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11.
Micellar electrokinetic chromatography is used to separate dansylated nucleotides, both normal and modified species. The high separation power allows detection of minor components present in less than 1 part per thousand of the major components. Laser-excited fluorescence is used to detect the separated components at the 6 x 10(-18) mol level or 10(-9) M injected material. Combined with high-performance liquid chromatographic enrichment prior to labeling, this technique can be used to assess DNA damage in carcinogenesis studies. 相似文献
12.
D ← X resonance enhanced three-photon excitation spectrum of iodine was observed by a cw intracavity absorption technique. Vibrational quantum numbers of D ← X transitions are given for every major spectral feature. The corresponding one-photon enhancement from the B state is evident from the one-photon vibrational assignment. The spectroscopic constants for the D state are v00 = 40 998 cm?1 ω′0 = 113 cm?1 and ω′0χ′0 = 0.045 cm?. 相似文献
13.
A continuous-wave 280 nm light-emitting diode (LED) was used as the excitation source for native fluorescence detection of proteins in CE. The operating current and temperature of the LED were optimized in order to achieve high luminescence power. It was found that a forward current of 30 mA and a temperature of approximately 5 degrees C gave the best S/N. By using a set of two ball lenses to focus light from the LED, we achieved a spot of approximately 200 mum with a power of 0.1-0.2 mW on the detection window. Fluorescence was collected with a ball lens at 90 degrees angle through a bandpass filter onto a photomultiplier tube. In CZE an LOD of 20 nM for conalbumin was reached. In capillary gel electrophoresis all eight proteins from a commercial standard kit were detected with high S/N. For a 10 microg/mL total protein mixture, S/N was better than 3 for all proteins in solution. Further improvement in LOD should be possible on utilization of an LED with higher luminescence power. 相似文献
14.
A number of new β-(N-alkylamino) alanines have been synthesized from acetyldehydroalanine. Using keratin as a cystine-containing protein, it has been shown that, on treatment with a series of amines, β-(N alkylamino) alanine residues are formed in varying amounts in the protein, depending on the structure of amines applied. 相似文献
15.
The use of surfactants as additives was demonstrated for the first time in capillary isoelectric focusing (CIEF) to dynamically modify the surfaces of bare fused silica capillaries. These surfactants were zwitterionic sulfobetaines: dodecyldimethyl (3-sulfopropyl) ammonium hydroxide (C12N3SO3), hexadecyldimethyl (3-sulfopropyl) ammonium hydroxide (C16N3SO3) and coco (amidopropyl)hydroxyldimethylsulfobetaine (Rewoteric AM CAS U). They were added directly to the protein-ampholyte mixture, and remained in the capillary during isoelectric focusing and mobilization. The C16N3SO3 and CAS U coatings were shown effective in CEF. Separation of seven IEF protein standards was obtained, with significantly improved resolution compared to that from an uncoated silica capillary. The effect of these surfactants on the electroosmotic flow (EOF) in CIEF was determined. CAS U was effective in suppressing the EOF at neutral and alkaline pH conditions, C16N3SO3 was effective in suppressing EOF at acidic and neutral pH conditions. C12N3SO3 however had little effect on the EOF. The pH gradients formed inside these surfactant coated capillaries were recta-linear at pH 6 to 9 (R2 approximately equal to 0.99). Reproducibility of migration time and peak area was determined. For all three coatings, the migration time standard deviations were less than 1.6 min, and the relative standard deviations of area were below 10%. The protein recovery in the CAS U-modified capillary was quantitative or near-quantitative for five of the seven proteins studied. 相似文献
16.
17.
Marine organisms produce a fascinating range of structurally diverse secondary metabolites, which often possess unusual and sometimes unexpected biological activities. This structural diversity makes these marine natural products excellent molecular probes for the investigation of biochemical pathways. Recently, a number of novel and stereochemically complex macrolides, having a large macrolactone (22- to 44-membered) ring, that interact with the actin cycloskeleton have been isolated from different marine sources. Actin, like tubulin, is a major component of the cytoskeleton and has important cellular functions. Although the details of these interactions are still under investigation, these marine macrolides are becoming increasingly important as novel molecular probes to help elucidate the cellular functions of actin. Owing to their potent antitumor activities, these compounds, for example the aplyronines, also have potential for preclinical development in cancer chemotherapy. Their appealing molecular structures, with an abundance of stereochemistry, and biological significance, coupled with the extremely limited availability from the marine sources, have stimulated enormous interest in the synthesis of these compounds. This review summarizes the biological properties of these unusual marine natural products and features the recently completed total syntheses of swinholide A, scytophycin C, aplyronine A, mycalolide A--all of these being potent cytotoxic agents that target actin--and a diastereoisomer of ulapualide A. Rather than detailing each individual step of these multistep total syntheses, the different synthetic strategies, key reactions, and methods adopted for controlling the stereochemistry are compared. 相似文献
18.
Yong Zhu Jin-lian Hu Kwok-wing Yeung Hao-jun Fan Ye-qiu 《高分子科学》2006,(2):173-186
SMPU (shape memory polyurethane) non-ionomers and ionomers, synthesized with poly(c-caprolactone) (PCL), 4, 4'-diphenylmethane diisocyanate (MDI), 1,4-butanediol (BDO), dimethylolpropionic acid (DMPA) were measured with cyclic tensile test and strain recovery test. The relations between the structure and shape memory effect of these two series were studied with respect to the ionic group content and the effect of neutralization. The resulting data indicate that, with the introduction of asymmetrical extender, the stress at 100% elongation is decreased for PU non-ionomer and ionomer series, especially lowered sharply for non-ionomer series; the fixation ratio of ionomer series is not affected obviously by the ionic group content; the total recovery ratio of ionomer series is decreased greatly. After sufficient relaxation time for samples stretched beforehand, the switching temperature is raised slightly, whereas the recovery ratio measured with strain recovery test method is lowered with increased DMPA content. The characterization with FT-IR, DSC, DMA elucidated that, the ordered hard domain of the two series is disrupted with the introduction of DMPA which causes more hard segments to dissolve in soft phase; ionic groups on hard segment enhance the cohesion between hard segments especially at high ionic group content and significantly facilitate the phase separation compared with the corresponding non-ionomer at moderate ionic group content. 相似文献
19.
A multiple-pass study was undertaken with a layered silicate-thermoplastic olefin elastomer (TPO) nanocomposite to study the impact of processing history on the properties of the material. A set of 10 passes were completed through a co-rotating intermeshing twin-screw extruder with samples collected to monitor changes in the composite. The microstructure of the nanocomposite was characterized using TEM, XRD, FT-IR, steady and complex shear rheology, and mechanical testing. With progressive passes through the extruder, the TPO nanocomposite experienced both delamination of the organoclay as well as thermo-oxidative degradation. The onset and extent of degradation were found to be unaffected by the presence of the organoclay species in the polymer, though, inclusion of a maleated compatibilizer led to increased chain scission. The generated carbonyl groups along the polymer chain as a result of oxidation were speculated to have a significant effect on the developing percolating network of clay within the material and on the final rheological properties of the composite. Despite the occurrence of degradation in the nanocomposite during recycling, its rheological and mechanical properties remained significantly higher than those of the unfilled resin. 相似文献
20.
Combinatorial chiral separations were performed on a 96-capillary array electrophoresis system. A comprehensive enantioseparation protocol employing neutral and sulfated cyclodextrins as chiral selectors for common basic, neutral and acidic compounds was developed. By using only four judiciously chosen separation buffers, successful enantioseparations were achieved for 49 out of 54 test compounds spanning a large variety of pK and structures. Therefore, unknown compounds can be screened in this manner to identify the optimal enantioselective conditions in just one run. 相似文献