薯蓣皂苷及两种衍生固定相的制备、表征及性能评价
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摘要
本研究采用"一锅法",制备薯蓣皂苷键合硅胶固定相(D),苯基异氰酸酯、3,5-二甲基苯基异氰酸酯分别对其衍生,制备苯基异氰酸酯-薯蓣皂苷键合硅胶固定相(Phe-D)和3,5-二甲基苯基异氰酸酯-薯蓣皂苷键合硅胶固定相(DMP-D)。采用元素分析、电镜、热重分析和红外光谱等手段对三种固定相进行结构表征。以苯同系物、多环芳烃等溶质为探针,初步考察了三种新型固定相的色谱性能。结果表明薯蓣皂苷配体已键合至硅胶基质上,根据元素分析结果,按照含碳量计算得到D的表面键合量为152.61μmol/g,Phe-D的表面键合量为140.68μmol/g,DMP-D的表面键合量为151.97μmol/g;薯蓣皂苷及其衍生物固定相的反相色谱性能类似于十八烷基键合硅胶固定相(ODS),分离原理与疏水性作用有关。该衍生化反应简便易行,有望为薯蓣皂苷及其衍生物功能化色谱固定相的大规模制备提供方法学参考。
A kind of new stationary phase was prepared by one-pot reaction method which was dioscin bonded stationary phase( D),and two derivative stationary phases were prepared using phenyl isocyanate and 3,5-dimethyl phenyl isocyanate based on D,namely the phenyl isocyanate-dioscin bonded silica stationary phase( Phe-D) and the 3,5-dimethyl phenyl isocyanate-dioscin bonded silica stationary phase( DMP-D). Elemental analysis,scanning Electron Microscope( SEM),thermogravimetric Analysis and infrared spectroscopy were done to investigate the structural characteristics of dioscin and its derivative stationary phases. The results verified that the dioscin ligand has successfully bonded to the silica base material and the derivatization reactions had taken place properly. Benzene homologues and PAHs were used as solute probes to evaluate the chromatographic performance of three new stationary phases. The results showed that three new stationary phases had typical reversed-phase chromatographic performance,which were similar to the ODS,and the separation principle was related to hydrophobic effect. According to the results of elemental analysis,the surface bonding amount of D was 152. 61 μmol/g,the phe-D was 140. 68 μmol/g,and the DMP-D was 151. 97 μmol/g. The bonding and derivatization methods were considered simple to apply,and provided the methodological reference for preparing stationary phases of dioscin and its two derivative functionalized silica gel on a large scale.
A kind of new stationary phase was prepared by one-pot reaction method which was dioscin bonded stationary phase( D),and two derivative stationary phases were prepared using phenyl isocyanate and 3,5-dimethyl phenyl isocyanate based on D,namely the phenyl isocyanate-dioscin bonded silica stationary phase( Phe-D) and the 3,5-dimethyl phenyl isocyanate-dioscin bonded silica stationary phase( DMP-D). Elemental analysis,scanning Electron Microscope( SEM),thermogravimetric Analysis and infrared spectroscopy were done to investigate the structural characteristics of dioscin and its derivative stationary phases. The results verified that the dioscin ligand has successfully bonded to the silica base material and the derivatization reactions had taken place properly. Benzene homologues and PAHs were used as solute probes to evaluate the chromatographic performance of three new stationary phases. The results showed that three new stationary phases had typical reversed-phase chromatographic performance,which were similar to the ODS,and the separation principle was related to hydrophobic effect. According to the results of elemental analysis,the surface bonding amount of D was 152. 61 μmol/g,the phe-D was 140. 68 μmol/g,and the DMP-D was 151. 97 μmol/g. The bonding and derivatization methods were considered simple to apply,and provided the methodological reference for preparing stationary phases of dioscin and its two derivative functionalized silica gel on a large scale.
引文
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2 Zou HF(邹汉法),Zhang YK(张玉奎),Lu PZ(卢佩章).HPLC(高效液相色谱法)[M].Beijing:Science Press,1998:79-125.
3 Li LS(李来生),Chen XQ(陈雄泉),Yang HR(杨汉荣),et al.Preparation and characterization of a baicalin-bonded stationary phase for high performance liquid chromatograph[J].Chin J Anal Chem(分析化学),2007,35:1279-1284.
4 Armstrong DW,Tang YB,Chen SS,et al.Macrocyclic anatibiotics as a new class of chiral selectors for liquid chromatography[J].Anal Chem,1994,66:1473-1484.
5 Ekborg-Ott KH,Armstrong DW.Evaluation of the concentration and enantiomeric purity of selected free amino acids in fermented malt beverages(beers)[J].Chirality,1996,8(1):49-57.
6 Ekborg-Ott KH,Liu Y,Armstrong DW.Highly enantioselective HPLC separations using the covalently bonded macrocyclic antibiotic,ristocetin A,chiral stationary phase[J].Chirality,1998,10:434.
7 Ekborg-Ott KH,Kullman JP,Wang X,et al.Evaluation of the macrocyclic antibiotic avoparcin as a new chiral selector for HPLC[J].Chirality,1998,10:627.
8 House David W.Chiral stationary phase based on yohimbine[P].US6132606,2000-10-17.
9 Liu MF(刘妙芬),Li LS(李来生),Yang HR(杨汉荣).Study on the preparation and evaluation of a thioether-bonded silica gel stationary phase via bisalkoxysilyl coupling reagent for HPLC[J].Chin J Anal Lab(分析试验室),2009,28(4):1-5.
10 Chen HM(陈会明),Li LS(李来生),Ma HP(马海萍),et al.Study on the preparation of emodin-bonded silica stationary phase and its application in separation of nucleoside bases by HPLC[J].Chin J Anal Lab(分析试验室),2010,29(3):14-18
11 Li LS(李来生),Chen H(陈红),Ma HP(马海萍),et al.Preparation,characterization and evaluation of the magnolol bonded silica gel liquid chromatography stationary phase[J].Chem J Chinese U(高等学校化学学报),2012,33:707-713.
12 Zhou RD(周仁丹),Li LS(李来生),Cheng BP(程彪平),et al.Preparation and evaluation of a novel bois(β-cyclodextrin)-bonded SBA-15 chiral stationary phase for HPLC[J].Acta Chimica Sinica(化学学报),2014,72:720-730.
13 Zhou RD(周仁丹),Li LS(李来生),Cheng BP(程彪平),et al.Preparation and evaluation of a new nitroaniline derivative(β-cyclodextrin)-bonded SBA-15 chiral stationary phase for HPLC[J].Chem J Chinese U(高等学校化学学报),2014,35:1152-1160.
14 Gu XJ(谷晓娟),Han YQ(韩亚琼),Shen BC(沈报春),et al.Preparation,characterization and application of ginsenoside Rg1-bonded silica gel stationary phase(Ⅱ)[J].Nat Prod Res Dev(天然产物研究与开发),2014,26:824-829.
15 Han YQ(韩亚琼),Gu XJ(谷晓娟),Shen BC(沈报春),et al.Preparation,characterization and application of ginsenoside Rg1-bonded silica gel stationary phase(Ⅰ)[J].Nat Prod Res Dev(天然产物研究与开发),2014,26:268-272.
16 Li XY(李心怡),Gu XJ(谷晓娟),Shen BC(沈报春),et al.A new stationary phase for HPLC[J].Nat Prod Res Dev(天然产物研究与开发),2015,27:78-784.
17 Yin Y(尹艳),Guan HY(关红雨),Zhang XN(张夏楠).Review on enzymes and genes related to the biosynthesis of steroidal saponins[J].Nat Prod Res Dev(天然产物研究与开发),2016,28:1332-1336.
18 Kimata K,Iwaguchi K,Onishi S,et al.Chromatographic characterization of silica C18packing materials.Correlation between a preparation method and retention behavior of stationary phase[J].J Chromatogr Sci,1989,27:721-728.
19 Layne J.Characterization and comparison of the chromatographic performance of conventional,polar-embedded,and polar-endcapped reversed-phase liquid chromatography stationary phases[J].J Chromatogr A,2002,957:149-164.
20 Li WJ(李文婧),Zhao LJ(赵丽娟),Wei CHL(魏缠玲),et al.Preparation and evaluation of chromatographic properties of sulfobetaine zwitterionic hydrophilic interaction chromatography stationary phase[J].Chin J Chromatogr(色谱),2017,35:382-387.