Multiple tandem mass spectrometry-based investigation of the behaviour of some thiazol-benzimidazolones and 2-benzimidazolylsulfanyl ethanones

The behaviour in electrospray conditions of a series of thiazol-benzimidazolones and 2- benzimidazolylsulphanyl ethanones has been studied by means of multiple tandem mass spectrometry experiments. Even though the experimental conditions were the same, different behaviour is observed for the two classes of compounds. In the case of thiazol-benzimidazolones, the formation of a protonated complex with CH3OH employed as solvent is observed, but in the case of 2-benzimidazolylsulphanyl ethanones the formation of MNa+ ions is privileged. This behaviour has been related to molecular structure. The collisionally-induced decompositions of MH+ ions have been rationalised in terms of the Stevenson-Audier and even-electron rules, as well as on the basis of proton affinity data. Thus, protonated thiazol-benzimidazolones undergo facile loss of CO and a series of different decomposition pathways involving cleavage of the thiazolone ring that reflect the structure of the neutral fragments. In contrast, the decompositions of the protonated 2-benzimidazolylsulphanyl ethanones are mainly related to the piperazine moiety, suggesting that the protonation takes place on this substructural unit.     

Some remarks on factoriality of certain hypersurfaces in \mathbb{P}^4

Let V be a reduced and irreducible hypersurface of degree k 3. In this paper we prove that if the singular locus of V consists of ₂ ordinary double points, ₃ ordinary triple points and if ₂ + 4₃ < (k – 1)², then any smooth surface contained in V is a complete intersection on V.Received: 7 January 2004     

A Lower Bound for the Height of a Rational Function at S-unit Points

Let a,b be given, multiplicatively independent positive integers and let >0. In a recent paper jointly with Y. Bugeaud we proved the upper bound exp(n) for g.c.d.(aⁿ–1, bⁿ–1); shortly afterwards we generalized this to the estimate g.c.d.(u–1,v–1)<>u,v) for multiplicatively independent S-units u,vZ. In a subsequent analysis of those results it turned out that a perhaps better formulation of them may be obtained in terms of the language of heights of algebraic numbers. In fact, the purposes of the present paper are: to generalize the upper bound for the g.c.d. to pairs of rational functions other than {u–1,v–1} and to extend the results to the realm of algebraic numbers, giving at the same time a new formulation of the bounds in terms of height functions and algebraic subgroups of G_m².     

Variations on Weyl's theorem

In this note we study the property (w), a variant of Weyl's theorem introduced by Rako?evi?, by means of the localized single-valued extension property (SVEP). We establish for a bounded linear operator defined on a Banach space several sufficient and necessary conditions for which property (w) holds. We also relate this property with Weyl's theorem and with another variant of it, a-Weyl's theorem. We show that Weyl's theorem, a-Weyl's theorem and property (w) for T (respectively T^*) coincide whenever T^* (respectively T) satisfies SVEP. As a consequence of these results, we obtain that several classes of commonly considered operators have property (w).     

Hermitian matrices and cohomology of Kähler varieties

We give some upper bounds on the dimension of the kernel of the cup product map $H^{1}(X,\mathbb{C}) \otimes H^{1}(X,\mathbb{C}) \to H^{2}(X,\mathbb{C})We give some upper bounds on the dimension of the kernel of the cup product map , where X is a compact K?hler variety without Albanese fibrations.     

Capillary electrophoresis–electrospray mass spectrometry and HR–ICP–MS for the detection and quantification of 10B-boronophenylalanine (10B–BPA) used in boron neutron capture therapy

Boron neutron capture therapy (BNCT) is a bimodal radiotherapeutic treatment based on the irradiation of neoplastic tissues with neutrons after the tissues have selectively accumulated molecules loaded with nuclides with large neutron capture cross-sections (such boron-10). Boron-10 carriers have been tested to a limited extent, and clinical trials have been conducted on sulfhydryl borane (¹⁰B-BSH) and boronophenylalanine (¹⁰B-BPA). However, precise and accurate measurements of boron-10 concentrations (0.1–100 μg/g) in specimens and samples of limited size (μg scale) are needed in order to be able to biologically characterise new compounds in predictive tissue dosimetry, toxicology and pharmacology studies as well as in clinical investigations. A new approach based on fast separation and detection of ¹⁰B-BPA performed by coupling capillary electrophoresis to electrospray mass spectrometry is reported. This method allows the quantitative analysis and characterisation of ¹⁰B-BPA in a short time with a high separation efficiency. Detection limits of 3 μM for ¹⁰B-BPA and 30 ng/mL for ¹⁰B were obtained with CE–ESI–MS. A quantification limit of 10 μM for ¹⁰B-BPA (100 ng/mL for ¹⁰B) was attained. The total boron-10 concentration was determined by high-resolution inductively coupled mass spectrometry in order to validate the method. Boron-10 isotope measurements were carried out by HR–ICP–MS at medium resolution (R=4000) due to the presence of an isobaric interference at mass 10. Good agreement was obtained between the values from CE–ESI–MS and those from HR–ICP–MS. The method has been successfully used to determine the ¹⁰B-BPA in two lines of cultured cells.     

Phenol production in benzene/air plasmas at atmospheric pressure. Role of radical and ionic routes

Benzene can be efficiently converted into phenol when it is treated by either corona or dielectric barrier discharge (DBD) plasmas operating at atmospheric pressure in air or mixtures of N(2) and O(2). Phenol produced by corona discharge in an atmospheric pressure chemical ionization source (APCI) has been detected as the corresponding radical cation C(6)H(5)OH(+*) at m/z 94 by an ion trap mass spectrometer. On the other hand, phenol has been observed also as neutral product by gas chromatography-mass spectrometry analysis (GC-MS) after treatment in a DBD plasma. Experiments aimed at shading light on the elementary processes responsible for benzene oxidation were carried out (i) by changing the composition of the gas in the corona discharge source; (ii) by using isotopically labeled reagents; and (iii) by investigating some relevant ion-molecule reactions (i.e. C(6)H(6)(+*) + O(2), C(6)H(5)(+) + O(2)) via selected guided ion beam measurements and with the help of ab initio calculations. The results of our approach show that ionic mechanisms do not play a significant role in phenol production, which can be better explained by radical reactions resulting in oxygen addition to the benzene ring followed by 1,2 H transfer.