Angela Cuzzola

A preliminary study on iron species as heterogeneous catalysts for the degradation of linear alkylbenzene sulphonic acids by H2O2

Abstract Different eco-sustainable methods based on the activation of H2O2 promoted by iron species in homogeneous and heterogeneous phase, in the presence and absence of solar irradiation was compared in order to evaluate their effectiveness in the wastewater treatment. Commercial linear alkylbenzene sulphonic acids (LAS) have been chosen as model compound, being a pollutant largely used in different fields. Supported iron species were identified as new promising class of photo-activable and recyclable catalysts.

Drug Delivery with a Calixpyrrole–trans-Pt(II) Complex

A meso-p-nitroaniline-calix[4]pyrrole derivative trans-coordinated to a Pt(II) center was synthesized and its structure solved by X-ray analysis. Adenosine monophosphate (AMP) was used as a model compound to evaluate the potential for the assisted delivery of the metal to the DNA nucleobases via the phosphate anion-binding properties of the calix[4]pyrrole unit. An NMR investigation of the kinetics of AMP complexation in the absence of an H-bonding competing solvent (dry CD(3)CN) was consistent with this hypothesis, but we could not detect the interaction of the calix[4]pyrrole with phosphate in the presence of water. However, in vitro tests of the new trans-calixpyrrole-Pt(II) complex on different cancer cell lines indicate a cytotoxic activity that is unquestionably derived from the coexistence of both the trans-Pt(II) fragment and the calix[4]pyrrole unit.

Expression of terpene synthase genes associated with the formation of volatiles in different organs of Vitis vinifera

Plants produce a plethora of volatile organic compounds (VOCs) which are important in determining the quality and nutraceutical properties of horticultural food products, including the taste and aroma of wine. Given that some of the most prevalent grape aroma constituents are terpenoids, we investigated the possible variations in the relative expression of terpene synthase (TPS) genes that depend on the organ. We thus analysed mature leaves, young leaves, stems, young stems, roots, rachis, tendrils, peduncles, bud flowers, flowers and berries of cv Moscato bianco in terms of their VOC content and the expression of 23 TPS genes. In terms of the volatile characterization of the organs by SPME/GC-MS analysis, flower buds and open flowers appeared to be clearly distinct from all the other organs analysed in terms of their high VOC concentration. Qualitatively detected VOCs clearly separated all the vegetative organs from flowers and berries, then the roots and rachis from other vegetative organs and flowers from berries, which confirms the specialization in volatile production among different organs. Our real-time RT-PCR results revealed that the majority of TPS genes analysed exhibited detectable transcripts in all the organs investigated, while only some were found to be expressed specifically in one or just a few organs. In most cases, we found that the known products of the in vitro assay of VvTPS enzymes corresponded well to the terpenes found in the organs in which the encoding gene was expressed, as in the case of (E)-β-caryophyllene synthases, α-terpineol synthase and α-farnesene synthase. In addition, we found groups of homologous TPS genes, such as (E)-β-caryophyllene and β-ocimene synthases, expressed distinctively in the various tissues. This thus confirmed the subfunctionalization events and a specialization on the basis of the organs in which they are mostly expressed.

Potential of a multiparametric optical sensor for determining in situ the maturity components of red and white Vitis vinifera wine grapes.

A nondestructive fluorescence-based technique for evaluating Vitis vinifera L. grape maturity using a portable sensor (Multiplex) is presented. It provides indices of anthocyanins and chlorophyll in Cabernet Sauvignon, Merlot, and Sangiovese red grapes and of flavonols and chlorophyll in Vermentino white grapes. The good exponential relationship between the anthocyanin index and the actual anthocyanin content determined by wet chemistry was used to estimate grape anthocyanins from in field sensor data during ripening. Marked differences were found in the kinetics and the amount of anthocyanins between cultivars and between seasons. A sensor-driven mapping of the anthocyanin content in the grapes, expressed as g·kg(-1) fresh weight, was performed on a 7-ha vineyard planted with Sangiovese. In the Vermentino, the flavonol index was favorably correlated to the actual content of berry skin flavonols determined by means of HPLC analysis of skin extracts. It was used to make a nondestructive estimate of the evolution in the flavonol concentration in grape berry samplings. The chlorophyll index was inversely correlated in a linear manner to the total soluble solids (°Brix): it could, therefore, be used as a new index of technological maturity. The fluorescence sensor (Multiplex) possesses a high potential for representing an important innovative tool for controlling grape maturity in precision viticulture.

Synthesis, X-ray Structure, and Anion-Binding Properties of a Cryptand-Like Hybrid Calixpyrrole

The novel cryptand in/out-3, containing two tripyrrolemethane units bridged by three 1,3- diisopropylidenbenzene arms, was readily synthesized by a convergent three-step synthesis. It binds fluoride by inclusion with excellent selectivity with respect to a number of other tested anions. The structure of the free receptor and that of its fluoride complex were investigated in solution by NMR spectroscopy. The solid-state X-ray structure of the free cryptand 3 was also determined.

NMR Detection of the Conformational Distortion Induced in Cyclodextrins by Introduction of Alkyl or Aromatic Substituents

The conformational features of alkylated, benzoylated, and benzylated cyclodextrins in solution were analysed by NOE and proton-selective relaxation methods and were compared to those of native compounds.

A comprehensive study for the validation of a LC–MS/MS method for the determination of free and total forms of urinary cortisol and its metabolites

Several pathological conditions can be related to the alteration of the urinary levels of cortisol (F) and its metabolites. The determination of each of them in the free and free plus conjugated form can provide a deeper insight into the impaired activity of the cortisol metabolism enzymes, thus improving the diagnosis protocol currently based only on the determination of total amount of urinary cortisol metabolites. In that view, an LC-MS/MS method for the determination of the free and total amount of urinary F, cortisone (E), tetrahydrocortisol (THF), allo-tetrahydrocortisol (A-THF) and tetrahydrocortisone (THE) was thus developed and validated. Deconjugation of glucocorticoids was carried out by enzymatic hydrolysis. Analytes were extracted by solid phase extraction, separated by liquid chromatography and analyzed via electro-spray ionization (negative ion mode) triple-quadrupole mass spectrometry in the selected reaction monitoring mode using a stable isotope-labeled internal standard. Baseline separation for all compounds, in particular the two stereoisomers A-THF and THF, was obtained. Matrix effects, not reported so far, were observed and minimized for the determination of urinary free E and THE. Validated range was 0.5-1000ng/mL for A-THF and THF, 5-800ng/mL for E and THE and 1-1000ng/mL for F, with R(2) values greater than 0.9981. The LOD and LOQ of the described method ranged from 0.1 to 3.0ng/mL, while the extraction recoveries resulted close to 100% for all the glucocorticoids determined. Precision and accuracy were well within ±10%. As suggested by the results obtained in the preliminary study on polycystic ovary syndrome (PCOS) urine samples, the method can be used to support clinical diagnosis of pathologies related to cortisol metabolism. In fact, levels of free and total glucocorticoids in control subjects were in agreement with previously reported data, as well as free and total A-THF/THF ratio in PCOS patients. Conversely, in the latter free F/E and A-THF+THF/THE ratios were lower than in control subjects (P<0.01), suggesting a possible alteration of 11β-HSD1 and 11β-HSD2 activity, to be further investigated.

Application of hyphenated mass spectrometry techniques for the analysis of urinary free glucocorticoids

Alteration of levels of glucocorticoids in plasma and urine can be related to several diseases. In particular, the determination of endogenous glucocorticoids in urine has been reported to provide information on cortisol and cortisone status, on the activities of steroid hormone enzymes and on glucocorticoid metabolism. In this study, the application of hyphenated mass spectrometry techniques (GC/MS without derivatization and LC/MS) for the simultaneous analysis of free urinary cortisol (F), cortisone (E), tetrahydrocortisol (THF), allo-tetrahydrocortisol (A-THF) and tetrahydrocortisone (THE) was evaluated. A sample preparation protocol by solid-phase extraction, mass spectrometry parameters and chromatographic conditions for both techniques were carefully optimized in terms of extracting phase and solvents, matrix effects, recovery, sensitivity and compound resolution. Baseline separation was achieved for the five underivatized analytes both in GC and LC. The LC/MS/MS technique was more suitable for the analysis of urine samples, being less influenced by matrix effects and showing excellent sensitivity and selectivity. A preliminary application of the reported method for the diagnosis of metabolic diseases was also described. The determination of each analyte in its free form, described for the first time in the paper, offers new perspectives in the application of glucocorticoid analysis for diagnostic purposes.

Identification and characterization of Fenton oxidation products of surfactants by electrospray mass spectrometry and by solid phase microextraction gas chromatography mass spectrometry. 2. Fatty alcohol polyethoxy sulphates

The Fenton reaction for the degradation of surfactants has been investigated and partial degradation products have been identified and characterized by mass spectrometry for the case of fatty alcohol polyethoxy sulphates. The polar water-soluble products were investigated by liquid chromatography/mass spectrometry (LC/MS) with electrospray ionization (ESI), and the volatile products leaving the mixture during the reaction were trapped by means of solid phase microextraction (SPME) and investigated by gas chromatography/mass spectrometry (GC/MS) with electron and chemical ionization. The oxidation leads to the formation of products with hydroxyl and epoxide groups due to insertion of oxygen atoms or with terminal ethoxylic moieties deriving from the loss of the hydrophilic sulphate group. The formation of volatile aldehydes is also observed, corresponding to the fragmentation between hydrocarbon and ethoxylic chains. The extent of mineralization is dependent on peroxide and iron(II) concentrations. Copyright 2000 John Wiley & Sons, Ltd.

Changes in olive oil volatile organic compounds induced by water status and light environment in canopies of Olea europaea L. trees

BACKGROUND Light and water are major factors in fruit development and quality. In this study, the effect of water and light in Olea europaea trees on volatile organic compounds (VOCs) in olive oil was studied over 2 years. Mature fruits were harvested from three zones of the canopy with different light exposure (64%, 42% and 30% of incident light) of trees subjected to full, deficit or complementary irrigation. VOCs were determined by SPME GC-MS and analysed by principal component analysis followed by discriminant analysis to partition treatment effects. RESULTS Fruit fresh weight and mesocarp oil content decreased in zones where intercepted light was less. Low light levels significantly slowed down fruit maturation, whereas conditions of water deficit accelerated the maturation process. The presence of cyclosativene and α-muurulene was associated with water deficit, nonanal, valencene with full irrigation; α-muurulene, (E)-2-hexanal were related to low light conditions, while trans-β-ocimene, α-copaene, (Z)-2-penten-1-ol, hexanal and nonanal to well exposed zones. The year strongly affected the VOC profile of olive oil. CONCLUSION This is the first report on qualitative changes in VOCs induced by light environment and/or water status. This information is valuable to better understand the role of environmental factors on the sensory quality of virgin olive oil.