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211.
Eloisa Liotta Rossella Gottardo Anna Bertaso Aldo Polettini 《Journal of mass spectrometry : JMS》2010,45(3):261-271
High‐resolution mass spectrometry (HRMS) enables the identification of a chemical formula of small molecules through the accurate measurement of mass and isotopic pattern. However, the identification of an unknown compound starting from the chemical formula requires additional tools: (1) a database associating chemical formulas to compound names and (2) a way to discriminate between isomers. The aim of this present study is to evaluate the ability of a novel ‘metabolomic’ approach to reduce the list of candidates with identical chemical formula. Urine/blood/hair samples collected from real positive cases were submitted to a screening procedure using ESI‐MS‐TOF (positive‐ion mode) combined with either capillary electrophoresis or reversed phase liquid chromatography (LC). Detected peaks were searched against a Pharmaco/Toxicologically Relevant Compounds database (ca 50 500 compounds and phase I and phase II metabolites) consisting of a subset of PubChem compounds and a list of candidates was retrieved. Then, starting from the mass of unknown, mass shifts corresponding to pre‐defined biotransformations (e.g. demethylation, glucuronidation, etc.) were calculated and corresponding mass chromatograms were extracted from the total ion current (TIC) in order to search for metabolite peaks. For each candidate, the number of different functional groups in the molecule was automatically calculated using E‐Dragon software (Talete srl, Milan, Italy). Then, the presence of metabolites in the TIC was matched with functional groups data in order to exclude candidates with structures not compatible with observed biotransformations (e.g. loss of methyl from a structure not bearing methyls). The procedure was tested on 108 pharmaco‐toxicologically relevant compounds (PTRC) and their phase I metabolites were detected in real positive samples. The mean list length (MLL) of candidates retrieved from the database was 7.01 ± 4.77 (median, 7; range, 1–28) before the application of the ‘metabolomic’ approach, and after the application it was reduced to 4.08 ± 3.11 (median 3, range 1–17). HRMS allows a much broader screening for PTRC than other screening approaches (e.g. library search on mass spectra databases). The ‘metabolomic’ approach enables the reduction of the list of candidate isomers. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
212.
Oliviero G Amato J Borbone N D'Errico S Galeone A Mayol L Haider S Olubiyi O Hoorelbeke B Balzarini J Piccialli G 《Chemical communications (Cambridge, England)》2010,46(47):8971-8973
The biophysical and biological properties of unprecedented anti-HIV aptamers are presented. The most active aptamer (1L) shows a significant affinity to the HIV protein gp120. 相似文献
213.
Heroux L Krungleviciute V Calbi MM Migone AD 《The journal of physical chemistry. B》2006,110(25):12597-12602
We present the combined results of a computer simulation and adsorption isotherm investigation of CF4 films on purified HiPco nanotubes. The experimental measurements found two substeps in the adsorption data. The specific surface area of the sample and the coverage dependence of the isosteric heat of adsorption of the films were determined from the measurements. The simulations, conducted for homogeneous bundles of close-ended tubes, also found two substeps in the first layer data: one corresponding to adsorption on the grooves and a second one, at higher pressures, corresponding to adsorption on the outside surface of the tubes. Our computer simulations are in very good agreement with the experimental data. 相似文献
214.
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216.
On subtractive varieties,I 总被引:6,自引:0,他引:6
Aldo Ursini 《Algebra Universalis》1994,31(2):204-222
A varietyV is subtractive if it obeys the laws s(x, x)=0, s(x, 0)=x for some binary terms and constant 0. This means thatV has 0-permutable congruences (namely [0]R ºS=[0]S ºR for any congruencesR, S of any algebra inV). We present the basic features of such varieties, mainly from the viewpoint of ideal theory. Subtractivity does not imply congruence modularity, yet the commutator theory for ideals works fine. We characterize i-Abelian algebras, (i.e. those in which the commutator is identically 0). In the appendix we consider the case of a classical ideal theory (comprising: groups, loops, rings, Heyting and Boolean algebras, even with multioperators and virtually all algebras coming from logic) and we characterize the corresponding class of subtractive varieties.Presented by A. F. Pixley. 相似文献
217.
Sabatini L Barbieri A Tosi M Roda A Violante FS 《Rapid communications in mass spectrometry : RCM》2005,19(2):147-152
8-Hydroxy-2'-deoxyguanosine (8OHdG), one of the major oxidative DNA lesions induced by radical agents, is commonly used as a biomarker for oxidative stress, nowadays preferably in urine. In the absence of a commercially available internal standard a micro-high-performance liquid chromatography/electrospray ionization tandem mass spectrometry (micro-HPLC/ESI-MS/MS) method, suitable for routine analysis of 8OHdG in human urine using external calibration, was developed. Evaluation of the matrix effect showed that the method allows highly sensitive and accurate quantitation despite the absence of an internal standard. HPLC analysis was performed using gradient elution at a flow rate of 10 microL min(-1) using a capillary reversed-phase column and an injection volume of 0.5 microL, with detection of 8OHdG in positive multiple reaction monitoring (MRM) mode. The absolute limit of detection was 0.35 fmol using m/z 168 as a quantifier (fragment) ion. A linear (R2> 0.999) calibration curve in urine was obtained over a range 0.2-10 ng mL(-1). This method is about 20 times more sensitive than previously described procedures, and is characterized by high accuracy (mean 90%) and good reproducibility (RSD <10%). The optimized method was applied to determination of 8OHdG in 18 urinary samples derived from three healthy volunteers. 8OHdG urinary excretion ranged from 3.0-7.9 microg/day, and a large intra-individual variation was found. This method, which effectively circumvents the need for isotopically labeled 8OHdG (internal standard), is suitable for routine monitoring of exposure to DNA-damaging factors in a large number of subjects. 相似文献
218.
Critical micelle concentration (CMC) is a fundamental parameter in the evaluation of the biological activity of natural and synthetic bile salts. The CMC is logarithmically related to the free energy of solute micellization in aqueous solution. Hydrophobic and hydrogen bonding interaction energies were identified as the primary contributors to this free energy and the logarithm of the CMC was modeled as a linear function of relevant chemical group contributions to the solvent accessible molecular surface area of the solute. The structures (three-dimensional atomic coordinates) of 23 mono-, di-, and tri-hydroxyl bile acids were generated and optimized by energy minimization. The accessible surface area for each structure was computed and partitioned according to calculated charge distribution and polar group orientation. Experimental CMC values were fitted to these computed quantities by least squares multiple linear regression. Two regression equations, based on slightly different surface area partition schemes, were derived and compared. Their significance in explaining the aggregation process and in predicting the CMC of new bile salts is discussed. 相似文献
219.
Rosaria Ciajolo Mohamud A. Jama Angela Tuzi Aldo Vitagliano 《Journal of organometallic chemistry》1985,295(2):233-238
The complex η5-[Pd(CH2CHCMeCH2CH2CHCMe2)-(MeCN)](BF4), a model for a key intermediate in diene polymerization, crystallizes in the monoclinic space group P21/c, a 11.362(2), b 13.655(4), c 10.046(2) Å, β 134.80(1)°. The structure was solved by conventional Patterson and Fourier syntheses and refined by full matrix least squares techniques to a final discrepancy index R = 0.058 for 1710 independent reflections. The palladium and nitrogen atoms, the center of gravity of the allyl triangle, and the middle point of the coordinated double bond are coplanar. The side chain of the organic moiety is located in the syn position with respect to the η3-allyl group. The orientation of the coordinated double bond, which forms an angle of 26° with the coordination plane, is novel for palladium(II) complexes. 相似文献
220.
Augusto De Renzi Achille Panunzi Michaelangelo Scalone Aldo Vitagliano 《Journal of organometallic chemistry》1980,192(1):129-132
Amination of PtII-allene complexes of the type cis[PtCl2(Me2CCCHR)(PPh3)] gives the new four-membered C, N chelate aminoalkenyl complexes [Me2(PPh3)Cl]. These undergo ready insertion of carbon monoxide into the CPt σ-bond; the resulting acyl complexes are oxidized by hydrogen peroxide to aminoacidato complexes, and the free unsaturated β-aminoacids can be recovered in good yield by ligand displacement. 相似文献