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71.
Current work has evaluated uncertainty associated to quantification of several organic compounds present in particulate matter of atmospheric aerosols, setting out the stages of analytical procedure that contribute most to the global uncertainty. Several sources of uncertainty have been identified, which were clustered into five main contributions: sampling, extraction, clean-up, derivatization and analysis. A discussion of the main contributions to the overall uncertainty is reported, allowing authors to locate the largest ones and plan future improvements. Combined uncertainties ranged between 10-18% (alkanes), 12-16% (PAHs), 10-18% (alcohols) and 9-21% (acids). The analytical procedure was validated by analysing a standard reference material (SRM1649a, urban dust). Also, the proposed method was applied to the analysis of four samples of particulate matter. 相似文献
72.
Three new compounds bearing furyl, aryl, or thienyl moieties linked to an imidazo-crown ether system (1, 2, and 3) were synthesized and fully characterized by elemental analysis, infrared, UV-vis absorption, and emission spectroscopy, X-ray crystal diffraction, and MALDI-TOF-MS spectrometry. The interaction toward metal ions (Ca(2+), Cu(2+), Ni(2+), and Hg(2+)) and F(-) has been explored in solution by absorption and fluorescence spectroscopy. Mononuclear and binuclear metal complexes using Cu(2+) or Hg(2+) as metal centers have been synthesized and characterized. Compounds 2 and 3 show a noticeable enhancement of the fluorescence intensity in the presence of Ca(2+) and Cu(2+) ions. Moreover compound 3 presents a dual sensory detection way by modification of the fluorimetric and colorimetric properties in the presence of Cu(2+) or Hg(2+). EPR studies in frozen solution and in microcrystalline state of the dinuclear Cu(II)3 complex revealed the presence of an unique Cu(2+) type. 相似文献
73.
de la Pinta N Martín S Urtiaga MK Barandika MG Arriortua MI Lezama L Madariaga G Cortés R 《Inorganic chemistry》2010,49(22):10445-10454
The family of compounds [Mn(dca)(2)(bpa)] (1), [Fe(dca)(2)(bpa)] (2), [Co(dca)(2)(bpa)] (3), [Zn(dca)(2)(bpa)] (4), and [Ni(dca)(bpa)(2)]dca·6H(2)O (5), with dca = dicyanamide and bpa = 1,2-bis(4-pyridyl)ethane, has been synthesized. These compounds have been characterized by single crystal (1, 2, 4, and 5) and powder X-ray diffraction (3), by Fourier transform infrared (FTIR), UV-vis, and electron paramagnetic resonance (EPR) spectroscopies, and by magnetic measurements. Compound 1 crystallizes in the monoclinic C2/c space group, Z = 4, with a = 16.757(6), b = 9.692(3), and c = 13.073(4) ?, and β = 123.02(2)°; Compound 2 crystallizes in the monoclinic C2/c space group, Z = 4, with a = 16.588(5), b = 9.661(3), c = 12.970(5) ?, and β = 123.16(3)°; Compound 4 crystallizes in the monoclinic C2/c space group, Z = 4, with a = 16.519(2), b = 9.643(2), c = 12.943(2) ?, and β = 123.15(1)°; Compound 5 crystallizes in the monoclinic C2/c space group, Z = 4, with a = 18.504(4), b = 19.802(3), and c = 8.6570(18) ?, and β = 99.74(2)°. The compounds 1-4 are isostructural and show a one dimensional (1D) disposition, with the metal(II) ions bridged by double μ(1,5) dca ligands and unusually by a third bridge consisting of the bpa ligand, which adopts a very low torsion angle to accommodate in the structure. This kind of structure is unusual, even considering the voluminous bpa bridge. The compound 5 shows a 3D structure with layers of Ni-bpa joined by single dca bridges. Magnetic susceptibility measurements show antiferromagnetic couplings, increasing for 1-3. Compound 5 shows very slight antiferromagnetic interactions. 相似文献
74.
Kinetic and mechanistic aspects of the vitamin B2 (riboflavin [Rf])-sensitized photo-oxidation of the imidazoline derivates (IDs) naphazoline (NPZ) and tetrahydrozoline (THZ) were investigated in aqueous solution. The process appears as important on biomedical grounds, considering that the vitamin is endogenously present in humans, and IDs are active components of ocular medicaments of topical application. Under aerobic visible light irradiation, a complex picture of competitive interactions between sensitizer, substrates and dissolved oxygen takes place: the singlet and triplet (3 Rf*) excited states of Rf are quenched by the IDs: with IDs concentrations ca. 5.0 m m and 0.02 m m Rf, 3 Rf* is quenched by IDs, in a competitive fashion with dissolved ground state oxygen. Additionally, the reactive oxygen species: O2 (1 Δg ), O2 •− , HO• and H2 O2 , generated from 3 Rf* and Rf •− , were detected with the employment of time-resolved methods or specific scavengers. Oxygen uptake experiments indicate that, for NPZ, only H2 O2 was involved in the photo-oxidation. In the case of THZ, O2 •− , HO• and H2 O2 were detected, whereas only HO• was unambiguously identified as THZ oxidative agents. Upon direct UV light irradiation NPZ and THZ generate O2 (1 Δg. ), with quantum yields of 0.2 (literature value, employed as a reference) and 0.08, respectively, in acetonitrile. 相似文献
75.
Marcio Vidotti Vinícius R. Gonçales Vinicius S. Quartero Barbara Danc Susana I. Córdoba de Torresi 《Journal of Solid State Electrochemistry》2010,14(4):675-679
The present work describes the synthesis of platinum nanoparticles followed by their electrophoretic deposition onto transparent
fluorine-doped tin oxide electrodes. The nano-Pt-modified electrodes were characterized by voltammetric studies in acidic
solutions showing a great electrocatalytic behavior towards H+ reduction being very interesting for fuel cell applications. Morphological characterization was performed by atomic force
microscopy on different modified electrodes showing a very rough surface which can be tuned by means of time of deposition.
Also, nickel hydroxide thin films were galvanostatically grown onto these electrodes showing an interesting electrochemical
behavior as sharper peaks, indicating a faster ionic exchange from the electrolyte to the film. 相似文献
76.
77.
Pedro R. Aranda Susana Moyano Luis D. Martinez Irma E. De Vito 《Analytical and bioanalytical chemistry》2010,398(2):1043-1048
A new, simple, and selective method for preconcentration and determination of Cr(VI) in aqueous samples. After adsorption
in “batch mode” on Aliquat 336-AC, determinations were made directly on the solid by X-ray fluorescence spectrometry, which
had the advantage of not requiring the step of elution of the chromium retained. The enrichment factor was calculated considering
that the tablets obtained from 10 mL solution of Cr(VI) (1000 μg L-1) had a final thickness of 0.64 mm and a diameter of 16.7 mm; the volume deposited on the pellet was 0.14 cm3. The preconcentration factor obtained was 71-fold, which was highly satisfactory for chromium trace analysis by XRF. Finally,
the method was successfully applied to the determination of Cr(VI) in drinking water samples. 相似文献
78.
Classification of wines from five Spanish origin denominations by aromatic compound analysis 总被引:1,自引:0,他引:1
Wine is a complex matrix in which aroma compounds play an important role in the characterization of the flavor pattern of a given wine. Twelve volatile compounds were determined in 244 samples of Spanish red wines from different denominations of origin: Rioja, Navarra, Valdepe?as, La Mancha, and Cari?ena. The samples were analyzed by GC using headspace solid-phase microextraction. The concentration (mg/mL) intervals obtained were 3-methyl-butyl acetate (3.9 to 116), 3-methyl-1-butanol (93 to 724), ethyl hexanoate (0.8 to 39), 1-hexanol (0.3 to 6.7), ethyl octanoate (1.4 to 41), diethyl succinate (0.2 to 13), 2-phenyl ethyl acetate (0 to 5.3), hexanoic acid (0 to 8.3), geraniol (0 to 3.0), 2-phenylethanol (1.5 to 56), octanoic acid (0 to 20), and decanoic acid (0 to 3.3). Wines were classified by multivariate statistical methods: principal component analysis, and lineal discriminant analysis. A correct differentiation among wines according to their origin was obtained by lineal discriminant analysis. 相似文献
79.
Jonathan P. Williams Hazel I. A. Phillips Iain Campuzano Peter J. Sadler 《Journal of the American Society for Mass Spectrometry》2010,21(7):1097-1106
The three-dimensional conformation of a protein is an important property and plays a key role in its biological activity.
We show here that ion mobility-mass spectrometry (IM-MS) can be used to detect conformational changes in the protein ubiquitin
in the gas phase induced by reaction with the anticancer drug cisplatin. The primary adduct was ubiquitin-{Pt(NH3)2} under denaturing conditions. Up to three different conformations appear to be generated upon platination depending on the
charge state. The collision cross-sections (Ω) for each conformation indicate that the conformations of the platinated protein
are contracted in size compared with unmodified ubiquitin with generally smaller Ω values. Ion mobility-tandem MS allowed
determination of the platinum binding site without a requirement for prior Chromatographic separation. A rapid 30-min digestion
of cisplatin-modified ubiquitin with trypsin allowed the platination site to be identified as the N-terminal methionine following
low-energy collision-induced dissociation (CID) studies of the modified peptide. The data were generated using a Traveling-Wave
based ion mobility-MS approach. Such cisplatin-induced shape changes may have a significant effect on its function in vivo.
This work highlights the usefulness of the ion-mobility mass spectrometry technique for shedding new light on such protein
interactions. 相似文献
80.
Mata S Cortijo V Caminati W Alonso JL Sanz ME López JC Blanco S 《The journal of physical chemistry. A》2010,114(43):11393-11398
The Fourier transform microwave spectra of the hydrated forms of the tautomeric pair 2-pyridinone/2-hydroxypyridine (2PO/2HP) have been investigated in a supersonic expansion. Three hydrated species, 2PO-H?O, 2HP-H?O, and 2PO-(H?O)?, have been observed in the rotational spectrum. Each molecular complex was confidently identified by the features of the 1?N quadrupole hyperfine structure of the rotational transitions. The presence of water affects the tautomeric equilibrium -N═C(OH)- ? -NH-C(═O)-, which is shifted to the enol form for the bare molecules 2PO/2HP but to the keto tautomer for the hydrated forms. 相似文献