High-performance liquid chromatographic/tandem mass spectrometric identification of the phototransformation products of tebuconazole on titanium dioxide

Tebuconazole is a widely used fungicide. The formation of by-products on irradiated titanium dioxide as a photocatalyst was evaluated. Several species derived from tebuconazole degradation were identified and characterized by HPLC/MS(n). A pattern of reactions accounting for the observed intermediates is proposed. Different parallel pathways are operating (and through these pathways the transformation of the molecule proceeds), leading to a wide range of intermediate compounds. All these molecules are more hydrophylic than tebuconazole. The main steps involved are (1) the hydroxylation of the molecule with the formation of three species having [M + H](+) 324; the hydroxylation occurs on the C-1 carbon and on the aromatic ring in the two ortho-positions; (2) the cleavage of a C--C bond with the release of the tert-butyl moiety and the formation of a species having m/z 250; analogously to step 1, also on this species a further hydroxylation reaction occurs; (3) through the loss of the triazole moiety with the formation of a structure with m/z 257.     

Isolation of three new naturally occurring compounds from the culture of Micromonospora sp. P1068

Bioassay guided isolation of an antibacterial extract prepared from the fermentation broth of a Micromonospora sp. P1068 led to the isolation of eight compounds identified as (3R) 3,4',7-trihydroxy-isoflavanone (1), 3-hydroxydehydrodaidzein, daidzein (2), 3-methyl-1H-indole-2-carboxylic acid (3), 1H-indole-3-carboxaldehyde (4), 3-(p-hydroxyphenyl)-N-methylpropionamide, N-methylphloretamide (5), phenyl acetic acid (6), 2-hydroxy phenyl acetic acid (7) and 4-hydroxy-5-methoxy-benzoic acid (8). Compounds 1 and 5 were found to be novel chemical entities while 3 was isolated from a natural source for the first time. All compounds were evaluated for their antimicrobial activities against a panel of clinically significant microorganisms. Compound 4 was active against Staphylococcus aureus (MIC, 32 microg/ml), Enterococcus faecium (MIC, 32 microg/ml) and Escherichia coli (MIC, 64 microg/ml).     

Entanglement and factorized ground states in two-dimensional quantum antiferromagnets

Making use of exact results and quantum Monte Carlo data for the entanglement of formation, we show that the ground state of anisotropic two-dimensional S=1/2 antiferromagnets in a uniform field takes the classical-like form of a product state for a particular value and orientation of the field, at which the purely quantum correlations due to entanglement disappear. Analytical expressions for the energy and the form of such states are given, and a novel type of exactly solvable two-dimensional quantum models is therefore singled out. Moreover, we show that the field-induced quantum phase transition present in the models is unambiguously characterized by a cusp minimum in the pairwise-to-global entanglement ratio R, marking the quantum-critical enhancement of multipartite entanglement.     

Cholesterol oxidation in meat-based baby foods

Cholesterol oxidation in commercial meat-based homogenized and freeze-dried baby foods was examined. The 7 major products of this reaction were determined by gas chromatography coupled with mass spectrometry (GC-MS). As far as single cholesterol oxidation products (COP) are concerned, 7-ketocholesterol was the major product of direct cholesterol oxidation in the 2 groups of analyzed samples, and this study confirmed that it is a useful marker of the whole cholesterol oxidation process. Nevertheless, the amounts of cholesterol-5beta,6beta-epoxide were often similar to and sometimes higher than the amounts of 7-ketocholesterol, thus showing a strong development of both direct and indirect cholesterol oxidation pathways. Total COP content was significantly higher in freeze-dried than in homogenized products. Moreover, in freeze-dried samples, the COP content per serving was quite variable and, in 2 samples, it was close to or even higher than 500 microg. The greater development of cholesterol oxidation in the freeze-dried samples was confirmed by their highest total COP/cholesterol percent ratios. A constant correlation between the fatty acid composition and the development of cholesterol oxidation was not found, although a positive correlation between unsaturated fatty acid content and total COP content occasionally exists in samples of the same brand.     

Extraction of electrolytes from aqueous solutions and their spectrophotometric determination by use of acid-base chromoionophores in lipophylic solvents

The formation of non-absorbing complexes in an organic phase has been exploited for the spectrophotometric determination of ionic analytes in aqueous solutions. The method is based on liquid-liquid extraction of aqueous solution with lipophylic organic phases containing an acid-base chromoionophore, a neutral lypophilic ligand (neutral carrier) selective to the analyte and a cationic (or anionic) exchanger. The method avoids all difficulties of the preparation of the very thin membranes used in optodes, so that it can advantageously be used for the study of the role physical-chemical parameters of the system in order to optimize them and to prepare, if necessary, an optimized optode. Two lipophylic derivatives of Nile Blue and 4',5-dibromofluorescein have been synthesized, in order to ensure their permanence within organic phase. Two different neutral carriers previously characterized by us as ionophores for liquid-membrane Ion Selective Electrodes have been employed. Three different ionic exchangers have been tested. Furthermore, a model allowing the interpolation of experimental data and the determination of the thermodynamic constant of the ionic-exchange equilibrium has been developed and applied.     

MRI characterization of residual mediastinal masses in Hodgkin's disease: long-term follow-up

Our purpose was to evaluate the role of MRI in distinguishing fibrous from active residual masses in treated Hodgkin's disease. Forty patients with residual mediastinal mass larger than 1.5 cm underwent MRI 1, 3, 6, and 12 months after the end of cycles of prescribed chemotherapy or combined chemoradiotherapy. The MRI examinations were performed on a 0.5 and a 1.5 T systems, using T(1) before and after gadolinium injection and T(2)-weighted sequences. Each time the residual mass was evaluated in size and signal intensity on spin echo (SE) T(2)-weighted images and on SE T(1)-weighted images after contrast medium. Low signal intensity and low contrast enhancement were considered signs of inactive residues; homogeneous high signal intensity and high contrast enhancement were indicative of active residual disease; heterogeneous signal intensity and heterogeneous contrast enhancement were indicative of partial remission or necrotic/inflammatory phenomena. MR showed high diagnostic accuracy in the evaluation of Hodgkin's mediastinal residues after treatment, if performed at least 6 months after the end of therapy, reaching the highest sensitivity and specificity values at 12 month follow-up (considering the three parameters-T(2) signal intensity, contrast-enhancement, and size-all together). If we consider the single parameters individually, we can observe that size variation remains the more valuable parameter to predict or to exclude a relapse. MR diagnostic accuracy at the 6-month follow-up was lower due to the higher incidence of inhomogeneous pattern. The accuracy of MR performed at 1 and at 3 months after the end of therapy was not satisfying. This represents a clinical problem because the most important clinical decisions have to be taken just in this early post-treatment phase.     

Detection of XY behavior in weakly anisotropic quantum antiferromagnets on the square lattice

We consider the Heisenberg antiferromagnet on the square lattice with S=1/2 and very weak easy-plane exchange anisotropy; by means of the quantum Monte Carlo method, based on the continuous-time loop algorithm, we find that the thermodynamics of the model is highly sensitive to the presence of tiny anisotropies and is characterized by a crossover between isotropic and planar behavior. We discuss the mechanism underlying the crossover phenomenon and show that it occurs at a temperature which is characteristic of the model. The expected Berezinskii-Kosterlitz-Thouless transition is observed below the crossover: a finite range of temperatures consequently opens for experimental detection of noncritical 2D XY behavior. Direct comparison is made with uniform susceptibility data relative to the S=1/2 layered antiferromagnet Sr2CuO2Cl2.     

"Oscillating" metallocene catalysts: what stops the oscillation?

The 150 MHz (13)C NMR microstructural analysis of polypropylene samples produced with two representative "oscillating" metallocene catalysts of largely different steric hindrance, namely [(2-(3,5-di-tert-butyl-4-methoxyphenyl)indenyl)(2)ZrP](+) and [(2-phenylindenyl)(2)ZrP](+) (P = polymeryl), and the implications on the origin of the stereocontrol are presented and discussed in detail. The original mechanistic proposal of an "oscillation" between a rac-like (isotactic-selective) and a meso-like (nonstereoselective) conformation cannot explain the observed polymer configuration. The isotactic-stereoblock nature of the polymers obtained with the former catalyst proves unambiguously that the active cation "oscillates" between the two enantiomorphous rac-like conformations at an average frequency that, even at high propene concentration, is only slightly lower than that of monomer insertion. The less-hindered [(2-phenylindenyl)(2)ZrP](+) gives instead a largely stereoirregular polypropylene, which is the logical consequence of a faster ligand rotation; however, depending on the use conditions (in particular, on the nature of the cocatalyst and the polarity of the solvent), the polymerization products may also contain appreciable amounts of a fairly isotactic fraction. The peculiar microstructure of this fraction, with isotactic blocks of the same relative configuration spanned by very short atactic ones, rules out the possibility that the latter are due to an active species in meso-like conformation and points rather to a conformationally "locked" rac-like species with restricted ring mobility. The hypothesis of a stereorigidity induced by the proximity to a counteranion, which would play the role of the interannular bridge in the rac-bis(indenyl) ansa-metallocenes, was tested by computer modeling on a [rac-(2-phenylindenyl)(2)ZrMe(C(3)H(6))][B(C(6)F(5))(4)] ion couple and found viable.