瓜环[n](n=7, 8)与盐酸法舒地尔的相互作用研究

波谱学杂志 ›› 2012, Vol. 29 ›› Issue (4): 554-563.

瓜环[n](n=7, 8)与盐酸法舒地尔的相互作用研究

陈秀丽, 朱卫国, 姜松, 杨春雪, 邹大鹏^*

郑州大学化学与分子工程学院，河南省化学生物与有机化学重点实验室，河南郑州 450052

收稿日期:2012-01-06 修回日期:2012-03-08 出版日期:2012-12-05 发布日期:2012-12-05
通讯作者: 邹大鹏,zdp@zzu.edu.cn E-mail:zdp@zzu.edu.cn
基金资助:
河南省基础与前沿技术研究计划资助项目（122300413203）.

Interaction between Cucurbit[n]uril (n=7, 8) and Fasudil Hydrochloride Studied by NMR Spectroscopy

CHEN Xiu-Li, ZHU Wei-Guo, JIANG Song, YANG Chun-Xue, ZU Da-Feng^*

Key Laboratory of Chemical Biology and Organic Chemistry of Henan Province, College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450052, China

Received:2012-01-06 Revised:2012-03-08 Online:2012-12-05 Published:2012-12-05
Contact: ZU Da-Feng,zdp@zzu.edu.cn E-mail:zdp@zzu.edu.cn
Supported by:
河南省基础与前沿技术研究计划资助项目（122300413203）.

摘要/Abstract

摘要：

分别以NMR技术、电喷雾质谱、紫外光谱和红外光谱等分析方法考察了瓜环[n](n=7, 8)与盐酸法舒地尔的相互作用. 实验结果显示, 盐酸法舒地尔与两种瓜环都形成了1∶1的包结配合物, 但其主客体配合物的作用模式随着瓜环空腔大小的不同而各不相同. 通过紫外吸收光谱法计算出瓜环[n](n=7, 8)与盐酸法舒地尔的包结常数分别为2 524 L/mol, 1 216 L/mol, 其范围在200 L/mol~10 000 L/mol之内，这说明瓜环对盐酸法舒地尔具有潜在的药物缓释作用.

关键词: 瓜环[n](n=7, 8), 盐酸法舒地尔, 包结配合物, NMR技术

Abstract:

The host-guest chemistry of systems containing fasudil hydrochloride (FSDE) and cucurbit[n]uril (CB[n], n=7, 8) was investigated by NMR, ESI-MS, UV-Vis and IR spectroscopy. The experiment results indicated that the guest fasudil hydrochloride and CB[n] (n=7, 8) host could form a stable 1∶1 (molar ratio) inclusion complex, in which the positions of CB[7] and CB[8] were different because of the sizes of their cavities. The inclusion constant of fasudil hydrochloride with CB\[7\] and CB[8] was 2 524 L/mol and 1 216 L/mol, respectively. The binding constant was in the range of 200 L/mol~10 000 L/mol, indicating that CB[7] and CB[8] could be used as possible slow-released agents.

Key words: cucurbit[n]uril, fasudil hydrochloride, inclusion complex, NMR

中图分类号:

O482.53

陈秀丽, 朱卫国, 姜松, 杨春雪, 邹大鹏. 瓜环[n](n=7, 8)与盐酸法舒地尔的相互作用研究[J]. 波谱学杂志, 2012, 29(4): 554-563.

CHEN Xiu-Li, ZHU Wei-Guo, JIANG Song, YANG Chun-Xue, ZU Da-Feng. Interaction between Cucurbit[n]uril (n=7, 8) and Fasudil Hydrochloride Studied by NMR Spectroscopy[J]. Chinese Journal of Magnetic Resonance, 2012, 29(4): 554-563.

参考文献

[1] Behrend R, Meyer E, Rusche F. Ueber condensationsproducteaus glycoluril und formaldehyd[J]. Justus Liebigs Ann Chem, 1905, 339: 1-37. 

[2] Freeman W A, Mock W L, Shih N Y. Cucurbituril[J]. J Am Chem Soc, 1981, 103: 7 367-7 368.

[3] Lagona J, Mukhopadhyay P, Chakrabrti S, et al. The cucurbit\[n\]uril family\[J\]. Angew Chem Int Ed, 2005, 44(31): 4 844-4 870.

[4] Kim J, Jung I S, Kim S Y, et al. New cucurbituril homologues: syntheses, isolation, characterization, and X-ray crystal structures of cucurbit[n]uril(n=5, 7 and 8)[J]. J Am Chem Soc, 2000, 122(3): 540-541.

[5] Isaacs L. Cucurbit[n]urils: from mechanism to structure and function[J]. Chem Commum, 2009: 619-629.

[6] Liu S M, Zavalij P Y, Isaacs L. Cucurbit[10]uril[J]. J Am Chem Soc, 2005, 127(48): 16 798-16 799.

[7] Lorenzo S, Day A, Craig D, et al. The frst endoannular metal halide-cucurbituril: cis SnCl₄(OH₂)2@cucurbit\[7\]uril\[J\]. Cryst Eng Comm, 2001, 49: 1-7.

[8] Kim H J, Jeon W S, Ko Y H, et al. Inclusion of methylviologen in cucurbit\[7\]uril\[J\]. Proc Natl Acad Sci USA, 2002, 99(8): 5 007-5 011.

[9] Day A I, Arnold A P, Blanch R J, et al. Controlling factors in the synthesis of cucurbituril and its homologues[J]. J Org Chem, 2001, 66(24): 8 094-8 100.

[10] Jeon Y J, Bharadwaj P K, Choi S W, et al. Supramolecular amphiphiles: spontaneous formation of vesicles triggered by formation of a charge-transfer complex in a host[J]. Angew Chem Int Ed, 2002, 41(23): 4 474-4 476.

[11] Fedin V P, Sokolov M N, Dybstev D N, et al. Supramolecular assemblies of [Mo₃Se4Cl_x(H₂O)_9-x](4-x)+ with cucurbituril; complementarity control through the variation of x[J]. Inorg Chim Acta, 2002, 331(1): 31-38.

[12] Lee J W, Ko Y H, Park S H, et al. Novel pseudorotaxane-terminated dendrimers: supramolecular modification of dendrimer periphery[J]. Angew Chem Int Ed, 2001, 40(4): 746-749.

[13] Buschmann H J, Cleve E, Schollmeyer E. Cucurbituril as a ligand for the complexation solutions of cations in aqueous solutions[J]. Inorg Chim Acta, 1992, 193(1): 9397.

[14] Mock W L, Shih N Y. Cycloaddition induced by cucurbituril. A case of pauling principle catalysis[J]. J Org Chem, 1983, 48(20): 3 619-3 620.

[15] Pemberton B C, Barooah N, Srivatsava D K, et al. Supramolecular photocatalysis by confinement-photodimerization of coumarins within cucurbit\[8\]urils[J]. Chem Commum, 2010, 46: 225-227.

[16] Cong H, Zhao F F, Zhang J X, et al. Rapid transformation of veratryl alcohol to veratraldehyde in presence of cucurbit[8]uril[J]. Catal Commum, 2009, 11(3): 167-170.

[17] Zou D P, Andersson S, Zhang R, et al. Selective binding of cucurbit[7]uril and β-cyclodextrin with a redox-active molecular triad Ru(bpy)³MV²⁺ naphthol[J]. Chem Commun, 2007, 4 734-4 736.

[18] Sun S G, Zhang R, Andersson S, et al. Host guest chemistry and light driven molecular lock of Ru(bpy)₃ viologen with cucurbit[7, 8]urils[J]. J Phys Chem, 2007, 111(47): 13 357-13 363.

[19] Sun S G, Zhang R, Andersson S, et al. The photoinduced long-lived charge-separated state of Ru(bpy)³methylviologen with cucurbit[8]uril in aqueous solution[J]. Chem Commun, 2006, 4 195-4 197.

[20] Chen Mu-zi(陈木子), Wang Lu(王璐), Zhang Hai-lu(张海禄), et al. NMR analysis of targeted drug gfitinib(靶向新药吉非替尼的核磁共振波谱研究)[J]. Chinese J Magn Reson (波谱学杂志), 2011, 28(3): 413-418.

[21] Cedric Loge. Synthesis and pharmacological study of Rho kinase inhibitors: pharmacomodulations on the lead compound fasudil[J]. J Enzyme Inhib Med Chem, 2003, 18(2): 127-138.

[22] Ma Yan-hui(马艳辉), Huang Ying(黄英), Zhu Qian-jiang(祝黔江), et al. Inclusion interaction of cucurbit\[8\]uril with methotrexate(八元瓜环与抗癌药物甲氨蝶呤的超分子相互作用)\[J\]. Chem J Chinese Universities (高等学校化学学报), 2011, 32(11): 2 544-2 547.

[23] Yang Xiao-na(杨晓娜), Jiang Song(姜松), Li Xin-jian(李新建), et al. Interaction of cucurbit[n]uril(n=6~8) with buflomedil(瓜环[n](n=6~8)与盐酸丁咯地尔的相互作用)[J]. Chem J Chinese Universities (高等学校化学学报), 2010, 31(12): 2 425-2 430.

[24] Zou D P, Andersson S, Zhang R, et al. A host-induced intramolecular charge-transfer complex and light-driven radical cation formation of a molecular triad with cucurbit\[8\]uril[J]. J Org Chem, 2008, 73(10): 3 775-3 783.

[25] Zou Da-peng(邹大鹏), Kang Jian-xun(康建勋), Liu Hong-min(刘宏民), et al. Sythesis of a new C10 higher carbon sugar and its structure elucidation by NMR and ESI-MS/MS (新型C10高碳糖的NMR和ESI-MS-MS研究)[J]. Chinese J Magn Reson(波谱学杂志), 2004, 21(4): 397-403.
[26] Zhao Yu-mei(赵玉梅), Tang Li-he(汤立合), Miao Zhen-chun(缪振春), et al. NMR and sterochchemistry studies of fexofenadine hydrochloride(盐酸非索非那定的NMR归属和立体化学研究)[J]. Chinese J Magn Reson(波谱学杂志), 2011, 28(2): 265-271.

[27] Feng Qin-zhong(冯钦忠), Zhou Jian-wei(周建威). Quantitative analysis of cantharidin by ¹H NMR and UV(关于斑蝥素¹H NMR和UV测定结果的商榷)[J]. Chinese J Magn Reson(波谱学杂志), 2011, 27(1): 121-125. 

[28] Pérez E M, S-nchez L, Fern-ndez G, et al. exTTF as a building block for fullerene receptors. Unexpected solvent-dependent positive homotropic cooperativity[J]. J Am Chem Soc, 2006, 128(22): 7 172-7 173.

[29] Day A I, Arnold A P, Blanch R J, et al. Controlling factors in the synthesis of cucurbituril and its homologues[J]. J Org Chem, 2001, 66(24): 8 094-8 100.

[30] Connors K A. Binding Constants[M]. New York: Willy Press, 1987. 141-161.