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51.
A. Gustavo González M. Ángeles Herrador Agustín G. Asuero 《Accreditation and quality assurance》2005,10(7):386-391
The uncertainty evaluation of mass measurements when using “in-house” calibrated analytical balances is revisited according
to the Guide to the expression of Uncertainty Measurement (GUM). The calibration of analytical balances is discussed according
to the guidelines of several bodies such as ASTM, UKAS and DKD/PTB. The remainder components of uncertainty can be estimated
from the balance data sheet specifications. 相似文献
52.
A laser flash photolysis and pulse radiolysis study of primary photochemical processes of flumequine
Bazin M Bosca F Marin ML Miranda MA Patterson LK Santus R 《Photochemistry and photobiology》2000,72(4):451-457
The 355 nm laser flash photolysis of argon-saturated pH 8 phosphate buffer solutions of the fluoroquinolone antibiotic flumequine produces a transient triplet state with a maximum absorbance at 575 nm where the molar absorptivity is 14,000 M(-1) cm(-1). The quantum yield of triplet formation is 0.9. The transient triplet state is quenched by various Type-1 photodynamic substrates such as tryptophan (TrpH), tyrosine, N-acetylcysteine and 2-deoxyguanosine leading to the formation of the semireduced flumequine species. This semireduced form has been readily identified by pulse radiolysis of argon-saturated pH 8 buffered aqueous solutions by reaction of the hydrated electrons and the CO2*- radicals with flumequine. The absorption maximum of the transient semireduced species is found at 570 nm with a molar absorptivity of 2,500 M(-1) cm(-1). In argon-saturated buffered solutions, the semireduced flumequine species formed by the reaction of the flumequine triplet with TrpH stoichiometrically reduces ferricytochrome C (Cyt Fe3+) under steady state irradiation with ultraviolet-A light. In the presence of oxygen, O2*- is formed but the photoreduction of Cyt Fe3+ by O2*- competes with an oxidizing pathway which involves photo-oxidation products of TrpH. 相似文献
53.
A robust tandem HPLC method coupling size-exclusion (Shodex Asahipak GS-320HQ) and reversed phase (Vydac 218TP54) columns with ultraviolet detection was developed for quantitative determination of interferon-gamma (IFN-gamma) in Chinese hamster ovary cell culture supernatant. The 2D-HPLC system was linked up by a 6-port 2-position low hold-up volume switch valve. Compared to a commercial ELISA kit for IFN-gamma, the coupled column LC approach was able to detect and quantify soluble IFN-gamma, regardless of the glycoprotein's molecular/conformational variability and sample background. Each LC-LC analysis took 90 minutes inclusive of column regeneration. The relative standard deviation of measurements (n = 5) was less than 3%. The limit of detection (LOD) was determined to be 0.35 microg IFN-gamma. 相似文献
54.
55.
The 2,2-diphenylcyclopropyl group was employed to accelerate reactions of alpha-methoxy radicals containing beta-leaving groups, to trap the products of either migration or heterolysis of the leaving group, and to provide a useful chromophore for laser flash photolysis kinetic studies. The reporting group biases reactions in favor of heterolytic fragmentation and most likely intercepts radical cations in ion pairs. The 1-methoxy-1-methyl-2-(diethylphosphatoxy)-2-(2,2-diphenylcyclopropyl)ethyl radical (3a) reacted faster than the kinetic resolution of the instrument (k > 2 x 10(8) s(-1)) in all solvents studied, and the 2-acetoxy analogue (3b) reacted much faster than related radicals that do not contain the cyclopropyl group (e.g., k = 1.1 x 10(6) s(-1) in CH3CN at ambient temperature). The rate constants and Arrhenius parameters for reactions of 3b indicated that the rate-limiting step in the reaction was heterolytic cleavage. The 1,2-dimethoxy-1-methyl-2-(2,2-diphenylcyclopropyl)ethyl radical (26) reacted in a general acid-catalyzed heterolysis reaction, and rate constants for protonation of the beta-methoxy group by a series of carboxylic acids were determined. The results suggest that acid-catalyzed reactions of beta-alkoxy radicals might be employed in synthetic conversions. 相似文献
56.
A Laplace Transform (LT) method is used to improve the results obtained in a quasi-elastic scattering (QELS) experiment. This is designed to determine the characteristic parameters of a bimodal solution of spherical and rod-like macromolecules. The theoretical study and the experimental simulation are carried out for low light levels and the results show that the LT technique provides a real alternative to the second order correlation function, g(2)(τ), in QELS measurements for these particularly difficult experimental conditions. 相似文献
57.
58.
M. C. Villa-lojo E. Beceiro-GonzÁlez E. Alonso-Rodríguez D. Prada-Rodríguez 《International journal of environmental analytical chemistry》2013,93(3):377-389
Abstract The speciation of arsenic in the environment is among others controlled by reduction, methylation and oxidation processes and therefore influenced by the prevailing redox conditions. In this study we have analyzed sediments taken from La Coruña estuary in the north west of Spain. Inorganic (trivalent and pentavalent) and the organic (MMA and DMA) arsenic speciation is related to Eh, Fe and Mn load. The various of the arsenic species concentration and other parameters was analyzed at different depths in some of the sampling points. Low arsenic concentrations (1–10 μg·g–1) were found. In spite of oxidising conditions (Eh values between 31–96 mV), most of the samples showed a higher As(V) percentage than As (III). Principal component analysis was made to see a sample groups and the results showed that speciation depends on reducing conditions (Eh and Mn). 相似文献
59.
Unexpected reactivity of pyridinium salts toward alkynyl Fischer complexes to produce oxo‐heterocycles
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María Inés Flores‐Conde Fabiola N. de la Cruz Julio López J. Óscar C. Jiménez‐Halla Eduardo Peña‐Cabrera Marcos Flores‐Álamo Francisco Delgado Miguel A. Vázquez 《应用有机金属化学》2018,32(3)
The unprecedented reaction of ketone‐containing aromatic pyridinium salts 3a ‐ e and alkynyl Fischer complexes 1a ‐ f proceeds via a mild domino process to provide 4,6‐disubstituted pyran‐2‐ones 5a ‐ k and 2,3,5‐trisubstituted furans 6a ‐ h (45‐97%). According of the results of isotopic labeling experiments, a mechanism involving an initial Michael addition appears to be the key step, obtaining a mesomeric structure responsible for the formation of both products. 相似文献
60.
Dr. Lina M. Aguirre-Díaz Marcelo Echeverri Dr. Katherine Paredes-Gil Dr. Natalia Snejko Dr. Berta Gómez-Lor Prof. Dr. Enrique Gutiérrez-Puebla Prof. Dr. M. Ángeles Monge 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(16):5298-5306
Three new cadmium-based coordination polymers, denoted [Cd(hfipbb)(4,4’-bipy)] ( CdPF-1 ), [Cd(hfipbb)(2,2’-bipy)] ( CdPF-2 ), and [Cd(hfipbb)(1,10-phen)] ( CdPF-3 ), have been hydrothermally synthesized by using the well-known V-shaped organic linker 4,4’-(hexafluoroisopropylidene)bis(benzoic acid) (H2hfipbb), together with different nitrogenated auxiliary linkers. Considering the d10 configuration of the transition metal selected, the luminescent properties for these CdPF-n materials were explored, finding that materials CdPF-2 and CdPF-3 act as excellent sensors in the detection of explosive nitro aromatic compounds. The photoluminescence properties of CdPF-2 and CdPF-3 revealed that significant and sensitive fluorescence quenching was observed toward NP (nitrophenol) for CdPF-2 and PA (picric acid) for CdPF-3 in MeOH suspensions. 相似文献