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121.
González-Gago A Brandsma SH Leonards PE de Boer J Marchante-Gayón JM Garcia Alonso JI 《Analytical and bioanalytical chemistry》2011,401(8):2639-2649
A gas chromatography electron capture negative ionization mass spectrometry (GC(ECNI)MS) procedure for the determination of
priority polybrominated diphenyl ethers (PBDEs; congeners 28, 47, 99, 100, 153 and 154) in water samples at regulatory EU
levels has been developed. The method is based on the use of 81Br-labelled PBDEs for isotope dilution analysis and the measurement of 79Br/81Br isotope ratios in gas chromatography peaks with the electron capture negative ionization technique. The suitability of
this ion source for the precise and accurate measurement of bromine isotope ratios has been demonstrated. The general ECNI-IDMS
procedure was evaluated by the analysis of NIST SRM 1947 (Lake Michigan fish tissue) with satisfactory results. For the analysis
of water samples, 500 mL of the samples were spiked with the labelled PBDEs and extracted with 10 mL isooctane for 30 min.
The extract was evaporated down to ca. 100 μL and injected in the GC(ECNI)MS. Detection limits ranged from 0.014 −1 to 0.089 pg mL−1 depending on the congener. Recoveries from real water samples, spiked at a level of 0.5 pg mL−1, ranged from 77% to 102%. 相似文献
122.
Aloe plants have been widely documented in artists’ treatises dating from the sixteenth to the nineteenth century as a source
of colorant to achieve lustrous golden glazes on tin- and silver-foiled objects and warm-toned finishes on musical instruments,
such as violins. Aloe extracts contain characteristic anthraquinone and phenolic components which impart a distinctive orange
tone and fluorescence to mixtures containing them. Because of the low concentration of colorant in the coatings and its probable
degradation by high temperature during manufacture, the identification of aloe in heated oil–resin mixtures represents an
analytical challenge. For this reason, the possible presence of aloe in glazes and coatings has been largely overlooked. This
paper describes various analytical approaches to the identification of aloe in historic samples, from comparison with results
obtained from reference standards and mock-up samples. Complementary analytical techniques including thermally assisted hydrolysis
and methylation–gas chromatography–mass spectrometry, high-performance liquid chromatography, laser desorption–mass spectrometry,
matrix-assisted laser desorption-ionization-mass spectrometry and surface-enhanced Raman scattering were used. Different chemical
markers were identified by the individual methods and the advantages and limitations of each technique for the identification
of aloe in oil–resin varnishes are discussed. 相似文献
123.
Fu R Wang X Li C Santiago-Miranda AN Pielak GJ Tian F 《Journal of the American Chemical Society》2011,133(32):12370-12373
The feasibility of using solid-state magic-angle-spinning NMR spectroscopy for in situ structural characterization of the LR11 (sorLA) transmembrane domain (TM) in native Escherichia coli membranes is presented. LR11 interacts with the human amyloid precursor protein (APP), a central player in the pathology of Alzheimer's disease. The background signals from E. coli lipids and membrane proteins had only minor effects on the LR11 TM resonances. Approximately 50% of the LR11 TM residues were assigned by using (13)C PARIS data. These assignments allowed comparisons of the secondary structure of the LR11 TM in native membrane environments and commonly used membrane mimics (e.g., micelles). In situ spectroscopy bypasses several obstacles in the preparation of membrane proteins for structural analysis and offers the opportunity to investigate how membrane heterogeneity, bilayer asymmetry, chemical gradients, and macromolecular crowding affect the protein structure. 相似文献
124.
Aubert V Ordronneau L Escadeillas M Williams JA Boucekkine A Coulaud E Dragonetti C Righetto S Roberto D Ugo R Valore A Singh A Zyss J Ledoux-Rak I Le Bozec H Guerchais V 《Inorganic chemistry》2011,50(11):5027-5038
A series of cationic Ir(III) substituted bipyridyl ()(N(∧)N (N(∧)N-bpy) complexes incorporating electron-donor and -acceptor substituents, [Ir(C(∧)N-ppy-R')(2)(N(∧)N-bpy-CH═CH-C(6)H(4)-R)][X] (X(-) = PF(6)(-) or C(12)H(25)SO(3)(-)), 2 (a, R = NEt(2) and R' = Me; b, R = O-Oct and R' = Me; c, R = NO(2) and R' = C(6)H(13); C(∧)N-ppy = cyclometalated 2-phenylpyridine, [Ir(C(∧)N-ppy-Me)(2)(N(∧)N-bpy-CH═CH-thienyl-Me)][PF(6)], 2d, and the dithienylethene (DTE)-containing complex 2e have been synthesized and characterized, and their absorption, luminescence, and quadratic nonlinear optical (NLO) properties are reported. Density functional theory (DFT) and time-dependent-DFT (TD-DFT) calculations on the complexes facilitate a detailed assignment of the excited states involved in the absorption and emission processes. All five complexes are luminescent in a rigid glass at 77 K, displaying vibronically structured spectra with long lifetimes (14-90 μs), attributed to triplet states localized on the styryl-appended bipyridines. The second-order NLO properties of 2a-d and related complexes 1a-d with 1,10-phenanthrolines have been investigated by both electric field induced second harmonic generation (EFISH) and harmonic light scattering (HLS) techniques. They are characterized by high negative EFISH μβ values which decrease when the ion pair strength between the cation and the counterion (PF(6)(-), C(12)H(25)SO(3)(-)) increases. The EFISH response is mainly controlled by metal-to-ligand charge-transfer/ligand-to-ligand charge-transfer (MLCT/L'LCT) processes. A combination of HLS and EFISH techniques is used to evaluate both the dipolar and octupolar contributions to the total quadratic hyperpolarizability, demonstrating that the major contribution is controlled by the octupolar part. The incorporation of a photochromic DTE unit into the N(∧)N-bpy ligand (complex 2e) allows the luminescence to be switched ON or OFF. The photocyclisation of the DTE unit can be triggered by using either UV (365 nm) or visible light (430 nm), leading to an efficient quenching of the ligand-based 77 K luminescence, which can be restored upon irradiation of the closed form at 715 nm. In contrast, no significant modification of the EFISH μβ value is observed upon photocyclization, suggesting that the quadratic NLO response is dominated by the MLCT/L'LCT processes, rather than by the intraligand excited states localized on the substituted bipyridine ligand. 相似文献
125.
Gomez AG de Silveira G Doan H Cheng CH 《Chemical communications (Cambridge, England)》2011,47(20):5876-5878
We demonstrate an alternative route to tune the morphology of zeolite L crystals using C(2)H(5)OH as the co-solvent in the synthesis gel. A low aspect ratio (0.2 to 0.4) of zeolite L crystals was obtained at lower synthesis temperature (150 °C) and shorter synthesis duration (3 days). 相似文献
126.
We prove that the fields of asymptotic lines of a real hyperbolic homogeneous polynomial are isotopic to the corresponding fields of its hyperbolic homogeneous part. We also show some combinatorial identities which are related to such isotopy. 相似文献
127.
Inhibitive properties of the antibacterial sulfa drug sulfathiazole—IUPAC name being 4-amino-N-(1,3-thiazol-2-yl) benzene sulfonamide—on the corrosion of carbon steel in 1.0 M HCl solution were investigated using weight loss measurements, electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). Sulfathiazole is a good adsorption inhibitor, and the inhibition efficiency increases with increasing concentration. Adsorption is spontaneous and is best described by Temkin isotherm. XPS analysis showed, at this stage, that the main product of corrosion is a nonstoichiometric Fe3+ oxide/oxyhydroxide consisting of a mixture of Fe2O3, α, and γ-FeO(OH) and/or Fe(OH)3, where α, γ-FeO(OH) is the main phase. 相似文献
128.
Hui Ming Jin Adriana Felix Majorri Aroyave 《中国化学快报》2007,18(5):577-580
The isothermal and cyclic oxidizing kinetics of Co-40Cr alloy and its lanthanum ion-implanted samples were studied at 1000℃ in air by thermal-gravity analysis (TGA). Scanning electronic microscopy (SEM) and transmission electronic microscopy (TEM)) were used to examine the oxidized film's morphology and the structure after oxidation. Secondary ion mass spectrum (SIMS) method was used to examine the binding energy change of chromium caused by La-doping and its in?uence on formation of Cr2O3 film. Laser Raman spectrum was used to examine the tress changes within oxidized films. It was found that lanthanum implantation remarkably reduced the isothermal oxidizing rate of Co-40Cr and improved the anti-cracking and anti-spalling properties of Cr2O3 film. The reasons were that the implanted lanthanum reduced the grain size and internal stress of Cr2O3 oxide, increased the high temperature plasticity of oxidized film. Lanthanum mainly existed in the outer surface of Cr2O3 film in the forms of fine La2O3 and LaCrO3 spinel particles. 相似文献
129.
A new on-line Gd preconcentration and determination system associated to flow injection (FI) method was developed. 2,2′-(1,8-dihydroxy-3,6-disulfonaphthylene-2,7-bisazo) bisbenzenearsonic acid (Arsenazo III) was used as a complexing agent at pH 2.5. A reactor containing the polyamide membrane was used for the retention of the Gd complex by chemofiltration. The complex was then removed from the reactor with buffer solution pH 9. The variables affecting the combined on-line preconcentration-absorptiometric method have been evaluated and optimised. The coupling of the on-line preconcentration and spectrophotometric flow through detection led to a detection limit of 15 μg l−1 for a preconcentration time of 5 min at 2 ml/min. The method was successfully applied to biological samples. 相似文献
130.
Adriana Vlez Feij Maria Alice Parente Mara Behlau Srgio Haussen Maria Cecília De Veccino Beatriz Castellar de Faria Martignago 《Journal of voice》2004,18(3):341-347
The objective is to investigate the presence of dysphonic symptoms in multiple sclerosis (MS) patients and to compare quantitative acoustic parameters in multiple sclerosis patients and normal individuals. The method of study was an 8-month controlled cross-sectional that was carried out with 106 individuals (30 MS, 76 controls). Both groups included males and females from 20 to 55 years. Exclusion criteria were prior vocal disorder, laryngeal microsurgery, recent endotracheal intubation, tumors, laryngeal, lung or mediastinal metastases, respiratory disease, and other associated neurological diagnoses. For dysphonic symptoms (qualitative variables), associations were assessed using Mantel-Haenszel's chi2 test, with Yates correction or the Fisher exact test when necessary. Statistical significance was set at p< or =0.05. Dysphonia was observed in 70% of MS individuals versus 33% of controls (p=0.01). Association was found between MS and dysphonia (OR: 2.2, CI 95%: 1.13-4.25). Fundamental frequency was higher among MS patients (p=0.01). Fundamental frequency deviation was significantly higher in MS women (but not men) than controls (p=0.00). Jitter was higher in MS men than in all other groups (p=0.00). Results suggest that evaluation and treatment of MS patients should be revised, evaluating voice alterations in relation to other signs. MS seems to intensify gender effect on fundamental frequency deviation, noise, and jitter, with MS women presenting fewer voice variations than men. 相似文献