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31.
The critical step in the determination of water solubilitiy (S w) and octanol-water partition coefficient (K ow) of hydrophobic organic chemicals by using the generator-column technique and the slow-stirring procedure, respectively, is the exact quantification of the low water-phase concentrations of the substances under investigation. We have tested the applicability of solid-phase microextraction (SPME) and gas chromatography with seven chlorinated organic compounds. The substances cover a S w range from 500 mg/L to 7 ng/L and a log K ow range from 3 to 8. The results show that SPME can be a valuable alternative to common preconcentration techniques in the quantification of hydrophobic organics in pure and octanol-saturated water. The apparent SPME distribution constants K SPME (obtained with the 100 μm-PDMS fiber for analyte’s partitioning between fiber coating and aqueous sample) do not correlate directly with octanol/water partition coefficients and thus cannot be recommended as a surrogate parameter for K ow. 相似文献
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33.
Andreas Bornø Carl J. Hulston Gerrit van Hall 《Journal of mass spectrometry : JMS》2014,49(8):674-680
In the present study, different MS methods for the determination of human muscle protein fractional synthesis rate (FSR) using [ring‐13C6]phenylalanine as a tracer were evaluated. Because the turnover rate of human skeletal muscle is slow, only minute quantities of the stable isotopically labeled amino acid will be incorporated within the few hours of a typical laboratory experiment. GC combustion isotope ratio MS (GC‐C‐IRMS) has thus far been considered the ‘gold’ standard for the precise measurements of these low enrichment levels. However, advances in liquid chromatography‐tandem MS (LC‐MS/MS) and GC‐tandem MS (GC‐MS/MS) have made these techniques an option for human muscle FSR measurements. Human muscle biopsies were freeze dried, cleaned, and hydrolyzed, and the amino acids derivatized using either N‐acetyl‐n‐propyl, phenylisothiocyanate, or N‐methyl‐N‐(tert‐butyldimethylsilyl)trifluoroacetamide (MTBSTFA) for GC‐C‐IRMS, LC‐MS/MS, and GC‐MS/MS analysis, respectively. A second derivative, heptafluorobutyric acid (HFBA), was also used for GC‐MS/MS analysis as an alternative for MTBSTFA. The machine reproducibility or the coefficients of variation for delta tracer‐tracee‐ratio measurements (delta tracer‐tracee‐ratio values around 0.0002) were 2.6%, 4.1%, and 10.9% for GC‐C‐IRMS, LC‐MS/MS, and GC‐MS/MS (MTBSTFA), respectively. FSR determined with LC‐MS/MS compared well with GC‐C‐IRMS and so did the GC‐MS/MS when using the HFBA derivative (linear fit Y = 1.08 ± 0.10, X + 0.0049 ± 0.0061, r = 0.89 ± 0.01, P < 0.0001). In conclusion, (1) IRMS still offers the most precise measurement of human muscle FSR, (2) LC‐MS/MS comes quite close and is a good alternative when tissue quantities are too small for GC‐C‐IRMS, and (3) If GC‐MS/MS is to be used, then the HFBA derivative should be used instead of MTBSTFA, which gave unacceptably high variability. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
34.
Frans C. Mijlhoff Gerrit H. Renes Kunio Kohata Kazuko Oyanagi Kozo Kuchitsu 《Journal of Molecular Structure》1977,39(2):241-252
The structure of 1,1-difluoroethylene was determined, from gas phase electron diffraction data obtained independently in Leiden and Tokyo and the rotational constants of F2CCH2, F2CCHD and F2CCD2 derived from the microwave study by Chauffoureaux. The two electron diffraction data agreed without significant discrepancy. From a joint least squares analysis of the diffraction and microwave data, the following rg bond distances and rz bond angles were derived: CC = 1.340 ± 0.006 Å, C-F = 1.315 ± 0.003 Å, C-H = 1.091 ± 0.010 Å, ∠C-C-F = 124.7 ± 0.3°, ∠C-C-H = 119.0 ± 0.4°, where the uncertainties represent estimated limits of error. 相似文献
35.
Gerrit K. Janssens Kenneth Sörensen Wout Dullaert 《Mathematical and Computer Modelling》2009,49(3-4):563-572
Stochastic marked graphs, a special class of stochastic timed Petri nets, are used for modelling and analyzing decision-free dynamic systems with uncertainties in timing. The model allows evaluating the performance of such systems under a cyclic process. Given the probabilistic characteristics of the transition times, the cycle time of the system can be determined from the initial marking. In this contribution, we compute an upper bound on the cycle time of a stochastic marked graph in case the probabilistic characteristics of the transition times are not fully specified. 相似文献
36.
Hyoungsoo Kim Sebastian Große Gerrit E. Elsinga Jerry Westerweel 《Experiments in fluids》2011,51(2):395-405
We describe a tomographic PIV system for the measurement of the internal flow in a droplet over a stagnant and a moving surface.
The flow condition is representative of the flow in an immersion droplet applied in a liquid immersion lithography machine.
We quantify the accuracy and reliability of the measurements and compare the shape of the reconstructed measurement volume
to shape measurements by means of shadowgraphy. First results indicate the internal flow pattern near the receding contact
line, showing a small recirculation region. 相似文献
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39.
Derk Balthazar de Graaf Yawar AbbasJohan Gerrit Bomer Wouter OlthuisAlbert van den Berg 《Analytica chimica acta》2015
Chloride is a crucial anion for various analytical applications from biological to environmental applications. In order to measure the chloride ion concentration, a measurement system is needed which can detect this concentration for prolonged times reliably. Chronopotentiometry is a technique which does not need a long term stable reference electrode and is therefore very suitable for prolonged ion concentration measurements. As the used electrode might be fouled by reaction products, this work focuses on a chronopotentiometric approach with a separated sensing electrode (sensor) and actuating electrode (actuator). Both actuation and sensor electrode are made of Ag/AgCl. A constant current is applied to the actuator and will start the reaction between Ag and Clˉ, while the resulting Clˉ ion concentration change is observed through the sensor, which is placed close to the actuator. The time it takes to locally deplete the Clˉ ions is called transition time. Experiments were performed to verify the feasibility of this approach. The performed experiments show that the sensor detects the local concentration changes resulting from the current applied to the actuator. A linear relation between the Clˉ ion concentration and the square root of the transition time was observed, just as was predicted by theory. The calibration curves for different chips showed that both a larger sensor and a larger distance between sensor and actuator resulted in a larger time delay between the transition time detected at the actuator and the sensor. 相似文献
40.
Martin Faber Anton H. Hofman Katja Loos Gerrit ten Brinke 《Macromolecular rapid communications》2016,37(11):911-919
Linear poly(4‐tert‐butoxystyrene)‐b‐poly(4‐vinylpyridine) (PtBOS‐b‐P4VP) diblock copolymers are synthesized using reversible addition–fragmentation chain transfer polymerization. The self‐assembly of four different PtBOS‐b‐P4VP diblock copolymers is studied using small‐angle X‐ray scattering and transmission electron microscopy and a number of interesting observations are made. A tBOS62‐b‐4VP28 diblock copolymer with a weight fraction P4VP of 0.21 shows a disordered morphology of P4VP spheres with liquid‐like short‐range order despite an estimated value of of the order of 50. Increasing the length of the 4VP block to tBOS62‐b‐4VP199 results in a diblock copolymer with a weight fraction P4VP of 0.66. It forms a remarkably well‐ordered lamellar structure. Likewise, a tBOS146‐b‐4VP120 diblock copolymer with a weight fraction P4VP of 0.33 forms an extremely well‐ordered hexagonal structure of P4VP cylinders. Increasing the P4VP block of this block copolymer to tBOS146‐b‐4VP190 with a weight fraction P4VP of 0.44 results in a bicontinuous gyroid morphology despite the estimated strong segregation of . These results are discussed in terms of the architectural dissimilarity of the two monomers, characterized by the presence of the large side group of PtBOS, and the previously reported value of the interaction parameter, , for this polymer pair.