosyldiacyglycerides from Phaeodactylum tricornutum by matrix-assisted laser desorption/ionization QTrap time-of-flight hybrid mass spectrometry

The pharmaceutical industry is interested in identifying novel target compounds. Due to their versatile pharmacological activities (e.g. antiviral, anti-carcinogen and immunosuppressive) sulfoquinovosyldiacylglycerides (SQDGs) are potential drug candidates. The present publication deals with the purification and structural characterization of SQDGs from three different strains of Phaeodactylum tricornutum. Besides detection of SQDGs (sn-1: C16:1/sn-2: C16:0 and sn-1: C20:5/sn-2: C16:0), two novel 2'-O-acylsulfoquinovosyldiacylglyerides (Ac-SQDGs, sn-1: C16:0/ sn-2: C16:0/2' C20:5 and sn-1: C20:5/sn-2: C16:0/2' C20:5) were identified by using matrix-assisted laser desorption/ionization (MALDI) QTrap time-of-flight (ToF) hybrid mass spectrometry (MS) with multistage MS(n). The analytical method enables the sn-position verification of fatty acids (MS(2)) as well as the confirmation of the regioposition of eicospentanoic acid at the sulfoquinovose (MS(3)).     

Statistical anisotropy from vector curvaton in D-brane inflation

We investigate the possibility of embedding the vector curvaton paradigm in D-brane models of inflation in type IIB string theory in a simple toy model. The vector curvaton is identified with the U(1)$U(1)$ gauge field that lives on the world volume of a D3-brane, which may be stationary or undergoing general motion in the internal space. The dilaton is considered as a spectator field which modulates the evolution of the vector field. In this set-up, the vector curvaton is able to generate measurable statistical anisotropy in the spectrum and bispectrum of the curvature perturbation assuming that the dilaton evolves as e^−?∝a²$e^{-?}\propto a^2$ where a(t)$a(t)$ is the scale factor. Our work constitutes a first step towards exploring how such distinctive features may arise from the presence of several light fields that naturally appear in string theory models of cosmology.     

Interference of flavonoids with enzymatic assays for the determination of free fatty acid and triglyceride levels

Flavonoids are bioactive food compounds with potential lipid-lowering effects. Commercially available enzymatic assays are widely used to determine free fatty acid (FFA) and triglyceride (TG) levels both in vivo in plasma or serum and in vitro in cell culture medium or cell lysate. However, we have observed that various flavonoids interfere with peroxidases used in these enzymatic assays, resulting in incorrect lower FFA and TG levels than actually present. Furthermore, addition of isorhamnetin or the major metabolite of the flavonoid quercetin in human and rat plasma, quercetin-3-O-glucuronide, to murine serum also resulted in a significant reduction of the detected TG levels, while a trend was seen for FFA levels. It is concluded that when applying these assays, vigilance is needed and alternative analytical methods, directly assessing FFA or TG levels, should be used for studying the biological effects of flavonoids on FFA and TG levels.     

Quantitative determination of ochratoxin A in vegetable foods

Summary A simple method for the quantitative determination of ochratoxin A (OA) in rice and other vegetable foods (oatmeal, coconut flakes and peas) is described. This procedure implies an acetonitrile-4% KCl -6N HCl (88+10+2) extraction of the acidic OA, subsequent twodimensional thin-layer chromatography (TLC) and detection by fluorescence after exposure to ammonia fumes (excitation at 340 nm; emission at 475 nm). The quantitative detection limit for OA in rice or coconut flakes is 2.4–4 g/kg and the recovery is 96%. For oatmeal and peas the detection limit is only 20 g/kg because of the interference by other metabolites.

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Quantitative Bestimmung von Ochratoxin A in pflanzlichen Nahrungsmitteln

Zusammenfassung Eine einfache Methode zur quantitativen Bestimmung von Ochratoxin A (OA) in Reis und anderen pflanzlichen Nahrungsmitteln (Haferflocken, Kokosflocken, und Erbsen) wird beschrieben. Zur Extraktion wird Acetonitril-4% KCl -6N HCl (88+10+2) benutzt. Nach der Aufbereitung wird eine Auftrennung durch zweidimensionale DC-Trennung (TLC) vorgenommen. Die quantitative Bestimmung erfolgt durch Fluorescenzphotometrie nach Behandlung der Platten mit gasförmigem Ammoniak (Anregung bei 340 nm, Emission bei 475 nm). Die quantitative Bestimmungsgrenze in Reis oder Kokosflocken beträgt 2,4–4 g/kg und die Wiederfindung (Reis) 96%. Für Haferflocken und Erbsen wurde wegen des Störeffektes durch andere Metaboliten nur eine quantitative Bestimmungsgrenze von 20 g/kg erreicht.

     

Quantum mechanical/molecular mechanical free energy simulations of the glutathione S-transferase (M1-1) reaction with phenanthrene 9,10-oxide

Glutathione S-transferases (GSTs) play an important role in the detoxification of xenobiotics in mammals. They catalyze the conjugation of glutathione to a wide range of electrophilic compounds. Phenanthrene 9,10-oxide is a model substrate for GSTs, representing an important group of epoxide substrates. In the present study, combined quantum mechanical/molecular mechanical (QM/MM) simulations of the conjugation of glutathione to phenanthrene 9,10-oxide, catalyzed by the M1-1 isoenzyme from rat, have been carried out to obtain insight into details of the reaction mechanism and the role of solvent present in the highly solvent accessible active site. Reaction-specific AM1 parameters for sulfur have been developed to obtain an accurate modeling of the reaction, and QM/MM solvent interactions in the model have been calibrated. Free energy profiles for the formation of two diastereomeric products were obtained from molecular dynamics simulations of the enzyme, using umbrella sampling and weighted histogram analysis techniques. The barriers (20 kcal/mol) are in good agreement with the overall experimental rate constant and with the formation of equal amounts of the two diastereomeric products, as experimentally observed. Along the reaction pathway, desolvation of the thiolate sulfur of glutathione is observed, in agreement with solvent isotope experiments, as well as increased solvation of the epoxide oxygen of phenanthrene 9,10-oxide, illustrating an important stabilizing role for active site solvent molecules. Important active site interactions have been identified and analyzed. The catalytic effect of Tyr115 through a direct hydrogen bond with the epoxide oxygen of the substrate, which was proposed on the basis of the crystal structure of the (9S,10S) product complex, is supported by the simulations. The indirect interaction through a mediating water molecule, observed in the crystal structure of the (9R,10R) product complex, cannot be confirmed to play a role in the conjugation step. A selection of mutations is modeled. The Asn8Asp mutation, representing one of the differences between the M1-1 and M2-2 isoenzymes, is identified as a possible factor contributing to the difference in the ratio of product formation by these two isoenzymes. The QM/MM reaction pathway simulations provide new and detailed insight into the reaction mechanism of this important class of detoxifying enzymes and illustrate the potential of QM/MM modeling to complement experimental data on enzyme reaction mechanisms.     

Improving pulse sequences for 3D DOSY: COSY-IDOSY

An improved pulse sequence for measuring diffusion-ordered COSY spectra is achieved by incorporating the diffusion encoding directly into the evolution and detection periods of a gradient-enhanced COSY sequence, giving improved sensitivity and a 32-fold reduction in minimum experiment time.     

Entanglement dynamics in open two-qubit systems via diffusive quantum trajectories

We use quantum diffusive trajectories to prove that the time evolution of two-qubit entanglement under spontaneous emission can be fully characterized by optimal continuous monitoring. We analytically determine this optimal unraveling and derive a deterministic evolution equation for the system's concurrence. Furthermore, we propose an experiment to monitor the entanglement dynamics in bipartite two-level systems and to determine the disentanglement time from a single trajectory.     

Polyphenolic profile by FIA/ESI/IT/MSn and antioxidant capacity of the ethanolic extract from the barks of Maytenus cajalbanica (Borhidi & O. Muñiz) Borhidi & O. Muñiz

Abstract

Medium and high polarity extracts from Maytenus species are known to contain polyphenolic compounds such as proanthocyanidins. The high polarity and structural complexity of these compounds make very difficult their isolation even by modern chromatographic techniques. Maytenus cajalbanica (Borhidi & O. Muñiz) Borhidi & O. Muñiz is endemic from Cuba. So far, there are reports neither of phytochemical work nor of biological evaluation of extracts from this subspecies. The goal of this work is to determine the polyphenolic profile and the antioxidant capacity of the ethanolic extract from the barks of Maytenus cajalbanica. FIA/ESI/IT/MSⁿ analysis allowed the identification of 5 flavan-3-ol monomers, 33 proanthocyanidins, 2 free flavonoids and their respective glycosides as major compounds of the ethanolic extract, which showed a strong radical scavenging capacity and a significant ferric reduction power. FIA/ESI/IT/MSⁿ technique led the rapid, effective and sensitive determination of the polyphenolic profile of Maytenus cajalbanica without previous separation.     

In1.06Ho0.94Ge2O7: a thortveitite‐type compound

A new indium holmium digermanate, In_1.06Ho_0.94Ge₂O₇, with a thortveitite‐type structure, has been prepared as a polycrystalline powder material by high‐temperature solid‐state reaction. This new compound crystallizes in the monoclinic system (space group C2/c, No. 15). The structure was characterized by Rietveld refinement of powder laboratory X‐ray diffraction data. The In³⁺ and Ho³⁺ cations occupy the same octahedral site, forming a hexagonal arrangement on the ab plane. In their turn, the hexagonal arrangements of (In/Ho)O₆ octahedral layers are held together by sheets of isolated diortho groups comprised of double tetrahedra sharing a common vertex. In this compound, the Ge₂O₇ diortho groups lose the ideal D_3d point symmetry and also the C_2h point symmetry present in the thortveitite diortho groups. The Ge—O—Ge angle bridging the diortho groups is 160.2 (3)°, compared with 180.0° for Si—O—Si in thortveitite (Sc₂Si₂O₇). The characteristic mirror plane in the thortveitite space group (C2/m, No. 12) is not present in this new thortveitite‐type compound and the diortho groups lose the C_2h point symmetry, reducing to C₂.