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61.
A method for fast in situ measurement of adsorption kinetics based on a finite bath was developed. We modified the conventional finite bath by replacing the external loop by a dip probe which enables in situ measurement of the concentration change in the contactor. Deposition of adsorbent particles on the reflection surface of the dip probe compromised measurements. Different membranes, a polyamide, a polypropylene and a nylon membrane were tested to protect the internal reflection surface of the dip probe from fouling with adsorbent particles. The nylon membrane provided efficient protection and high mass transfer evaluated by response time experiments. Unspecific adsorption of the model protein on the membrane could also be excluded. To corroborate the measurements of the dip probe the results were compared to a conventional finite bath and to a shallow-bed. The uptake curves for human polyclonal IgG at different concentrationes (0.1-3 g/l) on rProtein A Sepharose FF and MabSelect were used as model system. The effective diffusion coefficients were determined using a pore diffusion model. These values were in good agreement for all methods. 相似文献
62.
W.John Albery David Clark Humphrey J.J. Drummond Anthony J.M. Coombs William K. Young Clive E.W. Hahn 《Journal of Electroanalytical Chemistry》1992,340(1-2)
A novel electrochemical sensor for the determination of CO2 in expired breath is described. The sensor works by generating
from the reduction of O2 in dimethyl sulphoxide (DMSO) in a generating pulse. There is a rapid titration reaction between the
and any CO2 present. In the recovery pulse the amount of unreacted
is determined. The larger the concentration of CO2 the less
is found in the recovery pulse. The solubilities and diffusion coefficients of O2 and CO2 in DMSO have been determined using rotating disc voltammetry and rotation speed step experiments. The stoichiometry, the product, and the rate constant of the titration reaction have been determined using ring—disc voltammetry and laser Raman spectroscopy. The operation and the effect of adventitious water on the sensor are described. Results are presented which show that the sensor can indeed measure the breath-by-breath rhythm of expired CO2 from a human subject. 相似文献
63.
Uwe Bhme Franziska Bendrath Betty Günther 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(11):o631-o632
In the title compound, C8H22Cl2N2Si3, the central Si atom is tetrahedrally coordinated by two Cl and two N atoms in a molecule that has crystallographically imposed C2 symmetry. Comparison is made with the isomorphous structure having titanium instead of silicon at the central position in the diazacyclopentane ring [Tinkler, Deeth, Duncalf & McCamley (1996). Chem. Commun. pp. 2623–2624]. 相似文献
64.
65.
Contributions to the Chemistry of Phosphorus. 105. 1,2,34-Tetraphenyl-1,4-bis(trimethylsilyl)-tetraphosphane and 1,2,3,4-Tetraphenyltetraphosphane 1,2,3,4-Tetraphenyl-1,4-bis(trimethylsilyl)-tetraphosphane, Me3Si? (PPh)4? SiMe3 ( 1 ), is obtained by reacting K2(PPh)4 with trimethylchlorosilane under suitable conditions. Compound 1 disproportionates almost easier than the corresponding triphosphane (Me3Si)2(PPH)3. Of the six possible diastereomers only 1a (erythro, meso, erythro), 1b (erythro, d,l, erythro), 1 d (threo, d,l, threo), and 1 f (erythro, threo, threo) can be detected in solution by 31P-NMR spectroscopy. In consequence of rapid inversion at the P atoms a dynamic equilibrium exists between the different isomers. The assignment of the 31P-NMR-spectroscopically observed spin systems to the corresponding diastereomers results from the dependence of the 1JPP-coupling constants on the dihedral angle between vicinal free electron pairs as well as on the observed frequency distribution. In the alcoholysis of 1 the corresponding hydride H? (PPh)4? H ( 2 ) is formed as the main product. It could be isolated in spite of its instability. At room temperature 2 disproportionates rapidly forming mainly (PPh)4 and H2(PPh)2 (ratio 1:2) at first; later on also H2(PPh)3, H2PPh, and (PPh)5 are found. The corresponding rearrangements follow a four-center mechanism involving predominantly P? P bonds. 相似文献
66.
Determination of estrogenic steroids in surface water and wastewater by liquid chromatography-electrospray tandem mass spectrometry 总被引:1,自引:0,他引:1
An analytical method is presented which permits trace level determination of 17alpha-ethynylestradiol (EE2), 17beta-estradiol (E2), and estrone (E1). Using this method, the estrogenic steroids were analyzed in drinking water, surface water, and wastewater (sewage influents and effluents) at concentrations down to 0.1 ng/L. Sample volumes between 100 and 500 mL are concentrated using automated solid-phase extraction. Analysis is performed by liquid chromatography with detection by tandem mass spectrometry. Applying simple clean-up procedures and internal standard calibration, recovery losses resulting from matrix-dependent ion suppression during electrospray ionization could be compensated for all of the investigated compounds. Recoveries around 100% were obtained for all analytes after correction using the internal standards. Limits of quantification (LOQ) were between 0.1 and 0.4 ng/L for purified sewage, surface, ground, and drinking water and between 1 and 2 ng/L in the case of raw sewage. Water treatment by wastewater treatment plants (WWTPs) or by a surface water treatment plant affected the removal of all estrogenic steroids. Thus, E1, E2, and EE2 were removed in the municipal WWTPs to the extent of 93%, 93%, and 80%, respectively. In the effluents of the WWTP in Ruhleben (Berlin, Germany), E1, E2, and EE2 were detected at the low ng/L level. E2 and EE2 were, however, not present in the Berlin surface water above the LOQ (0.2 ng/L). E1 was the only compound that could be detected in surface water samples. After additional surface water treatment it was still detectable but only at trace-level concentrations with a mean value of 0.16 ng/L. 相似文献
67.
M. H. Baik W. J. Cho P. S. Hahn 《Journal of Radioanalytical and Nuclear Chemistry》2004,260(3):495-502
Surface sorption experiments of U(VI) onto the surfaces of a Korean granite rock are carried out in order to investigate the
kinetics and reversibility of U(VI) sorption as a function of pH and surface types such as fresh intact surfaces and natural
fracture surfaces. It was shown that the effect of pH is significant in the sorption of U(VI) onto both types of the granite
surfaces. However the sorption rates do not greatly depend upon the pH regardless of the surface types. A two-step first order
kinetic behavior dominates onto both the intact surfaces and natural fracture surfaces of granite and that the linearization
approach of the kinetic model agrees well with experimental sorption data. The desorption results showed that the sorption
process of U(VI) was a little irreversible for the two types of granite surfaces regardless of pH and surface types. This
kinetic approach could give a better understanding of U(VI) sorption onto granite surfaces depending on pH and surface types.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
68.
S. Kallus A. Hahn G. Golemme C. Algieri P. Timmins J.D.F. Ramsay 《Journal of Sol-Gel Science and Technology》2003,26(1-3):721-725
The synthesis of zeolite membranes and thin films using the secondary growth process is briefly described. In this process colloidal zeolite particles (sols) are prepared hydrothermally and then subsequently deposited on substrates to produce uniform layers of controlled thickness, as illustrated with silicalite and zeolite-A. The formation and growth of the zeolite sols has been investigated in situ by small angle neutron scattering (SANS). SANS measurements on silicalite sols at progressively higher concentrations have provided details of the colloid interactions which lead to zeolite gel-layer structures which are uniform and free of defects. 相似文献
69.
Uwe Gropengiesser 《Journal of statistical physics》1995,79(5-6):1005-1012
We compare various evlutionary strategies to determine the ground-state energy of the ±J spin glass. We show that the choice of different evolution laws is less important than a suitable treatment of the free spins of the system At least one combination of these strategies does not give the correct results, but the ground states of the other different strategies coincide. Therefore we are able to extrapolate the infinit-size ground-state energy for the square lattice to –1.401±0.0015 and for the simple cubic lattice to –1.786±0.004. 相似文献
70.