【作者】 杨曦；

【导师】 沈静茹；

【作者基本信息】 中南民族大学 ， 分析化学， 2007， 硕士

【摘要】 本文简述了手性化合物拆分的意义和环糊精及其衍生物在这方面的作用;介绍了与论文内容相关的β-环糊精及其衍生物在HPLC固定相和光度分析中的应用现状。合成了双-[-6-氧-（-3-间硝基苯磺酰基-丁二酸-1,4-单酯-4-）-]-β-环糊精（简称:β-CD-M₂ ）,并对反应条件进行优化。将合成的β-CD-M₂进行分离和纯化,通过对β-CD-M₂的傅立叶红外图谱、紫外扫描图谱、核磁、元素分析、以及X射线粉末衍射（XRD）谱图分析可基本确认目标衍生物已合成,未见文献报道。用β-CD-M₂合成高效液相色谱固定相,对该固定相做了初步表征,将该衍生物用来构筑涂敷型和键合型两种液相色谱固定相,利用实验室现有的设备来装填液相色谱柱,用来对芳香醇类物质进行手性拆分,可以在选定的条件下成功分离α-苯乙醇、1-苯丙醇和扁桃酸。并初步探讨其作用机理。通过对比,键合型固定相是共价键合在硅胶上的,受溶剂和温度的限制较小,在正相和反相条件下都可以使用,得到的色谱峰形也比较对称,在使用时间近8个月的情况下,柱效没有明显的降低。另外将该衍生物用来构筑抗坏血酸模拟酶来测定饮料中的抗坏血酸含量。对模拟酶构筑条件进行研究,借助氧化型辅酶Ⅰ烟酰胺腺嘌呤二核苷酸（NAD）作为氢的受体,反应中生成的辅酶Ⅰ还原型烟酰胺腺嘌呤二核苷酸（NADH）量与抗坏血酸量呈一定化学计量关系,通过在340nm处测定NADH的吸光值变化来进行定量分析。通过实验可得最佳NAD用量是40μL（15.20g.l-1）;Vc与模拟酶的最佳摩尔比为27:1,最佳缓冲液选用pH=10.50的甘氨酸-氢氧化钠缓冲液。在最佳条件下3min内可使底物抗坏血酸反应完全。抗坏血酸在2.95μg.mL^-1- 26.50μg.mL^-1之间,线性良好,其回归方程为y=0.107+0.00345x,相关系数r=0.998。检测下限为1.00μg.mL^-1。以市售的饮料为检测对象,对其营养成分Vc的含量进行测定。在选定的最佳条件下进行测定,对饮料样品中的抗坏血酸含量的检测结果为0.38mg.mL^-1,在饮料所标识的范围内(0.25 mg.mL^-1—0.50 mg.mL^-1)。更多还原

【Abstract】 This paper outlined the effect of enantiomeric separation in chiral compounds and effect of chiral separation withβ-cyclodextrin andβ-cyclodextrin derivatives. It introduced the application ofβ-cyclodextrin andβ-cyclodextrin derivatives in stationary phase of HPLC and photometric analysis. Bis [6-oxygen-（3-m- nitrobenzene sulfonyl-amber acid-1, 4 uniester-4）]-β-CD （abbr.β-CD-M₂） was synthesized and the reaction conditions were optimized. The synthesizedβ-CD-M₂ was separated and purified and the goal derivative was confirmed by characterization with Fourier transform infrared spectra, ultraviolet map scanning, NMR, elemental analysis and XRD which had not seen on literature report.The stationary phase of HPLC was synthesized byβ-CD-M₂ with silica gel. Two kinds of stationary phase in liquid chromatogram were constructed, which includes the coating type and bonded phase with theβ-CD-M₂.The columns were prepared using equipments in our laboratory and enantiomeric of aromatic alcohol was separated. The results showed thatα–benzene ethanol, benzene propanol and mandelic acid could be separated successfully under the selected condition and the mechanism was also analyzed. By comparing the bonded phase with the coating type phase, the restricting of solvent and temperature in the bonded phase was relatively[0] light because it was linked to silica by chemical bond. The experiments could be carried out under either the normal phase or the reverse phase [0]and the peak shape of chromatogram is also symmetrical. The effect of theoretical plates of the column was not reducing after 8 months.The ascorbic acid （abbr. AA） could be detected in beverage by a mimic ascorbic acid dehydrogenase with theβ-CD-M₂. The reaction conditions were optimized. The optimum dosage of NAD was 0.2027 g.L-1 and the optimum buffer solution was glycine-sodium hydroxide buffer solution pH10.50. In addition, the optimum ratio of mole between the AA and the mimic enzyme was 27:1. Under optimum conditions, a good liner correlation of the AA was 2.95μg.mL^-1—26.50μg.mL^-1 and the correlation equation was y=0.107+0.00345x（r=0.998） and the detection limit was 1.00μg.mL^-1. The concentration of AA in the beverage sample was 0.38mg.mL^-1 which was within range of the Maidong beverage label (0.25 mg.mL^-1～0.50 mg.mL^-1).更多还原