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901.
Mixed-mode hydrophilic interaction/cation-exchange chromatography (HILIC/CEX) is a novel high-performance technique which has excellent potential for peptide separations. Separations by HILIX/CEX are carried out by subjecting peptides to linear increasing salt gradients in the presence of high levels of acetonitrile, which promotes hydrophilic interactions overlaid on ionic interactions with the cation-exchange matrix. In the present study, HILIC/CEX has been compared to reversed-phase liquid chromatography (RP-HPLC) for separation of mixtures of diastereomeric amphipathic alpha-helical peptide analogues, where L- and D-amino acid substitutions were made in the centre of the hydrophilic face of the amphipathic alpha-helix. Unlike RP-HPLC, temperature had a substantial effect on HILIC/CEX of the peptides, with a rise in temperature from 25 to 65 degrees C increasing the retention times of the peptides as well as improving resolution. Our results again highlight the potential of HILIC/CEX as a peptide separation mode in its own right as well as an excellent complement to RP-HPLC. 相似文献
902.
In order to characterize the effect of temperature on the retention behaviour and selectivity of separation of polypeptides and proteins in reversed-phase high-performance liquid chromatography (RP-HPLC), the chromatographic properties of four series of peptides, with different peptide conformations, have been studied as a function of temperature (5-80 degrees C). The secondary structure of model peptides was based on either the amphipathic alpha-helical peptide sequence Ac-EAEKAAKEX(D/L)EKAAKEAEK-amide, (position X being in the centre of the hydrophobic face of the alpha-helix), or the random coil peptide sequence Ac-X(D/L)LGAKGAGVG-amide, where position X is substituted by the 19 L- or D-amino acids and glycine. We have shown that the helical peptide analogues exhibited a greater effect of varying temperature on elution behaviour compared to the random coil peptide analogues, due to the unfolding of alpha-helical structure with the increase of temperature during RP-HPLC. In addition, temperature generally produced different effects on the separations of peptides with different L- or D-amino acid substitutions within the groups of helical or non-helical peptides. The results demonstrate that variations in temperature can be used to effect significant changes in selectivity among the peptide analogues despite their very high degree of sequence homology. Our results also suggest that a temperature-based approach to RP-HPLC can be used to distinguish varying amino acid substitutions at the same site of the peptide sequence. We believe that the peptide mixtures presented here provide a good model for studying temperature effects on selectivity due to conformational differences of peptides, both for the rational development of peptide separation optimization protocols and a probe to distinguish between peptide conformations. 相似文献
903.
Hui Chen 《Analytica chimica acta》2003,478(1):31-36
A high sensitive flow-injection chemiluminescence method for determination of calf thymus DNA and herring sperm DNA has been developed. The method is based on the chemiluminescence reaction of Rhodamine B-cerium(IV)-thermally denatured DNAs in sulfuric acid media. The proposed procedure allows quantitation of DNAs in the range 2.6×10−5 to 0.26 μg ml−1 for calf thymus DNA and 5.0×10−8 to 5.0×10−5 μg ml−1 for herring sperm DNA with correlation coefficients 0.9998 and 0.9996 (both n=11), respectively. The detection limits (3σ) are 6.5×10−6 μg ml−1 for calf thymus DNA and 4.3×10−8 μg ml−1 for herring sperm DNA. The possible mechanism of chemiluminescence in the system is discussed. 相似文献
904.
Morais S Pandey PC Chen W Mulchandani A 《Chemical communications (Cambridge, England)》2003,(10):1188-1189
We report a novel method for screening and quantifying tubulin-binding antimitotic agents that promote microtubule formation. The method is based on the shift in the peak of the fluorescence emission difference spectrum of tubulin complexed to metal free tetrakis(4-carboxyphenyl)porphyrin (TCPP) in the presence of antimitotic agents. Taxol (paclitaxel), an anti-tumor drug approved for the treatment of a variety of cancers, caused the appearance of a new fluorescence peak at 645 nm at concentrations as low as 125 nM, the intensity of which was a function of the paclitaxel concentration. Cephalomannine caused the induction of a new fluorescence peak at 651 nm only above 1 muM. Baccatin did not induce the appearance of any new peak within detectable operating measurement conditions. These observations are in accordance with the biological activities/cytotoxicities of these compounds. Accordingly, it is proposed that the new method can be used for high throughput screening of antimitotic compounds. 相似文献
905.
采用共沉淀并加法制备了B位掺杂烧绿石型稀土复合氧化物纳米微晶Y2Sn2-xFexO7-δ(x=00~10)。制备的纳米微晶属于立方晶系,Fd3m,晶胞参数与掺杂量呈线性关系。通过Msbauer、TGDTA,气相色谱和γ射线辐照等技术研究了纳米微晶对CO的催化选择性能。结果表明,纳米微晶对CO的催化选择性明显高于一般粉料对CO的选择性;纳米微晶对CO的选择性与掺杂量有关;未辐照的纳米微晶,当掺杂量x=06时,其对CO的选择性为最高,辐照后的纳米微晶,当掺杂量x=04时,其对CO的选择性为最高 相似文献
906.
Cao Ning-Jun Xu Qin Chen Chee-Shan Gong C. S. Chen L. F. 《Applied biochemistry and biotechnology》1994,(1):521-530
Cellulose gel with < 10% of crystallinity was prepared by treatment of microcrystalline cellulose, Avicel, with zinc chloride
solution at a ratio of zinc chloride to cellulose from 1.5 to 18 (w/w). The presence of zinc ions in the cellulose gels enhanced
the rate of hydrolysis and glucose yield. The evidence obtained from X-ray diffraction, iodine absorption experiments; and
Nuclear Magnetic Resonance spectra analysis suggested the presence of zinc-cellulose complex after Avicel was treated with
zinc chloride. Zinc-cellulose complex was more susceptible to hydrolysis than amorphous cellulose. Under the experimental
condition, cellulose gels with zinc ions were hyrolyzed to glucose with 95% theoretical yield and a concentration of 14% (w/v)
by cellulases within 20 h. The same gel was hydrolyzed by acid to glucose with 91.5% yield and a concentration of 13.4% (w/v). 相似文献
907.
The neutral part of the acetone extract from the bark of Pinus luchuensis Mayer has been investigated and found to consist of alkanes (C22–C34) and triterpenes of serratene type. The triterpenes are 3β–methoxyserrat–14–en–21–one, serrat–14–en–3, 21–dione, 3β–hydroxyserrat–14–en–21–one, 3β–21α–dimethoxyserrat–l4–ene and 3β–methoxyserrat–14–en–21α–ol. 相似文献
908.
909.
Chiral Lewis acid-catalyzed asymmetric Baylis-Hillman reactions 总被引:1,自引:0,他引:1
An effective chiral Lewis acid-catalyzed asymmetric Baylis-Hillman reaction is described. Good to high enantioselectivities were obtained using 3 mol % chiral catalyst. Novel camphor-derived dimerized ligands were prepared from the condensation of (+)-ketopinic acid with the corresponding diamines and hydrazine under acidic conditions. When alpha-naphthyl acrylate was used as a Michael acceptor, the reaction is complete within 20 min with high stereoselectivity and in reasonable chemical yields. 相似文献
910.
The potential energy surfaces for CH(3)CONH(2) dissociation into CH(3) + CONH(2), CH(3)CO + NH(2), CH(3)CN + H(2)O, and CH(3)NH(2) + CO in the ground and lowest triplet states have been mapped with DFT, MP2, and CASSCF methods with the cc-pVDZ and cc-pVTZ basis sets, while the S(1) potential energy surfaces for these reactions were determined by the CASSCF/cc-pVDZ optimizations followed by CASSCF/MRSDCI single-point calculations. The reaction pathways leading to different photoproducts are characterized on the basis of the computed potential energy surfaces and surface crossing points. A comparison of the reactivity among HCONH(2), CH(3)CONH(2), and CH(3)CONHCH(3) has been made, which provides some new insights into the mechanism of the ultraviolet photodissociation of small amides. 相似文献