Organic metabolites in exhaled human breath—A multivariate approach for identification of biomarkers in lung disorders

The gas chromatographic profiles of exhaled air from lung cancer patients have been investigated. The breath from healthy volunteers, smokers and non-smokers, and lung cancer patients without treatment and under radio and/or chemotherapy, was collected using Tedlar bags. Different profiles for healthy people and cancer patients could be recognized by multivariate analysis and significant diagnostic compounds could be established. Target compounds showed to be linear and branched hydrocarbons between C₁₄ and C₂₄. Solid phase microextraction (SPME) coupled to gas chromatography mass spectrometry GC–(TOF)-MS was used. The method showed good precision (RSD below 26%) and limit of detection ranged from 0.04 to 8.0 ppb. These findings show a high potential for establishment of laboratorial screening methods. Validation studies in a larger number of patients are being done.     

Identification of Ensis siliqua samples and establishment of the catch area using a species-specific microsatellite marker

European Council Regulation 104/2000 states that fishery products must be labeled to indicate commercial designation of species, the production method, and the catch area. Therefore, traceability of seafood implies knowledge of the species offered to retail and their origin. Ensis siliqua is a bivalve intensively fished in Europe and sold in fresh and canned forms. Although several published methods clearly differentiate Ensis genus species, none of those assess the origin of the commercial samples. In the present study, a microsatellite marker (Esi-UDC3055F) was developed to establish the catch area of E. siliqua samples. Amplification yielded a fragment of 275 or 302 base pairs, depending on whether they were Iberian or Irish populations. The usefulness of this method was also assessed in commercial samples. The results of this study provide a reliable methodology for the identification of catch area in European E. siliqua commercial samples. The coupling of this methodology with existing techniques for razor clam species identification provides a powerful tool for traceability and labeling enforcement.     

Influence of the counterion and the solvent molecules in the spin crossover system [Co(4-terpyridone)2]Xp.nH2O

A series of new complexes belonging to the [Co(4-terpyridone)2]X(p) x nS family (4-terpyridone = 2,6-bis(2-pyridyl)-4(1H)-pyridone) have been synthesized and characterized, using X-ray single crystal determination and magnetic susceptibility studies, to be X = [BF4]- (p = 2) and S = H2O for polymorphs 1 and 2, X = [BF4]- (p = 1) and [SiF6]2- (p = 0.5) and S = CH(3)OH for 3, X = [SiF6]2- (p = 1) and S = 3CH3OH and H2O for 4, X = [Co(NCS)4]2- (p = 1) and S = 0.5CH3OH for 5, X = I- (p = 2) and S = 5H2O for 6, X = [PF6]- (p = 1) for 7, and X = [NO3]- (p = 2) for 8. Compounds 1-7 can be grouped in three sets according to the space group in which they crystallize: (i) P1 triclinic (1, 3), (ii) P2(1) monoclinic (2), and (iii) P2(1)/c monoclinic (4-7). The tridentate 4-terpyridone ligands coordinate the Co(II) ions in a mer fashion defining essentially tetragonally compressed [CoN6] octahedrons. The Co-N axial bonds involving the pyridone rings are markedly shorter than the Co-N equatorial bonds collectively denoted as Co-N(central) and Co-N(distal), respectively. The differences in the average Co-N(central) or Co-N(distal) distances observed for 1-7 reflect the different spin states of Co(II). Complexes 7 and 4' are fully high spin (HS), while 5 and 6 are low spin (LS). However, the counterion [Co(NCS)4]2- in complex 5 is high spin. Complexes 1, 2, 3, and 8 exhibit spin-crossover behavior in the 400-100 K temperature region. Compounds 1 and 2 are polymorphs, and interestingly, 1 irreversibly transforms into 2 above 340 K because of a crystallographic phase transition which involves a drastic modification of the crystal packing. The relevant thermodynamic parameters associated with the spin transition of polymorph 2 have been estimated using the regular solution theory leading to DeltaH = 3.04 kJ mol(-1), DeltaS = 20 J K(-1) mol(-1), and Gamma = 0.95 kJ mol(-1).     

Study of the reaction of methyl 4‐nitrobenzenesulfonate and Br− in water–glycerol cationic micellar solutions

The reaction of methyl 4‐nitrobenzenesulfonate (MNB) and Br^? has been studied in water–glycerol (GLY) alkyltrimethylammonium bromide micellar solutions, with the weight percentage of glycerol up to 50%. A pseudophase kinetic model was used for quantitatively discussing the kinetic data. Results showed that the equilibrium‐binding constant for the organic substrate molecules to the cationic micelles decreases upon increasing the amount of glycerol present in the micellar reaction media. The second‐order rate constant of the reaction in the micellar pseudophase is practically independent of wt% of GLY. Similar results were found in other water–organic solvent alkyltrimethylammonium bromide micellar solutions for the same process. However, the dependence of the reaction rate, for a given surfactant concentration, on the wt% of organic solvent is weaker for glycerol than for the other organic solvents. This was explained by considering that the cationic micellar ionization degree is nearly independent of wt% GLY. As a consequence, bromide ions concentration in the interfacial region (the reaction site) does not change by varying wt% of GLY. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 845–582, 2008     

Study of the reaction methyl 4‐nitrobenzene‐sulfonate + Cl− in mixed hexadecyltrimethyl‐ammonium chloride‐triton X‐100 micellar solutions

The reaction methyl 4‐nitrobenzenesulfonate + Cl^? was studied in hexadecyltrimethylammonium chloride (CTAC) in the absence and presence of 0.1 M NaCl, as well as in mixed CTAC/Triton X‐100 (polyoxyethylene(9.5)octylphenyl ether) aqueous micellar solutions with CTAC molar fractions of 0.9, 0.8, 0.7, and 0.6. Conductivity measurements were used to obtain critical micellar concentrations and micellar ionization degrees of the various micellar reaction media. From these data, thermodynamic information on the cationic/nonionic mixed micellar solutions was obtained. Micellar effects on the observed rate constant were explained by pseudophase kinetic models. The estimated second‐order rate constants in the micellar pseudophase of the different micellar reaction media showed that pure CTAC and mixed CTAC/Triton X‐100 micelles, at the high cationic surfactant molar fractions studied, provide reaction sites of similar characteristics at the interfacial region. This was in agreement with previous structural studies carried out on mixed CTAC/Triton X‐100 micellar solutions. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 35: 45–51, 2003     

Characterization of Cr/SiO2 catalysts and ethylene polymerization by XPS

Cr/SiO₂ catalysts with 1 or 3 wt.% Cr loadings and different chromium precursors were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). A method to determine chromium species in the sample was developed through the decomposition of the Cr 2p XPS spectrum in Cr⁶⁺ and Cr³⁺ standard spectra. The results of the binding energy from the Cr 2p region and of the distribution of chromium species allowed to evaluate the dynamic photo-reduction of the surface chromium species during XPS analysis. Photo-reduction of surface Cr⁶⁺ to Cr³⁺ species was verified for all samples supported in silica, depending on the precursor and chromium content. Bulk CrO₃ and Cr₂O₃ standards did not reveal variation in the binding energy of Cr 2p_3/2, but a physical mixture of CrO₃ with SiO₂ presented photo-reduction. The behavior of this mixture resembled to the catalysts and suggests the participation of the surface hydroxyls of silica in the photo-reduction process. XPS intensity measurements for assessing dispersion of chromium oxide were used to compare the calcined and reduced catalysts to different chromium precursors. Polyethylene chains were detected by in situ XPS, while oligomerization products were not observed.     

Use of surface plasmon resonance to study the adsorption of detergents on poly(dimethylsiloxane) surfaces

This paper demonstrates the use of surface plasmon resonance to study adsorption (either reversible or irreversible) of detergents on PDMS surfaces in real time. The surface plasmon resonance measurements can directly provide information about the adsorption/desorption processes of detergents on the surface revealing the durability of the adsorbed layer and the anticipated degree of the EOF. Hydroxypropyl methylcellulose very strongly adsorbs onto PDMS and can be considered both a semipermanent layer and stable semipermanent coating. Adsorbed SDS or CTAB layers were stable for several minutes upon rinsing the surface with solution not containing the detergent. It was shown that SDS coated onto PDMS in microchips has the potential to afford similar separations in PDMS as found in conventional fused silica capillaries.     

Effects of head group size on the reaction methyl 4‐nitrobenzenesulfonate + Br− in water‐ethylene glycol cetyltrialkylammonium bromide micellar solutions

The reaction methyl 4‐nitrobenzenesulfonate + Br^? has been studied in water‐ethylene glycol cetyltrialkylammonium bromide (alkyl = methyl, ethyl, propyl, and butyl) micellar solutions by changing surfactant concentration as well as the weight percentage of ethylene glycol present in the bulk phase. The pseudophase model was adequate to rationalize quantitatively the micellar kinetic effects. Information about the influence of the head group size on the second‐order rate constant of the process and on the binding equilibrium constant of the organic substrate to the cationic micelles in water–ethylene glycol mixtures was obtained. Kinetic data taken from the literature were compared to those obtained in this work in order to examine the different effects produced by an alcohol that is localized in the bulk phase, such as ethylene glycol, with those caused by an alcohol that distributes between the bulk and micellar pseudophases, such as 1‐butanol. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 346–352, 2007     

Determination of Spin State in Dinuclear Iron(II) Coordination Compounds Using Applied Field Mössbauer Spectroscopy

So far there has been no direct method to determine the spin state of molecules in dinuclear iron(II) compounds. The molecular fractions of high spin (HS) and low spin (LS) species have been deduced from magnetic susceptibility and zero field Mössbauer spectroscopy data irrespective of whether they belong to LS-LS, LS-HS and HS-HS pairs. However, the distinction of pairs becomes possible if Mössbauer measurements are carried out in an external magnetic field. The proposed method opens new possibilities in the study of spin crossover phenomena in dinuclear compounds.