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81.
Benn TM Pycke BF Herckes P Westerhoff P Halden RU 《Analytical and bioanalytical chemistry》2011,399(4):1631-1639
There is a growing concern about the human and environmental health effects of fullerenes (e.g., C(60)) due to their increasing application in research, medicine, and industry. Toxicological and pharmacokinetic research requires standard methods for extraction and detection of fullerenes from biological matrices such as urine. The present study validates the use of liquid-liquid extraction (LLE) and solid-phase extraction (SPE) methods in conjunction with liquid chromatography-mass spectrometry (LC-MS) for the quantitative determination of C(60) in human and synthetic urine as compared with ultrapure water. Glacial acetic acid, which is necessary to prevent emulsions during LLE, inhibited C(60) detection by LC-MS, but this could be mitigated with evaporation. Aqueous C(60) aggregates (nC(60)) were spiked at 180 μg/L into the components of a synthetic urine recipe to determine their individual impacts on extraction and detection. Urea, creatinine, and a complex protein (i.e., gelatin) were found to impair SPE, leading to a low recovery rate of 43 ± 4% for C(60) spiked into human urine. In contrast, C(60) was consistently recovered from synthetic matrices using LLE, and recovery in human urine was 80 ± 6%. These results suggest that LLE combined with LC-MS is suitable for studying the clearance of fullerenes from the body. LLE is a robust technique that holds promise for extracting C(60) from other complex biological matrices (e.g., blood, sweat, amniotic fluid) in toxicological studies, enabling a better understanding of the behavior of fullerenes in human and animal systems and facilitating a more comprehensive risk evaluation of fullerenes. 相似文献
82.
A method for the quantitative determination of non-steroidal anti-inflammatory drugs (NSAIDs) in sewage sludge was developed and validated. The target compounds were extracted using pressurized hot water extraction (PHWE) and then purified and preconcentrated by three-phase hollow fiber liquid phase microextraction (HF-LPME) followed by LC–ESI-MS analysis. The PHWE was optimized with regard to the pH of solvent as well as other operational parameters. The optimum conditions were 0.01 M NaOH as the extraction solvent, temperature of 120 °C, pressure of 100 bar, static time 5 min, 5 cycles, flush volume 90% and purge time 60 s. Spike recoveries for sludge samples spiked at 200 ng g−1 were in the range of 101–109% but for the native drugs in non-spiked sludge samples, recoveries were 38.9%, 59.8%, 90.3% and 47.8% for ketoprofen, naproxen, diclofenac and ibuprofen, respectively. Donor phase pH, ionic strength and extraction time were optimized for HF-LPME after PHWE. The optimum conditions were 2 h extraction at pH 1.5 without salt addition. Enrichment factors in the range of 947–1213 times were achieved (extraction recoveries were 23.6–30.3%) for HF-LPME after PHWE. The matrix effect on the ionization of drugs in LC–ESI-MS was also investigated. The results show that there is a smaller matrix effect (−8.9% to +14.6%) in comparison with other published values obtained using solid phase extraction (SPE) for clean-up after pressurized liquid extraction (PLE). Method detection limits (MDLs) and method quantification limits (MQLs) for different drugs were in the range of 0.4–3.7 ng g−1 and 1.5–12.2 ng g−1 in dried sludge samples, respectively. The characteristics of the proposed method were compared with those of other published works. The considerably lower ion suppression/enhancement and minimum use of organic solvents (a few microliters of di-n-hexyl ether) in the sample preparation step are two highlighted advantages of the proposed method in comparison with previously published works. The method was applied to determine NSAIDs in sewage sludge from Källby wastewater treatment plant (Lund, Sweden) in April, June, August and October 2010. The highest concentration level was recorded for ibuprofen in the April sewage sludge sample (588 ng g−1) and all of the selected NSAIDs were detected in all the samples analyzed. 相似文献
83.
Shmilovits-Ofir M Miller Y Gerber RB 《Physical chemistry chemical physics : PCCP》2011,13(19):8715-8722
Vibrational energy flow and conformational transitions following excitation of the OH stretching mode of the most stable conformer of glycine are studied by classical trajectories. "On the fly" simulations with the PM3 semiempirical electronic structure method for the potential surface are used. Initial conditions are selected to correspond to the ν=1 excitation of the OH stretch. The main findings are: (1) An an equilibrium-like ratio is established between the populations of the 3 lowest-lying conformers after about 10 picoseconds. (2) There is a high probability throughout the 150 ps of the simulations for finding the molecule in geometries far from the equilibrium structures of the lowest-energy conformers. (3) Energy from the initial excited OH (ν=1) stretch flows preferentially to 5 other vibrational modes, including the bending motion of the H atom. (4) RRK theory yields conformational transition rates that deviate substantially from the classical trajectory results. Possible implication of these results for vibrational energy flow and conformational transitions in small biological molecules are discussed. 相似文献
84.
Benny Sudakov 《Advances in Mathematics》2011,(1):601
The Ramsey number r(G) of a graph G is the minimum N such that every red–blue coloring of the edges of the complete graph on N vertices contains a monochromatic copy of G. Determining or estimating these numbers is one of the central problems in combinatorics.One of the oldest results in Ramsey Theory, proved by Erd?s and Szekeres in 1935, asserts that the Ramsey number of the complete graph with m edges is at most . Motivated by this estimate Erd?s conjectured, more than a quarter century ago, that there is an absolute constant c such that for any graph G with m edges and no isolated vertices. In this short note we prove this conjecture. 相似文献
85.
86.
The main aim of this short paper is to answer the following question. Given a fixed graph H, for which values of the degree d does a random d-regular graph on n vertices contain a copy of H with probability close to one? 相似文献
87.
88.
The electron transfer process in bacterial reaction centers is investigated. It is found that the side indole group Trp M252
in Rb sphaeroides (Trp M250 in Rps viridis) assists tunneling electron transfer by a distance of ∼14Å from pheophytin to quinone.
Reported at the VIIIth International Conference on Spectroscopy of Porphyrins and Their Analogs, Minsk, September 22–26, 1998.
Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 4, pp. 496–500, July–August, 1999. 相似文献
89.
Sverker Fredriksson Magnus Jändel Tomas Larsson 《Zeitschrift fur Physik C Particles and Fields》1982,14(1):35-39
The bulk of data from deep inelasticep, eD, μp, μN, νp and νN scattering is fitted with a new diquark model of nucleons. The proton is found to be mostly in au(ud) 0 state, where the (ud)0 diquark has spin and isospin zero. There is hence no trace ofSU(6) symmetry among diquarks in nucleons. 相似文献
90.
J. H. Bowie P. Y. White J. C. Wilson F. C. V. Larsson S.-O. Lawesson J.
Madsen C. Nolde G. Schroll 《Journal of mass spectrometry : JMS》1977,12(4):191-195
+E spectra derived from the non-decomposing anion of some sulphur compounds are independent of the pressure of the collision gas. The compounds chosen for study contain peaks produced from either ortho effects or skeletal rearrangement fragments in their conventional positive ion spectra. The dissociative +E spectra are either devoid of skeletal rearangement ions or alternatiely contain such peaks in small abundance. In contrast, peaks derived from ortho reactions are present in high abundance. 相似文献