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11.
Frequency-domain electron nuclear double resonance (ENDOR), two time-domain electron nuclear double resonance techniques, and electron spin echo envelope modulation spectroscopy are compared with respect to their merit in measurements of small hyperfine couplings to nuclei with intermediate gyromagnetic ratio such as 31P. The frequency-domain Mims ENDOR experiment is found to provide the most faithful line shapes. In the limit of long electron-nuclear distances of more than 0.5 nm, sensitivity of this experiment is optimized by matching the first interpulse delay to the transverse relaxation time of the electron spins. In the same limit, Mims ENDOR efficiency scales inversely with the sixth power of distance. Hyperfine splittings as small as 33 kHz can be detected, corresponding to an electron-31P distance of 1 nm. In systems, where a certain kind of nuclei is distributed in a plane, measurements of intermolecular hyperfine couplings can be analyzed in terms of a distance of closest approach of a paramagnetic center to that plane. By applying this technique to spin-labeled lipids in a fully hydrated lipid bilayer it is found that for a fraction of lipids, chain tilt angles can be 25 degrees larger than the mean tilt angle of the lipid chains. This model of all-trans hydrocarbon chains with a broad distribution of tilt angles is also consistent with orientation selection effects in high-field ENDOR spectra. 相似文献
12.
Jürgen Khler Gunnar Svensson Arndt Simon 《Angewandte Chemie (International ed. in English)》1992,31(11):1437-1456
Metal clusters, discrete or condensed, are characteristic of the structures of many compounds which contain transition metals in low oxidation states. The highly reduced oxoniobates support the concept of condensed clusters. They contain Nb6O12 clusters which are either isolated or linked at the apices of the Nb6 octahedra to form oligomeric chains or networks. The analysis of the bonding relationships allows the identification of different types of Nb atoms and thus the quantitative prediction of valence electron concentrations for finite or infinite structures composed of these condensed M6X12 clusters. 相似文献
13.
14.
Improved quantification limits in chiral capillary electrochromatography by peak compression effects
The peak compression effect has been applied to improve quantification limits in chiral capillary electrochromatography (CEC). A stationary phase based on the chiral selector vancomycin (Chirobiotic V) was used for separations of the enantiomers of mianserin. By adding solvents with a low dielectric constant, e.g. 2-propanol or tetrahydrofuran, to the sample solution, peak compression could be induced. The plate numbers for the minor enantiomer increased from approximately 100,000 to 1.4-1.6 million plates/m, when the composition of the mobile phase was adjusted so that the analyte eluted within either one of two system zones originating from the sample solution. A 10-fold improvement in the quantification limit for the minor enantiomer was obtained compared to elution under non-focused conditions. 相似文献
15.
The present paper describes constructional details and evaluations of an at-column injector for capillary GC. Injections were made via a sample loop on a 0.32 mm i.d. capillary column. Two rotary valves were employed to allow a wash of the sample loop and a backflush of the transfer line. Repeatability, calculated from absolute area counts for n-alkanes was between 0.3–1% RSD, for injected sample volumes between 5 and 100 μl. Promising results were also obtained with syringe-based injections on narrow bore (100 μ i.d.) columns. Repeatability on the basis of normalized area counts was in the order of 0.1–0.2% RSD, while solvent tailing was practically absent. 相似文献
16.
Guido W Vandermeulen Dariush Hinderberger Hui Xu Sergei S Sheiko Gunnar Jeschke Harm-Anton Klok 《Chemphyschem》2004,5(4):488-494
Herein we describe the structure and dynamics of self-assembled nano-objects generated from poly(ethylene glycol) based (PEG-ylated) coiled-coil hybrid block copolymers. Electron paramagnetic resonance (EPR) experiments on spin-labeled samples provided a strong indication for a parallel alignment of the peptide helices in at least the dimeric coiled-coil nano-object and indicated that the PEG chains are folded rather closely around the peptide core of the nano-objects. The EPR results were supported by AFM studies, which revealed the presence of discrete nanosized objects in thin, spin cast films of the block copolymers on mica substrates. Since their size and structure may be engineered via directed mutations in the amino acid sequence, these nano-objects may be interesting building blocks for the development of supramolecular materials with various potential applications. 相似文献
17.
Lee KJ Mao S Sun C Gao C Blixt O Arrues S Hom LG Kaufmann GF Hoffman TZ Coyle AR Paulson J Felding-Habermann B Janda KD 《Journal of the American Chemical Society》2002,124(42):12439-12446
Overexpression of the cell-surface glycosphingolipid G(M3) is associated with a number of different cancers, including those of the skin, colon, breast, and lung. Antibodies against the G(M3) epitope have potential application as therapeutic agents in the treatment of these cancers. We describe the chemoenzymatic synthesis of two G(M3)-derived reagents and their use in the panning of a phage-displayed human single-chain Fv (scFv) antibody library derived from the blood of cancer patients. Three scFv-phage clones, GM3A6, GM3A8, and GM3A15, were selected for recombinant expression and were characterized using BIAcore and flow cytometry. BIAcore measurements using the purified, soluble scFvs yielded dissociation constants (K(d)) ranging from 4.2 x 10(-7) to 2.1 x 10(-5) M. Flow cytometry was used to evaluate the ability of each scFv to discriminate between normal human cells (human dermal fibroblast, HDFa), melanoma cells (HMV-1, M21, and C-8161), and breast cancer cells (BCM-1, BCM-2, and BMS). GM3A6 displayed cross-reactivity with normal cells, as well as tumor cells, and GM3A15 possessed little or no binding activity toward any of the cell lines tested. However, GM3A8 bound to five of the six tumor cell lines and showed no measurable reactivity against the HDFa cells. Hence, we have demonstrated that a synthetic G(M3) panning reagent can be used to isolate a fully human scFv that is highly specific for native G(M3) on the surface of tumor cells. The result is a significant step toward effective immunotherapies for the treatment of cancer. 相似文献
18.
Peak compression effects in capillary electrochromatography of basic drug substances using a strong cation-exchanger 总被引:1,自引:0,他引:1
Peak compression effects in capillary electrochromatography of basic drug substances using a strong cation-exchanger have been studied. Extremely narrow peaks with apparent efficiencies of several million plates per meter could be obtained when the composition of the sample zone differed from that of the mobile phase. The increased efficiencies were predominately observed when the analyte had an elution time similar to that of the electroosmotic flow marker. Peak compression was found to be reproducible and could be obtained for all investigated basic drug substances by altering the composition of the mobile phase in such a way that the analyte co-eluted with the sample zone. An explanation of the observed phenomena is proposed. A sample zone differing in composition from the mobile phase will disturb the equilibrium between the stationary and mobile phase. The elution rate of an analyte will consequently be different when residing inside the sample zone. If the analyte migrates through the sample zone at a higher speed than the rest of the mobile phase and is strongly retained after passing through a boundary in the sample zone, a continuous stacking can be obtained trapping the analyte as a very narrow band. 相似文献
19.
Daniel Karlsson Jakob Dahlin Åsa Marand Gunnar Skarping Marianne Dalene 《Analytica chimica acta》2005,534(2):263-269
A method for the determination of isocyanates as di-n-butyl amine (DBA) derivatives using tandem mass spectrometry (MS/MS) and electrospray ionisation (ESI) is presented. Multiple-reaction monitoring (MRM) of the protonated molecular ions and corresponding deuterium-labelled d9-DBA derivatives resulted in selective quantifications with correlation coefficients >0.998 for the DBA derivatives of isocyanic acid (ICA), methyl isocyanate (MIC), ethyl isocyanate (EIC), propyl isocyanate (PIC), phenyl isocyanate (PhI), 1,6-hexamethylene diisocyanate (HDI), 2,4-, 2,6-toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), 4,4′-methylenediphenyl diisocyanate (MDI), 3-ring MDI, 4-ring MDI, HDI-isocyanurate, HDI-diisocyanurate, HDI-biuret and HDI-dibiuret. The instrumental precision for 10 repeated injections of a solution containing 0.1 μg ml−1 of the studied derivatives was <2%. Performing MRM of the product ion [DBA + H]+ (m/z = 130) from the protonated molecular ion resulted in the lowest detection limits, down to 10 amol (for TDI). Quantification of concentrations below 10−6 of the occupational exposure limit (OEL) for TDI during 10 min of air sampling was made possible. In an effort to control the formation of alkali adducts, addition of lithium acetate to the mobile phase and monitoring of lithium adducts was evaluated. Having lithium present in the mobile phase resulted in complete domination of [M + Li]+ adducts, but detection limits for the studied compounds were not improved. Different deuterium-labelled derivatives as internal standards were evaluated. (1) DBA derivatives of deuterium-labelled isocyanates (d4-HDI, d3-2,4-TDI, d3-2,6-TDI and d2-MDI), (2) d9-DBA derivatives of the corresponding isocyanates and (3) d18-DBA derivatives of the corresponding isocyanates. An increase in number of deuterium in the molecule of the internal standard resulted in an increase in instrumental precision and a decrease in correlation within calibration series. 相似文献
20.
Spectroscopic Investigations of Dicyanamidometallates(II), [M(NCNCN)4]2? of the Zinc Group The synthesis of homologeous tetrakis-(dicyanamido)metallates(II) [M(NCNCN)4]2? (M: Zn, Cd, Hg) is reported. The coordination type of the ambivalent anionic ligand is discussed on the basis of the IR, ESCA, 15N, and 13C NMR spectra of the new complexes. 相似文献