β-环糊精手性识别D/L-樟脑磺酸的NMR研究

波谱学杂志 ›› 2009, Vol. 26 ›› Issue (4): 457-465.

β-环糊精手性识别D/L-樟脑磺酸的NMR研究

1.波谱与原子分子物理国家重点实验室，武汉磁共振中心(中国科学院武汉物理与数学研究所)，湖北武汉 430071；2.中国科学院研究生院，北京 100049；3.武汉工程大学化工与制药学院，湖北武汉 430073

收稿日期:2009-05-30 修回日期:2009-06-10 出版日期:2009-12-05 发布日期:2009-12-05
基金资助:
国家自然科学基金资助项目（10474116，10674152）

Enantiomeric Discrimination of D/L-10-Camphoric Sulfonic Acid by β-Cyclodextrins Studied by NMR Spectroscopy

1.State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Center for Magnetic Resonace,(Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences), Wuhan 430071, China; 2.Graduate School of the Chinese Academy of Sciences, Beijing 100049, China; 3.School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430073, Chin

Received:2009-05-30 Revised:2009-06-10 Online:2009-12-05 Published:2009-12-05
Supported by:
国家自然科学基金资助项目（10474116，10674152）

摘要/Abstract

摘要：

利用高分辨液体NMR技术考察了D₂O中β-环糊精与手性药物D/L-樟脑磺酸对映体之间的相互作用，结果表明樟脑磺酸对映体能够进入β-环糊精的疏水空腔并与之发生手性相互作用. β-环糊精能够手性识别樟脑磺酸对映体. 化学计量关系实验和2D ROESY实验结果表明，樟脑磺酸对映体的疏水结构只能从β-环糊精疏水空腔的宽口端进入，并形成化学计量比为1∶1的非对映体络合物.

关键词: 核磁共振（NMR）, 手性识别, β-环糊精, 樟脑磺酸

Abstract:

Chiral recognition of β-cyclodextrin (β-CD) to chiral drug D/L-10-camphoric sulfonic acid (CSA) was investigated using high resolution liquidstate NMR spectroscopy. It was found that CSA can enter the hydrophobic cavity of β-CD and interact with it chirally. The results of 2D ROESY experiments suggested that the enantiomers of CSA enter into the hydrophobic cavity of β-CD from its wide brim, not from its narrow brim. Stoichiometry result showed a 1∶1 complex between the host and the guest. It was demonstrated that β-CD can be used to discriminate the enantiomers of CSA.

Key words: NMR, chiral recognition, β-cyclodextrin, camphoric sulfonic acid

中图分类号:

O482.53

黄少华, 柏正武, 冯继文. β-环糊精手性识别D/L-樟脑磺酸的NMR研究[J]. 波谱学杂志, 2009, 26(4): 457-465.

HUANG Shao-Hua, BAI Zheng-Wu, FENG Ji-Wen. Enantiomeric Discrimination of D/L-10-Camphoric Sulfonic Acid by β-Cyclodextrins Studied by NMR Spectroscopy[J]. Chinese Journal of Magnetic Resonance, 2009, 26(4): 457-465.

参考文献

[1] Rossi B, Verrocchio P, Viliani G, et al. Vibrational properties of ibuprofen-cyclodextrin inclusion complexes investigated by Raman scattering and numerical simulation[J]. J Raman Spectrosc, 2009, 40(4): 453-458.

[2] Rodriguez J, Elola M D, Encapsulation of small ionic molecules within alpha-cyclodextrins[J]. J Phys Chem B, 2009, 113(5): 1 423-1 428.

[3] McNally A, Forster R J, Keyes T E. Interfacial supramolecular cyclodextrin-fullerene assemblies: host reorientation and guest stabilization
[J]. Phys Chem Chem Phys, 2009, 11(5): 848-856.

[4] Slavetinska L, Mosinger J, Dracinsky M, et al. NMR study of host-guest complexes of disulfonated derivatives of 9, 10-diphenylanthracene and corresponding endoperoxides with cyclodextrins[J]. J Incl Phenom Macro Chem, 2008, 61(3/4): 241-250.

[5] Ribeiro J P, Bacchi S, Dell’Anna G, et al. A combined NMR, computational, and HPLC study of the inclusion of aromatic and fluoroaromatic compounds in cyclodextrins as a model for studying carbohydrate-aromatic interactions[J]. Eur J Org Chem, 2008, (35): 5 891-5 898.

[6] Kretschmann O, Steffens C, Ritter H. Cyclodextrin complexes of polymers bearing adamantyl groups: Host-guest interactions and the effect of spacers on water solubility [J]. Angew ChemInt Edit, 2007, 46(15): 2 708-2 711.

[7] Peng min(彭敏), Kong Xu-xin(孔旭新), Zhang Hui-ping(张惠平), et al. Interactions between α-cyclodextrin and small organic molecules like salicylic acid studied by NMR diffusion measurements(α-环糊精/水杨酸等包络物的NMR自扩散研究)[J]. Chinese J Magn Reson(波谱学杂志), 2005, 22(2): 141-147.

[8] Tang Ya-lin(唐亚林), Feng Juan(冯娟), Xiang Jun-feng(向俊峰), et al. Study of the dynamic structures and equilibria of β-cyclodextrin with cyanine dyes(β-环糊精与几种菁染料包合物的动态结构及包合平衡的NMR研究)[J]. Chinese J Magn Reson(波谱学杂志), 2001, 18(2): 161-167.

[9] Segura-Sanchez F, Bouchemal K, Lebas G, et al. Elucidation of the complexation mechanism between (+)-usnic acid and cyclodextrins studied by isothermal titration calorimetry and phase-solubility diagram experiments [J]. J Mol Recognit, 2009, 22(3): 232-241.

[10] Tang W, Ng S C. Facile synthesis of mono-6-amino-6-deoxy-alpha-, beta-, gamma-cyclodextrin hydrochlorides for molecular recognition, chiral separation and drug delivery[J]. Nat Protoc, 2008, 3(4): 691-697.

[11] Izake E L. Chiral discrimination and enantioselective analysis of drugs: An overview[J]. J Pharm Sci, 2007, 96(7): 1 659-1 676.

[12] Dodziuk H. Modern conformational analysis. Elucidating novel exciting molecular sructures[M]. New York: Wiley-VCH, 1995.

[13] Wistuba D, Schurig V. Recent progress in enantiomer separation by capillary electrochromatography [J]. Electrophoresis, 2000, 21: 4 136-4 158.

[14] Juvancz Z, Szejtli J. The role of cyclodextrins in chiral selective chromatography [J]. Trac-Trends Anal Chem, 2002, 21: 379-388.

[15] Lammerhofer M, Svec F, Fréchet J M J, et al. Separation of enantiomers by capillary electrochromatography[J]. J Chromatogr A, 2000, 19: 676-698.

[16] Schurig V. Separation of enantiomers by gas chromatography[J]. J Chromatogr A, 2001, 906: 275-299.

[17] Gubitz G, Schmid M G. Chiral separation principles in capillary electrophoresis[J]. J Chromatogr A, 1997, 792: 179-225.

[18] Pham D T, Clements P, Easton C J, et al. H-1 NMR studies of enantioselective host-guest complexation by modified beta-cyclodextrins and their europium(Ⅲ) complexes[J]. Tetrahedron-Asymmetry, 2008, 19: 167-175.

[19] Uccello-Barretta G, Sicoli G, Balzano F, et al. Highly efficient NMR enantiodiscrimination of 1,1,1,3,3-pentafluoro-2-(fluoromethoxy)-3-methoxypropane, a chiral degradation product of sevoflurane, by heptakis(2,3-di-O-acetyl-6-O-tert-butyldimethylsilyl)-beta-cyclodextrin[J]. Tetrahedron-Asymmetry, 2006, 17: 2 504-2 510.

[20] Dodziuk H, Kozminski W, Ejchart A. NMR studies of chiral recognition by cyclodextrins[J]. Chirality, 2004, 16: 90-105.

[21] Nunez-Aguero C J, Escobar-Llanos C M, Diaz D, et al. Chiral discrimination of ibuprofen isomers in beta-cyclodextrin inclusion complexes: experimental (NMR) and theoretical (MD, MM/GBSA) studies[J]. Tetrahedron, 2006, 62: 4 162-4 172.

[22] Fielding L.- Determination of association constants (Ka) from solutin NMR data[J]. Tetrahedron, 2000, 56: 6 151-6 170.

[23] Caron L, Tilloy S, Monflier E, et al. Study of the inclusion complexes of beta-cyclodextrin with the sodium salt of trisulfonated triphenylphosphine[J]. J Incl Phenom Macrocycl Chem, 2000, 38: 361-379.

[24] Schneider H J, Hacket F, Rudiger V, et al. NMR studies of cyclodextrins and cyclodextrin complexes[J]. Chem Rev, 1998, 98: 1 755-1 786.

[25] Bonini M, Rossi S, Karlsson G, et al. Self-assembly of beta-cyclodextrin in water. part 1∶cryo-TEM and dynamic and static light scattering
[J]. Langmuir, 2006, 22: 1 478-1 484.

[26] Rossi S, Bonini M, Lo Nostro P, et al. Self-assembly of beta-cyclodextrin in water. 2. electron spin resonance[J]. Langmuir, 2007, 23: 10 959-10 967.