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141.
The hydrogen-Lindlar catalyst system is effective for the highly regioselective reduction of α,β-unsaturated carbonyl compounds to the corresponding α,β-saturated compounds. 相似文献
142.
Giuliana Bianco Rosalia Zianni Giuseppe Anzillotta Achille Palma Vincenzo Vitacco Laura Scrano Tommaso R. I. Cataldi 《Analytical and bioanalytical chemistry》2013,405(7):2405-2410
We report on the content of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in 15 breast milk samples of nursing women living in the city of Taranto (Southern, Italy) or nearby. Breast milk samples were collected over the 2008–2009 period and analyzed by gas chromatography coupled with high-resolution mass spectrometry (GC-HRMS) upon accelerated solvent extraction (ASE) using acetone/n-hexane mixture 1:1 (v/v). The method was validated demonstrating good performing features. Profiles of PCDD/PCDF congeners in breast milk samples exhibited a prevalence of PCDFs compared to PCDDs. Toxic equivalents (TEQs in picogram per gram fat) of four breast milk were far above the legal limit for human consumption of 3.0 pg/g; their estimated daily and weekly dietary intake were almost 5–20 and 10–40 times higher, respectively, than the tolerable intake values established by the World Health Organization. Figure
Occurrence of the toxic micropollutants in breast milk samples of mothers living in or nearby Taranto 相似文献
143.
Tommaso R. I. Cataldi Giuliana Bianco Juliano Fonseca Philippe Schmitt-Kopplin 《Analytical and bioanalytical chemistry》2013,405(2-3):493-507
Gram-negative bacteria use N-acylhomoserine lactones (AHLs) as their command language to coordinate population behavior during invasion and colonization of higher organisms. Although many different bacterial bioreporters are available for AHLs monitoring, in which a phenotypic response, e.g. bioluminescence, violacin production, and β-galactosidase activity, is exploited, mass spectrometry (MS) is the most versatile detector for rapid analysis of AHLs in complex microbial samples, with or without prior separation steps. In this paper we critically review recent advances in the application of high-resolution MS to analysis of the quorum sensing (QS) signaling molecules used by Gram-negative bacteria, with much emphasis on AHLs. A critical review of the use of bioreporters in the study of AHLs is followed by a short methodological survey of the capabilities of high-resolution mass spectrometry (HRMS), including Fourier-transform ion cyclotron resonance (FTICR) MS and quadrupole time-of-flight (qTOF) MS. Use of infusion electrospray ultrahigh-resolution FTICR MS (12 Tesla) enables accurate mass measurements for determination of the elemental formulas of AHLs in Acidovorax sp. N35 and Burkholderia ubonensis AB030584. Results obtained by coupling liquid chromatography with a hybrid quadrupole linear ion trap-FTICR mass spectrometer (LC–LTQ-FTICRMS, 7-T) for characterization of acylated homoserine lactones in the human pathogen Pseudomonas aeruginosa are presented. UPLC–ESI-qTOF MS has also proved to be suitable for identification of 3O-C10HSL in Pseudomonas putida IsoF cell culture supernatant. Aspects of sample preparation and the avoidance of analytical pitfalls are also emphasized. Figure
LC separation and FTICR MS identification of 3-oxo-C12-HSL in bacterial isolates of P. aeruginosa (strain ATCC 9027) 相似文献
144.
Giuliana Bianco Salvatore Abate Cristiana Labella Tommaso R. I. Cataldi 《Rapid communications in mass spectrometry : RCM》2009,23(7):1065-1074
Liquid chromatography (LC) with positive ion electrospray ionization (ESI+) coupled to a hybrid quadrupole linear ion trap (LTQ) and Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) was employed for the simultaneous determination of caffeine and its metabolites in human urine within a single chromatographic run. LC/ESI‐FTICRMS led to the unambiguous determination of the molecular masses of the studied compounds without interference from other biomolecules. A systematic and comprehensive study of the mass spectral behaviour of caffeine and its fourteen metabolites by tandem mass spectrometry (MS/MS) was performed, through in‐source ion trap collision‐induced dissociation (CID) of the protonated molecules, [M+H]+. A retro‐Diels‐Alder (RDA) process along with ring‐contraction reactions were the major fragmentation pathways observed during CID. The base peak of xanthine precursors originates from the loss of methyl isocyanate (CH3NCO, 57 Da) or isocyanic acid (HNCO, 43 Da), which in turn lose a CO unit. Also uric acid derivatives shared a RDA rearrangement as a common fragmentation process and a successive loss of CO2 or CO. The uracil derivatives showed a loss of a ketene unit (CH2CO, 42 Da) from the protonated molecule along with the loss of H2O or CO. To assess the potential of the present method three established metabolite ratios to measure P450 CYP1A2, N‐acetyltransferase and xanthine oxidase activities were evaluated by a number of identified metabolites from healthy human urine samples after caffeine intake. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
145.
A study of the addition of boron enolates of methyl ketones to trans α,β-aziridine aldehydes is reported. The reaction proceeds with excellent anti stereoselectivity furnishing functionalized products, capable of other controlled transformations, some of which are described. 相似文献
146.
Giuliana Gorrasi Liberata Guadagno Vittoria Vittoria 《Colloid and polymer science》2003,281(5):469-475
The solvent induced crystallization phenomenon (SINC) was studied for syndiotactic polypropylene quenched from the melt at 0 °C and kept at this temperature a for long time. In these conditions a mesophase having the chains in trans-planar conformation was formed. The interaction polymer-solvent with liquids having different solubility parameters, derived by both the swelling and the weight uptake, considerably varies among the different liquids, showing a maximum corresponding to carbon tetrachloride ('=8.6). A smaller maximum was found for chloroform ('=9.3). These two maxima were attributed to interaction either with the amorphous phase or with the trans-planar mesophase. Infrared analysis showed that all the liquids induce a conformational transition from trans-planar to helix, and only a small residual fraction of chains in trans-planar conformation was detected for the samples immersed in the liquids and vacuum dried for many hours. The X-ray analysis showed that the quenched sample undergoes in the solvents a complex transformation, partially crystallizing into the helical form I and partially into the helical form II. All the liquids induced the same transformation, in spite of very different levels of interaction. 相似文献
147.
148.
149.
Pellei M Papini G Trasatti A Giorgetti M Tonelli D Minicucci M Marzano C Gandin V Aquilanti G Dolmella A Santini C 《Dalton transactions (Cambridge, England : 2003)》2011,40(38):9877-9888
New nitroimidazole and glucosamine conjugated heteroscorpionate ligands, namely 2,2-bis(3,5-dimethyl-1H-pyrazol-1-yl)-N-(2-(2-methyl-5-nitro-1H-imidazol-1-yl)ethyl)acetamide (L(MN)) and 1,3,4,6-tetra-O-acetyl-2-{[bis(3,5-dimethyl-1H-pyrazol-1-yl)acetyl]amino}-2-deoxy-β-D-glucopyranose (L(DAC)), respectively, were synthesized by direct coupling of preformed side chain acid and amine components. The related copper(II) complexes {[(L(MN))(2)Cu]Cl(2)}, and {[(L(DAC))(2)Cu]Cl(2)} have been prepared from the reaction of CuCl(2)*2H(2)O with L(MN) or L(DAC) ligand in methanol solution. Single crystal structural characterization was undertaken for the L(MN) ligand. In the absence of a coordinated metal core, the overall arrangement of the ligand is determined by some loose intra- and inter-molecular nonbonding contacts. X-Ray Absorption Spectroscopy (XAS) has been used to probe the local structure of the two copper(II) complexes, {[(L(MN))(2)Cu]Cl(2)} and {[(L(DAC))(2)Cu]Cl(2)}. The EXAFS analysis has permitted the identification of the local environment of the copper site. Copper interacts with 2 units of ligand in both complexes, and it is found to be 6-fold coordinated. Its local structure is described by four Cu-N and two Cu-O interactions to form a pseudo-octahedron core, with a 0.14 ? lengthening of the Cu-O bond length in the case of L(DAC) complex with respect to the L(MN) one, likely due to the higher steric hindrance of the glucosamine moiety. The XANES analysis agrees with these results, also confirming the Cu(II) formal copper oxidation state for both complexes. The new copper(II) complexes {[(L(MN))(2)Cu]Cl(2)} and {[(L(DAC))(2)Cu]Cl(2)} as well as the corresponding uncoordinated ligands were evaluated for their cytotoxic activity towards a panel of several human tumour cell lines. The results reported here indicate that both copper(II) complexes show similar spectra of cytotoxicity and very low resistance factors (RF < 2) against C13* ovarian cancer cells which have acquired resistance to cisplatin. 相似文献
150.
Masako Yamada Yoshihisa IwashitaToshiji Kanaya Norifumi L. YamadaHirohiko M. Shimizu Kenji MishimaMasahiro Hino Masaaki KitaguchiKatsuya Hirota Peter GeltenbortBruno Guerard Giuliana ManzinKen Andersen Jyotsana LalJohn M. Carpenter Markus BleuelShane J. Kennedy 《Physica B: Condensed Matter》2011,406(12):2453-2457
We are developing a high-resolution small angle neutron scattering instrument for very cold neutrons (VCN). Our concept includes a magnetic lens for focusing of the beam at the detector plane. The lens consists of one permanent-magnet sextupole array rotating outside another stationary sextupole array, to focus a pulsed white beam of neutrons. Thus the instrument operates in time of flight mode. The prototype magnetic lens has a bore of 15 mm diameter and length of 66 mm, producing a magnetic field gradient oscillating from 1.5×104 to 5.9×104 T/m2, with frequency ≤25 Hz. A torque-canceling magnet around the lens suppresses the torque of rotation from the outer array to 1/3.We have demonstrated the performance of the lens, over wavelength range from 30 to 48 Å, on the PF2-VCN beam line at the Institut Laue-Langevin, France. The focused beam image was the same size as the source, without chromatic aberration, with focal length of 1.14 m. We also studied the performance of this configuration for high-resolution SANS, in a compact geometry (just 5 m long). The measurable q range of this system was 0.009 Å−1≤q≤0.3 Å−1 or 0.004 Å−1≤q≤0.08 Å−1 for sample to detector distances of 100 and 465 mm, respectively. Here, we present the results of our lens characterization study along with the SANS results on a tri-block copolymer (F127 Pluronic) and on a stretched polymer blend (with the Shish-Kebab structure). 相似文献