Vol.2 No.2 (May 2012)
Inclusion Complex of Malachite Green with Cucurbituril and Detection of Malachite Green using Cucurbituril
摘要:利用荧光光谱滴定法研究孔雀石绿和葫芦脲的包结作用，在一定的浓度范围内，我们发现孔雀石绿的荧光强度随着葫芦脲的浓度的增加而增加，同时，最大发射峰的位置发生了一定程度的红移。我们利用了紫外–可见吸收光谱、荧光光谱、IR、1H NMR和量子化学计算等方法研究了水溶液中孔雀石绿与葫芦脲之间的包结行为，探讨了MG-CB的包结机理。相关的结果表明孔雀石绿与葫芦之间形成1:1的包结络合物。该方法的检出限是4.2 × 10–8 mol·L–1。
The interaction between malachite green (MG) and cucurbituril (CB7) had been studied based on fluores-cence and 1H NMR spectroscopic results. The interaction mechanism was also discussed concretely based on 1H NMR results. The fluorescence intensity of malachite green (MG) enhanced strongly and a slight red shift was observed at the maximum emission peak when added into cucurbituril. We had found that the formation of the complex at a 1:1 complex stoichiometry and the association constant was calculated by applying a deduced equation. The thermody-namic parameters such as ΔH and ΔS values were obtained according to Van’t Hoff equation, respectively. We prepared the solid inclusion complex from co-evaporation method and characterised it by 1H NMR、IR. For the efficient detection of malachite green, the limit of detection was 4.2 × 10–8 mol·L–1 from our experiments which will make our method applied to detect the malachite green in sewage effectively.
唐冬宝 , 孙军勇 , 武凯 , 李涛 , 周运友 (2012) 葫芦脲对孔雀石绿的包结作用及应用。 分析化学进展， 2， 7-13. doi: 10.12677/aac.2012.22002
 G. Y. Chen, S. Miao. HPLC determination and MS confirmation of malachite green, gentian violet, and their leuco metabolite residues in channel catfish muscle. Journal of Agricultural and Food Chemistry, 2010, 58(12): 7109-7114.
 D. J. Alderman. Malachite green: A review. Journal of Fish Disease, 1985, 8(3): 289-298.
 S. L. Stead, H. Ashwin, B. H. Johnston, A. Dallas, S. A. Kazakov, J. A. Tarbin, M. Sharman, J. Kay and B. J. Keely. An RNA-ap- tamer based on assay for the detection and analysis of malachite green and leucomalachite green residues in fish tissue. Ana- lytical Chemistry, 2010, 82(7): 2652-2660.
 F. Ding, W. Liu, F. Liu, Z. Y. Li and Y. Sun. A study of the interaction between malachite green and lysozyme by steady- state fluorescnece. Journal of Fluorescence, 2009, 19(5): 783- 791.
 S. Srivastava, R. Sinha and D. Roy. Toxicological effect of malachite green. Aquatic Toxicology, 2004, 66(3): 319-329.
 C. Berberidou, I. Poulios, N. P. Xekoukoulotaki and D. Mant- zavinos. Sonolytic, photocatalytic and sonophotocatalytic deg- radation of malachite green in aqueous solutions. Applied Ca- talysis B Environmental, 2007, 74(1-2): 63-72.
 W. C. Andersen, S. B. Turnipseed, C. M. Karbiwnyk, R. H. Lee, S. B. Clark, W. D. Rowe, M. R. Madson and K. E. Miller. Multiresidue method for the triphenylmethane dyes in fish, malachite green, crystal (gentian) violet and brilliant green. Analytica Chimica Acta, 2009, 637(1-2): 279-289.
 J. L. Allen, J. R. Meinertz. Post-column reaction for simultane- ous analysis of chromatic and leuco forms of malachite green and crystal violet by high-performance liquid chromatography with photometric detection. Journal of Chromatography A, 1991, 536: 217-222.
 S. M. Plakas, K. R. E. Said, G. R. Stehly and J. E. Roybal. Opti- mization of a liquid chromatographic method for determination of malachite green and its metabolites in fish tissues. Journal of AOAC International, 1995, 78(6): 1388-1394.
 J. A. Tarbin, K. A. Barnes, J. Bygrave and W. H. H. Farrington. Screening and confirmation of triphenylmethane dyes and their leuco metabolites in trout muscle using HPLC-vis and LC-elec- trospray MS. Analyst, 1998, 123(12): 2567-2571.
 C. Long, Z. Mai, B. Zhu, X. Zou, Y. Gao and X. Huang. New oxidant used for the post-column derivatization determination of malachite green and leucomalachite green residues in cultured aquatic products by high-performance liquid chromatography. Journal of Chromatography A, 2008, 1203(1): 21-26.
 C. Marquez, W. M. Nau. Polarizabilities inside molecular containers. Angewandte Chemie International Edition, 2001, 40(23): 4387- 4390.
 J. Lagona, P. Mukhopadhyay, S. Chakrabarti and L. Isaacs. The cucurbit[n]uril family. Angewandte Chemie International Edition, 2005, 44(31): 4844-4870.
 K. Kim, N. Selvapalam, Y. H. Ko, K. M. Park, D. Kim and J. Kim. Functionalized cucurbiturils and their applications. Che- mical Society Reviews, 2007, 36(2): 267-279.
 Y. Tan, S. W. Choi, J. W. Lee, Y. H. Ko and K. Kim. Synthesis and characterization of novel side-chain pseudopolyro-taxane containing cucurbituril. Macromolecules, 2002, 35(18): 7161- 7165.
 J. W. Lee, Y. H. Ko, S.-H. Park, K. Yamaguchi and K. Kim. Novel pseudorotaxane-terminated dendrimers: Supramolecule modification of dendrimer periphery. Angewandte Chemie In- ternational Edition, 2001, 40(4): 746-749.
 J. W. Lee, S. Samal, N. Selvapalam, H.-J. Kim and K. Kim. Cucurbituril homologues and derivatives: New opportunity in su- pramolecular chemistry. Accounts of Chemical Research, 2003, 36(8): 621-630.
 J. Mohanty, W. M. Nau. Refractive index effects on the oscillator strength and radiative decay rate of 2,3-diazabicyclo[2,2,2] oct-2-ene. Photochemical and Photobiological Science, 2004, 3(11-12): 1026-1031.
 C. Marquez, W. M. Nau. Polarizabilities inside molecular containers. Angewandte Chemie International Edition, 2001, 40(23): 4387-4390.
 S. D. Choudhury, J. Mohanty, H. Pal and A. C. Bhasikuttan. Cooperative metal ion binding to a cucurbituril-thioflavin T complex: Demonstration of a stimulus-responsive fluorescent supramolecular capsule. Journal of the American Chemical So- ciety, 2010, 132(4): 1395-1404.
 F. Xing, D. Hao, C. Kai, X. Xin, X. L. Shi, F. X. Sai, Q. Z. Yun, J. Z. Qian, T. Zhu, Y. Z. Xiao and W. Gang. Design and synthesis of self-assembly supramolecular entities based on noncovalent interaction of cucurbituril, metal ions, and hydroxybenzene or its derivatives. Crystal Growth & Design, 2010, 10(7): 2901- 2907.
 J. S. Liu, N. Jiang, J. Ma and X. Z. Du. Insight into unusual downfield NMR shifts in the inclusion complex of acridine or- ange with cucurbituril. European Journal of Organic Che- mistry, 2009, 2009(29): 4931-4938.
 J. Kim, I. S. Jung, S. Y. Kim, E. Lee, J. K. Kang, S. Sakamoto, K. Yamaguchi and K. Kim. New cucurbituril homologues: Syntheses, isolation, characterization, and x-ray crystal structures of cucurbit[n]uril (n = 5, 7, and 8). Journal of the American Che- mical Society, 2000, 122(3): 540-541.
 A. I. Day, A. P. Arnold, R. J. Blanch and B. Snushall. Control- ling factors in the synthesis of cucurbituril and its homologues. Journal of Organic Chemistry, 2001, 66(24): 8094-8100.
 Y. M. Jeon, J. Kim, D. Whang and K. Kim. Molecular container assembly capable of controlling binding and release of its guest molecules: Re-versible encapsulation of organic molecules in sodium ion complexed cucurbituril. Journal of the American Chemical Society, 1996, 118(40): 9790-9791.
 C. Marquez, R. R. Hudgins and W. M. Nau. The mechanism of host-guest complexation by cucurbituril. Journal of the Ame- rican Chemical Society, 2004, 126(18): 5806-5816.
 C. Marquez, H. Fang and W. M. Nau. Cucurbiturils: Molecular nanocapsules for time-resolved fluorescence-based assays. IEEE Transactions on Nano-Bioscience, 2004, 3(1): 39-45.
 A. C. Bhasikuttan, J. Mohanty, W. M. Nau and H. Pal. Efficient fluorescence enhancement and cooperative binding of an organic dye in a supra-bimolecular host-protein assembly. Angewandte Chemie International Edition, 2007, 46(22): 4120-4122.