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11.
A capillary electrophoresis (CE) method has been developed for simple and direct separation of cis- and trans-12,13-epoxy-9(Z)-octadecenoic acid and 9,10-epoxy-12(Z)-octadecenoic acid isomers. Separation was performed in micellar electrokinetic capillary chromatography (MEKC) using a buffer consisting of 25 mM borate (pH 9.20), 10 mM sodium dodecyl sulfate (SDS) and 10% v/v acetonitrile. The key variables, concentrations of SDS and organic modifier, were optimized by the application of a factorial experimental design. The use of a low micellar concentration, just above critical micelle concentration (CMC), in a background electrolyte containing an organic modifier not only made it possible to dissolve and separate highly hydrophobic fatty acid isomers, but also resulted in improved separation efficiency and selectivity. Separation efficiency up to 4 x 10(5) theoretical plates/m was achieved under an optimized condition. Also investigated were the influence of temperature on separation and the effect of organic modifier concentration on the dynamic exchange of the analytes between micelles and the bulk of the buffer solution. Direct UV was applied for detection of the fatty acids. 相似文献
12.
Human beta2-glycoprotein I (beta2gpI) is a phospholipid and heparin binding plasma glycoprotein involved in autoimmune diseases characterized by blood clotting disturbances (thrombosis) together with the occurrence of autoantibodies against beta2gpI. With the final goal of assessing autoantibody influence on binding interactions of beta2gpI we have studied the development of capillary electrophoresis (CE)-based assays for interactions of negatively charged ligands with beta2gpI. In the development of suitable conditions for analysis at neutral pH of this basic protein (pI about 8) we found the pH hysteresis behavior of fused silica surfaces useful since the protonated surface after an acid pre-wash counteracted protein adsorption efficiently in contrast to more laborious procedures including acrylamide/dimethylacrylamide coatings that did not permit analysis of this particular protein. This simple approach made estimates of heparin-beta2gpI interactions possible and the principle was shown also to work for detection of betagpI binding to anionic phospholipids. Utilizing the pH hysteresis effect may be a simple solution to the adsorption problems often encountered in analyses of proteins by CE. 相似文献
13.
Schoenmaker PJ Oomen JL Blomberg J Genuit W van Velzen G 《Journal of chromatography. A》2000,892(1-2):29-46
In this paper, we compare the current separation power of comprehensive two-dimensional gas chromatography (GCxGC) with the potential separation power of GC-mass spectrometry (GC-MS) systems. Using simulated data, we may envisage a GC-MS contour plot, that can be compared with a GCxGC chromatogram. Real examples are used to demonstrate the current potential of the two techniques in the field of hydrocarbon analysis. As a separation technique for complex hydrocarbon mixtures, GCxGC is currently about as powerful as GC-MS is potentially powerful. GC-MS has not reached its potential separation power in this area, because a universal, soft ionization method does not exist. The greatest advantage of GCxGC is, however, its potential for quantitative analysis. Because flame-ionisation detection can be used, quantitative analysis by GCxGC is much more robust, reliable and reproducible. 相似文献
14.
Jan Blomberg Peter J. Schoenmakers Jan Beens Robert Tijssen 《Journal of separation science》1997,20(10):539-544
In general, petrochemical products contain only a limited number of chemical classes of compounds (sample dimensionality). The enormous number of individual components within these classes, however, soon puts limitations upon a single chromatographic technique when it comes to adequate characterization of these products. Comprehensive two-dimensional gas chromatography (GC×GC) clearly opens the possibility of estimating the composition of hydrocarbon mixtures in a far more detailed fashion than hitherto possible. Although the emphasis of papers of GCxGC thus far almost exclusively applies to the unsurpassed peak-capacity, in the oil industry there is a need for characterization, rather than for analyzing all the individual compounds. In principle a GCxGC system can provide an almost perfect match between its intrinsic properties and the dimensionality of oil samples. To establish the applicability of GCxGC towards petrochemical analytical challenges, a commercially aavailable prototype instrument was subjected to an exhaustive characterization of a typical hydrocarbon precess stream and a fast characterization of a light gas oil. Although there are no fundamental limitations towards the quantitative aspects of a GCxGC system, this paper confines itself to qualitative results only. Quantitative aspects of GCxGC will be published in a forthcoming paper. 相似文献
15.
Dai QH Tommos C Fuentes EJ Blomberg MR Dutton PL Wand AJ 《Journal of the American Chemical Society》2002,124(37):10952-10953
The use of side chains as catalytic cofactors for protein mediated redox chemistry raises significant mechanistic issues as to how these amino acids are activated toward radical chemistry in a controlled manner. De novo protein design has been used to examine the structural basis for the creation and maintenance of a tryptophanyl radical in a three-helix bundle protein maquette. Here we report the detailed structural analysis of the protein by multidimensional NMR methods. An interesting feature of the structure is an apparent pi-cation interaction involving the sole tryptophan and a lysine side chain. Hybrid density functional calculations support the notion that this interaction raises the reduction potential of the W degrees /WH redox pair and helps explain the redox characteristics of the protein. This model protein system therefore provides a powerful model for exploring the structural basis for controlled radical chemistry in protein. 相似文献
16.
The reaction of 6-bromo-1-hexene with Mg was studied in order to obtain information on the role of the solvent during the formation of Grignard reagents. The 5-hexenyl radical (Rnc.) is known to cyclize rapidly and irreversibly to the cyclopentylmethyl radical (Rc.). Changes in yields of the cyclized and non-cyclized Grignard compounds have been found on varying the solvent. Information on the radical pairs involved is obtained from the yields of the three possible coupling products (RncRnc, RncRc and RcRc). Results are correlated to the intensity of the CIDNP spectra of the Grignard compounds. It is found that basicity and viscosity of the solvents influence the reactions at the site of single electron transfer. Formation of Grignard compounds via radical pairs increases: (a) with decreasing basicity of the solvent, (b) with decreasing viscosity of the solvent, and (c) on dilution of THF with benzene. It is proposed that interaction between the radical and the π-electron rich solvent benzene plays a role in reactions run in Bz/THF mixtures. 相似文献
17.
Earlier studies of electric field assisted LC (EF-LC) have shown that the effect on charged analytes of the application of an electric field over a capillary LC column is relatively small. Charged analytes can only be affected by the electric field while present in the mobile phase, which makes the effective time for influence of the electric field t(0) independent of retention time. Because the charged analytes only can be affected for a short time the electric field strength ought to be high in order to increase the impact of the electric field on the separation. We have, however, found that only a relatively low electric field strength can be used in EF-LC when pressure is used as main driving force. The useful field strength was limited by a dramatic increase in the current. This increase in current was found to origin from an increased concentration of buffer ions that have an electrophoretic mobility towards the pumped flow. 相似文献
18.
19.
Surfaces coated with poly(ethylene oxide) containing nonionic polymers are of interest in medical applications due to, among other things, the low adsorption of proteins on such surfaces. In this paper we have studied the interfacial properties of surfaces coated with PEO by measuring the forces acting between two such surfaces in water and across a protein solution as well as between one such surface and a surface carrying adsorbed proteins. One type of surface coating was a graft copolymer of poly(ethylene imine) and poly(ethylene oxide) where the cationic poly(ethylene imine) group anchored the polymer to negatively charged mica surfaces. Three different ways to prepare this coating was used and compared. It was found that this coating was not stable in the presence of lysozyme, a small positively charged protein, when the PEO graft density was low. The other type of coating was obtained by adsorbing ethyl(hydroxyethyl)-cellulose onto hydrophobised mica surfaces. The driving force for adsorption is in this case the hydrophobic interaction between nonpolar segments of the polymer and the surface. The EHEC coating was stable in the presence of lysozyme and the interactions between adsorbed layers of lysozyme and EHEC coated surfaces are purely repulsive due to long-range steric forces. 相似文献
20.
O. A. Alekseeva N. I. Sorokina M. K. Blomberg I. A. Verin T. Yu. Losevskaya V. I. Voronkova V. K. Yanovskii V. I. Simonov 《Crystallography Reports》2001,46(2):176-181
The structure of a crystal grown by crystallization from flux in the K2O-TiO2-Nb2O5-P2O5 system was studied by the methods X-ray diffraction analysis at room temperature. The crystals of the composition K2.47Nb2.85Ti1.15P2.5O17 are monoclinic, a = 13.7864(7) Å, b = 6.4078(3) Å, c = 16.9384(7) Å, β = 83.15(1)°, sp. gr. P2/n. The structure was solved by the direct method using the SHELXS86 program package and refined by the JANA96 program. The crystal structure consists of a three-dimensional framework of sharing-vertices (Nb,Ti)O6-octahedra and the PO4-tetrahedra and two types of channels along the diagonal [101] direction, which are statistically occupied by potassium cations providing ionic transport in the compound. 相似文献