Application of an innovative matrix solid-phase dispersion–solid-phase extraction–liquid chromatography–tandem mass spectrometry analytical methodology to the study of the metabolism of the estrogenic mycotoxin zearalenone in rainbow trout liver and muscular tissue

The metabolic fate of the estrogenic mycotoxin zearalenone in rainbow trout is presently unknown. In this study, the tissue concentration of zearalenone and its principal metabolites (α-zearalenol and β-zearalenol) was determined. A known amount of zearalenone was administered as a single bolus to ten fish, and the biological tissue concentration was determined at various times following administration. The analytes were extracted from liver and muscular tissue using an on-line matrix solid-phase dispersion–solid-phase extraction sample preparation protocol, and their concentration determined by HPLC–Turboionspray–tandem mass spectrometry. The results showed that zearalenone is mainly metabolized into α-zearalenol in both liver and muscular tissues. The maximum concentrations of each analyte found in liver were 76.1, 211.2 and 63.7?ng/g respectively for zearalenone, α-zearalenol and β-zearalenol, while in muscular tissue they were 10.7, 8.2 and 6.5?ng/g. These values were reached after 2?h in liver tissue and 12?h in muscular tissue. Moreover the data obtained showed that the elimination rate in liver is quite fast since 48?h after the exposure less than 7% of the maximum concentration found is still present. In muscular tissue, however, about one-third of the maximum concentration found is still present after 48?h.     

Catalytic activity of a ceria-lanthana system for 4-methylpentan-2-ol dehydration

A ceria-lanthana catalytic system prepared by the sol-gel technique proved to be active in 4-methylpentan-2-ol conversion, mainly leading to 4-methylpent-1-ene, a monomer for manufacturing polymers of high technological properties. The product distribution strongly depends on the acid-base features of the catalyst. The catalytic behavior of the samples was examined in the light of their acid-base properties. This revised version was published online in June 2006 with corrections to the Cover Date.     

L‐lysine and EDTA polymer mimics as resins for the quantitative and reversible removal of heavy metal ion water pollutants

Traditional precipitation methods for inorganic micropollutant removal from waters are increasingly being replaced by sorption methods based on both natural and synthetic materials. In this context, two novel effective heavy metal ions absorbers are presented. These resins, LYMA and LMT85, were crosslinked poly(amidoamine)s carrying amine and carboxyl groups in their repeating units. In particular, the LYMA‐repeating unit contains one carboxyl and two amine groups and is a mimic of L ‐lysine, whereas LMT85 contains two amine and five carboxyl groups and is a mimic of EDTA. Both resins were prepared at moderate cost by simple eco‐friendly procedures. The heavy metal ion set adopted as benchmark was Cu²⁺, Cd²⁺, Pb²⁺, Zn²⁺, Ni²⁺, and Co²⁺. LYMA proved selective for Cu²⁺ and Ni²⁺, the other ions tested being negligibly absorbed, whereas LMT85 proved capable of rapidly and quantitatively absorbing all the ions tested either singly or in mixed solution. The absorption process was reversible, and the resins were easily regenerated by acidification. The absorption of several metal ions imparted intense coloring to the resins, a feature possibly exploitable for analytical purposes. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

The Michael addition of indoles to alpha,beta-unsaturated ketones catalyzed by CeCl3.7H2O-NaI combination supported on silica gel

Alkylation of indoles by means of the Michael addition has been the subject of a number of investigation. It is well established that regioselectivity in the additions of indoles to electron-deficient alkenes is strongly controlled by the reaction medium. In a continuation of the work on developing greener and cleaner technologies, the cerium(III) chloride heptahydrate and sodium iodide combination supported on silica gel catalyzes the alkylation of various indoles with alpha,beta-unsaturated ketones giving 3-(3-oxoalkyl)indole derivatives in good yields. The substitution on the indole nucleus occurred exclusively at the 3-position, and N-alkylation products have not been observed.     

Liquid chromatography/tandem mass spectrometry for the identification and determination of trichothecenes in maize

A reliable, sensitive and selective liquid chromatography/tandem mass spectrometry (LC/MS/MS) method has been developed to determine four trichothecene mycotoxins (nivalenol, deoxynivalenol, fusarenon X and 3-acetyldeoxynivalenol) in maize. Sample preparation was performed by extracting the analytes with a mixture of acetonitrile and water, followed by a solid-phase extraction with Carbograph-4 cartridges as the purification step. For the LC/MS/MS analysis two interfacing systems, Turbo IonSpray (TISP) and atmospheric pressure chemical ionization (APCI), were compared in both negative and positive ion modes. LC and MS parameters were optimized to achieve better results and sensitivity. The effect of mobile phase modifiers such as ammonium acetate and formic acid on the ionization yield was also evaluated. The best results were obtained using the electrospray ionization (ESI) interface in negative ion mode and the multiple reaction monitoring mode (MRM) for the quantitation. The detection limits ranged between 10 ng/g for fusarenon X and 1.5 ng/g for deoxynivalenol. A linear working range was achieved with a standard deviation between 3 and 10% and recovery rates from the maize samples above 81%. The procedure was applied to the analysis of a set of maize samples collected from farms located in different areas of northern and central Italy. The investigated samples turned out to be contaminated primarily with deoxynivalenol and, to a minor extent, with its derivatives.     

Oriented thin films from soluble polythiophenes

The degree of orientation of thin films of eight different polymeric structures, belonging to the class of soluble polyalkylthiophenes (PATs) has been studied. Thin films of the polymers, obtained by spin coating onto glass substrates, were oriented by means of the rubbing technique. The degree of orientation is related to the regioregularity of the system: highly regioregular polymers can be oriented, while regiorandom materials are not oriented. The degree of orientation can be improved by thermal annealing of the oriented films. As a result of annealing, which was performed at different temperatures according to the thermal behavior of the polymers, it was possible to increase the polarization ratio for poly(3-decylthiophene) up to 12–13 as detected from the UV-vis spectra in polarized light. Moreover in the investigated PATs, both the key role of molecular weight and its distribution for achieving a high orientation degree has been assessed. Copyright © 2003 John Wiley & Sons, Ltd.     

Unprecedented eta(1)-P(basal) coordination of P(4)X(3) molecules (X = S, Se). An experimental and theoretical study of the apical vs basal complexation dichotomy

Reaction of [(triphos)Re(CO)(2)(OTf)] (1) [triphos = MeC(CH(2)PPh(2))(3); OTf = OSO(2)CF(3)] with P(4)S(3) and P(4)Se(3) yields pairs of coordination isomers, namely, [(triphos)Re(CO)(2)[eta(1)-P(apical)-P(4)X(3)]](+) (X = S, 2; Se, 5) and [(triphos)Re(CO)(2)[eta(1)-P(basal)-P(4)X(3)]](+) (X = S, 3; Se, 6). The latter represent the first examples of the eta(1)-P(basal) coordination achieved by the P(4)X(3) molecular cage. Further reaction of 2/3 and 5/6 mixtures with 1 affords the dinuclear species [[(triphos)Re(CO)(2)](2)[mu,eta(1:1)-P(apical,)P(basal)-P(4)X(3)]](2+) (X = S, 4; Se, 7) in which the unprecedented M-eta(1)-P(basal)/eta(1)-P(apical)-M' bridging coordination of the P(4)X(3) molecule is accomplished. A theoretical analysis of the bonding properties of the two coordination isomers is also presented. The directionality of apical vs basal phosphorus lone pairs is also discussed in terms of MO arguments.     

Asymmetric transfer hydrogenation: chiral ligands and applications

Hydrogen transfer reduction processes are attracting increasing interest from synthetic chemists in view of their operational simplicity and high selectivity. In this tutorial review the most significant advances recently achieved in the stereoselective reduction of unsaturated organic compounds catalyzed by homogeneous transition metal complexes are critically reviewed. A sharp growth of the synthetic applications of this technique in the synthesis of fine chemicals is predictable as the use of transition metal catalyzed reactions will become more familiar to synthetic chemists.     

Evolution of the Pt layer deposited on MgO(001) by pulsed laser deposition as a function of the deposition parameters: a scanning tunneling microscopy and energy dispersive X-ray diffractometry/reflectometry study

A combined ultrahigh vacuum scanning tunneling microscopy (STM-UHV) and energy dispersive X-ray diffractometry/reflectometry (EDXD/EDXR) study of the evolution of face-centered cubic (fcc) Pt layer growth on MgO(100) by pulsed laser deposition as a function of the process parameters such as deposition temperature and deposition duration has been carried out. The aim of this study is to define the best experimental conditions to obtain a controlled film deposition selective on the Pt growth direction (either [111] or [002]). The evolution of the Pt surface morphology as a function of the deposition temperature (T(dep)) from 300 to 700 degrees C has been studied with STM and ED techniques. Results show that the Pt surface, characterized at T(dep) = 300 degrees C by a 3D island morphology, evolves at higher temperatures to a morphology in which the original islands coexist with a distribution of orthogonal 2D stripes. The two features can be associated with the [111] and [002] Pt growth directions of the fcc phase, respectively. For T(dep) = 700 degrees C, the island morphology of the (111) face completely disappears, while the merging process of the (002) stripes reaches completion. The evolution of the morphology at T(dep) = 600 degrees C as a function of the deposition time and thickness has then been studied with STM-UHV, revealing an initial growth of mosaic-like 3D islands. These independent islands, already interconnected, expand along two orthogonal directions and, for longer deposition times, lead to the texture of orthogonal stripes. The EDXR characterization providing the morphological parameters of the films, i.e., thickness and roughness, confirms the above observation and quantifies the effect of such morphological changes on the surface roughness of the Pt film, an important parameter for applications of Pt films as underlayer in magnetic recording media.