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With four kinds of mobile phases,methanol-water,ethanol-water,2-propanol and acetonitrile-water(all containing 0.1%rifluroacetic acid),the displacement between solute and solvent in RPLC was proved to be universal in frontal analysls(FA).Based on the measured Z value in usual RPLC to be a constant and the quantitative determination of methanol increment in mobile phase in FA,the stoichiometric displacement(SD)between insulin and methanol was directly proved by the experiment.The SD was also proved to occur only on about the one-fourth of the maximum amount of adsorbed methanol in the bonded phase layer(BPL)without any dynamic problem of mass transfer,while in FA,the SD firstly occurs on the surface of the BPL and then gradually sinks into the deeper sites companied with a dynamic problem.Although the displaces soplvent by the same solute is less in the former case,the SD is independent of how deep of the solute enters the BPL.In addition,the adsorbed amount of solute on and adsorbent not only depends on the numbers of the adsorbed layer on the adsorbent surface,but also on the extent of the complete removal of the displace able solvent in the BPL.The pyhsical fundamental of the SD and the methodoloby for investigation were also discussed. 相似文献
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线性参数logI对反相液相色谱中的非极性小分子溶质体系的表征 总被引:2,自引:0,他引:2
从理论上阐明了计量置换平衡常数的对数logKa对液相色谱中计量置换保留模型的线性参数logI起着主导作用。logI表示溶质对固定相的亲合势,且具有热力学平衡常数的性质。 相似文献
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以溶质计量置换保留模型 (SDM R)为依据 ,通过研究 3种正链醇同系物溶剂置换剂对 14种正链醇同系物溶质色谱保留行为的影响 ,发现计量置换参数Z(对应 1mol溶质被吸附时从溶质与固定相接触处释放出的溶剂的总摩尔数 )、lgI(与 1mol溶质对固定相亲和势有关的常数 )和 j(与 1mol溶剂对固定相亲和势有关的常数 )均随着同系物置换剂相对分子质量的增大而减小 ,并呈现出线性变化 ,表明溶剂强度与溶剂分子的大小有关 ,分子愈大 ,溶剂洗脱能力愈强 ,并遵循同系物规律。 相似文献
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With frontal analysis(FA),the dependence of adsorption isotherms of insulin on the composition of mobile phase in reversed phase liquid chromatography (RPLC) has been investigated,This is also a good example to employ the stoichiometric displacement theory (SDT) for ivestigating solute adsorption in physical chemistry.Six kinds of mobile phase in RPLC were employed to study the effects on the elution curves and adsorption isotherms of insulin.the key points of this paper are:(1) the stability of insulin due to delay time after preparing,the organic solvent concentration,the kind and the concentration of ion-pairing agent in mobile phase were found to affect both elution curve and adsorption isotherm very seriously.(2)To obtain a valid and comparable result,the composition of the mobile phase employed in FA must be as same as possible to that in usual RPLC of either analytical scale or preparative purpose.(3)Langmuir Equation and the SDT were employed to imitate these obtained adsorption isotherms.The expression for solute adsorption from solution of the SDT was found to have a better elucidation to the insulin adsorption from mobile phase in RPLC. 相似文献
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从理论上阐明了热力学观点所定义的柱相比(即溶质的保留自由能变为零时的κ′值)与溶质种类、柱温、固定相以及溶剂种类的依赖关系。通过研究3种配基链长不同的固定相对7种非极性苯的取代物溶质保留行为的影响,发现柱相比与固定相对溶质吸附力有关;通过对9种正链烷溶质在4种温度下的保留行为的研究,发现了柱相比随温度升高而增大,也发现了柱相比与同系物溶质的碳数无关;通过对3种正链醇同系物,3种正链酸同系物,以及丙酮、乙腈和异丙醇共9种置换剂对9种烷基醇同系物溶质色谱保留行为影响的研究,发现柱相比随溶剂极性增大而减小。 相似文献
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比较了Snyder经验公式中的K0w 与S和溶质计量置换保留模型 (SDM R)中溶质保留参数Z(1mol溶剂化溶质被溶剂化固定相吸附时 ,在其接触表面处释放出溶剂或置换剂的总摩尔数 )与lgI(与 1mol溶质对固定相的亲和势有关的常数 )之间的定量关系。SDM R中的两个参数间不仅对同系物溶质可以有很好的线性关系 ,而且对非同系物溶质也有很好的线性关系。其线性关系的好坏主要取决于这两个参数数值范围的大小 ,与文献中报告的线性关系取决于是否单因素影响溶质的保留和完全由统计学规律决定的结论不同。 相似文献
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With insulin methanol-water,and the ion-pairing agent,hydrochloric acid and trifluroacetic acid(TEA),the character of the first plateau(FP)on the elution curve of frontal analysis in reversed phase liquid chromatography(RPLC)was investigated by on-line UV-spectrometry and identified with nuclear magnetic resonance(NMR) spectrometry and mass spectrometry.The profile of the FP is the same as that of a usual elution curve of methanol in frontal analysis(FA).When the insulin concentration was limited to a certain range,the height of the FP was found to be proportional to the insulin concentration in mobile phase and its length companying to shorten,The FP profile on the intersection of two tangents reflects the components of the microstructure in the depth direction of the bonded stationary phase layer and the desorption dynamics of the displaced components.The displaced methanol was quantitatively determined by NMR and on-line UV spectrometries.TFA with high UV absorbance can not be used as an ionpairing agent for the investigation of the FP in RPLC,but if can be used as a good marker to investigate the complicated transfer process of components in the stationary phase in RPLC.A stoichiometric displacement process between solute and solvent was proved to be valid in both usual and FA in RPLC.From the point of view of dynamics of mass transfer, the solutes can only contact to the surface of stationary phase in usual RPLC,while solute can penetrate into it in FA of RPLC.The solvation of insulin in methanol and water solution as an example indicating the usage of the FP in the FA was also investigated in this paper. 相似文献
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醋酸水流动相体系中硅胶键合相上生物大分子保留行为的研究 总被引:1,自引:0,他引:1
提出了以醋酸 水作为流动相的体系中 ,在ODS柱上分离生物大分子的反相高效液相色谱 (RPLC)方法。实验结果表明 ,醋酸 水的洗脱能力强于甲醇 水 三氟醋酸体系 ,在一定程度上克服了色谱分离中一些蛋白质的不可逆吸附且具有便于冷冻干燥的优点。用参数Z(1mol溶剂化溶质被溶剂化固定相吸附时从两者接触表面释放出置换剂的摩尔总数 ) ,logI(与 1mol溶质对固定相亲和势有关的常数 )和 j(与 1mol溶剂对固定相亲和势有关的常数 )对 9种蛋白质在此流动相体系中的保留进行了表征。 相似文献
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IntroductionFrontalchromatography (FC) ,anoldbranchinliquidchromatography (LC) ,1hasbeensuccessfullyem ployedinthesolutionofmanytheoreticalaswellasap pliedproblems—suchasmeasuringbindingconstantbe tweencomponents2 andkineticparametersofchemicalreactions ,3 ads… 相似文献
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建立荧光标记寡核苷酸反相离子对色谱分析方法,优化了流动相醋酸三乙胺浓度(0~0.15 mol/L), pH 4.5~7.0和洗脱强度等色谱条件.对5-mer, 10-mer和15-mer非标记和5'-羧基荧光素(5'FAM)标记寡核苷酸的保留进行比较分析,研究荧光标记寡核苷酸的保留机理,并分离TaqMan~(TM)探针等多种常用荧光标记寡核苷酸.结果显示,不同长度荧光标记寡核苷酸在0.01 mol/L醋酸三乙胺,pH 7.0的条件下获得最大分离.荧光标记寡核苷酸的保留与非标记寡核苷酸有明显差异,两者可完全分离.在一定长度范围内非标记寡核苷酸随长度的增加,保留时间增长;相反,荧光标记寡核苷酸的长度增加,保留时间减短.荧光染料疏水性对其标记的寡核苷酸在反相柱中的保留有较大影响,荧光染料疏水性越强,其标记寡核苷酸保留时间越长.但疏水性的影响程度随标记寡核苷酸长度增加而逐渐变小. 相似文献
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在脂肪酸-水流动相中小分子在反相高效液相色谱中的保留表征 总被引:11,自引:0,他引:11
在反相液相色谱(RPLC)中用Snyder经验议程和计量置换保留模型(SDM-R)中的参数对深质为脂肪醇同系物,流动相为脂肪酸同系物时深质的保留行为进行了研究,结果表明用SDM-R参数具有明显的优越性,另外,由于用Snyder经验公式中二参数之间的作园无法准确求得斜率,且其不具有明确的物理意义,而由SDM-R二参数作图,不但能准确求得斜率j(与1mol溶剂和固相结合能有关的常数),而且j具有明确的物理意义并符合碳数规律,所以,参数j有可能用于RPLC中表征深剂强度,由此得出,在RPLC中,对同一置换剂面言,随同系物溶质的Z(1mol深剂化深质被深剂化固定相吸附时,从二接解面释放出的置换剂分子数)和logI(与1mol深质和固定相亲和势有关的常数)值增大,它们的保留时间也增大,对同一深质而言,随着在同系物置换剂中碳链的增长,Z和logI值的减小,它的保留时间也缩短,同时还可得出,随着同系物置换剂j值的减小,它们的洗脱能力也增强. 相似文献
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《Analytical letters》2012,45(10):1878-1894
Abstract Two simple, rapid, and sensitive HPLC methods have been developed for the simultaneous determination of sulfamethoxazole and trimethoprim in their pure and dosage forms, one utilizing reversed phase HPLC and the other ion-pair HPLC. In the reversed phase HPLC method (A) the mobile phase consists of 0.05% aqueous solution of formic acid with pH adjusted to 4.5±0.2 with triethylamine : acetonitrile:tetrahydrofuran 50 : 49 : 1 (v/v), and the mobile phase pumped at flow rate of 1.0 ml min?1. An Appolo LC18 column (5.0 µm), 250 mm length × 4.6 mm diameter, was utilized as the stationary phase. Detection was affected spectrophotometrically at 254 nm. In the ion-pair HPLC method (B) the mobile phase consisted of methanol : buffer 35 : 65 (v/v) with the buffer composed of potassium dihydrogen phosphate 0.3 M and sodium heptan sulfonic acid 5.0 mM. To 500 ml of buffer was added 2.0 ml triethylamine, and then the pH was adjusted to 5.0 with phosphoric acid, and the mobile phase was pumped at a flow rate of 1.2 ml min?1. A Hypersil C18 column (5.0 µm), 150 mm length × 4.6 mm diameter, was utilized as the stationary phase. Detection was affected spectrophotometrically at 254 nm. Linearity ranges for sulfamethoxazole and trimethoprim were 1.0–110 and 1.5–98 µg ml?1, respectively, with method A and 0.5–100 and 1.0–125 µg ml?1, respectively, with method (B). Minimum detection limits obtained were 0.1969 and 0.3451 µg ml?1 for sulfamethoxazole and trimethoprim, respectively, with method A, and 0.1377 and 0.2454 µg ml?1 with method (B). The proposed methods were further applied to the analysis of tablets containing the two drugs, and the results were satisfied. 相似文献
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Study on Retention in Liquid Chromatography 总被引:2,自引:0,他引:2
Kiyokatsu JINNO 《色谱》2002,20(1):21-29
After joining the faculty at Toyohashi University of Technology (TUT) in 1978, the author has found two areas in separation sciences where microcolumn liquid chromatography (micro LC) can be beneficial One is the hyphenated techniques between many spectroscopic methods such as mass (MS), infrared (FT IR) and atomic emission (ICP), and micro LC The other one is rather difficult, but basic and theoretical approach which deals with retention mechanism in LC. 相似文献
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