瓜环对重金属环境污染物的分子识别
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摘要
所有的重金属超过一定浓度都对人体有害,而且重金属长期积累在生物体内通常不可降解。瓜环(Q[n],n=5-8or10)是一类与环糊精、冠醚具有类似结构的笼状大环化合物,它的两个端口“镶嵌”着一圈带负电性的羰基氧原子,可以与金属离子发生亲水性的端口作用。本文利用多种超分子物理化学方法考察了瓜环对重金属铅、镉的分子识别作用,为探索瓜环在重金属的环境监测与控制中的应用提供理论依据和有用信息。
首次利用差分脉冲伏安法考察了一种新型的改性瓜环—对称四甲基六元瓜环(TMeQ[6])对铅、镉离子的识别作用。结果表明:TMeQ[6]与铅、镉离子均形成物质的量之比为1:2的超分子配合物,配合物稳定常数分别为K_(TMeQ[6]-Pb)~(2+)=2.12×10~9 L~2·mol~(-2)、K_(TMeQ[6]-Cd)~(2+)=2.10×10~9 L~2·mol~(-2)。利用单晶x-射线衍射法对TMeQ[6]与铅离子作用形成的晶体进行测试,晶体结构分析结果表明TMeQ[6]与铅离子是以1:2的作用比,在瓜环的两端口发生相互作用。两种方法的测定结果相互佐证。
自然界的含铅、镉的污水中往往还会含有其他的金属,如锌、铁、铬等,本文利用差分脉冲伏安法考察了铁、亚钴、锌等过渡金属离子共存的条件下,TMeQ[6]对铅、镉的识别性能,结果表明:TMeQ[6]对铅、镉有明显的选择性识别作用。
利用原子吸收光谱法考察了普通六元瓜环(Q[6])固体粉末对水溶液中铅离子的捕集性能,分别考察了体系pH的影响,捕集动力学、热力学性质。结果表明:当作用体系pH 1.0-6.0时,随着体系pH值的增大,六元瓜环对铅离子的捕集能力逐渐增强;捕集动力学可用Lagergren拟二级速率方程来描述,线性相关系数达到0.99以上;捕集热力学等温线符合Freundlich方程;活性炭对比实验表明,活性炭捕集铅离子符合Langmuir等温模型,瓜环与活性炭对铅的捕集模式不相同;以静态模拟方式考察了Q[6]粉末捕集含铅废水的能力,表明在浓度为1.00×10~(-2) mol/L的含铅离子模拟水样中,加入了2.0 g/mmol Q[6]固体粉末后,Q[6]粉末对铅离子的捕集率可达到98.4%。
All of the heavy metals are harmful to the human body more than a certain concentration.They are the most insidious pollutants beeause of their nonbiodegradable nature and ability to persist for long periods.Benefit Cucurbit[n]urils have two identical portals surrounded by carbonyl groups,they are able to bind metal cations as macrocyclic ligands like as crown ethers,cryptands and calixarenes and create novel supramolecular structures.Therefore,this thesis concentrates reseaches on molecular recognition of the Cucurbit[n]urils with heavy metals,In this paper,a variety of physical and chemical methods of supramolecular investigated Cucurbiturils complex with heavy metals lead and cadmium,preparation to explore Cucurbit[n]urils advantages in medical, food,clinical and enviromental monitoring fields.
1.The complex information ofα,α',δ,δ'-tetramethylcucurbit[6]uril(TMeQ[6]) with the transition metal ions has been studied by differential pulse voltammetry(DPV) and X-ray crystallography.Binding constants were determined from voltammetric data,the Pb~(2+) and Cd~(2+) dications displayed high binding affinity to TMeQ[6](K_(Pb)~(2+)=2.12×10~9 M~(-2) and K_(Cd)~(2+)=2.10×10~9 M~(-2)) and forms 2:1(M~(2+)/TMeQ[6]) complexes.The crystal structure of TMeQ[6]-Pb~(2+) showed a 2:1(pb~(2+)/TMeQ[6]) complex in solid state which was consistent with the result in the solution state.
2.Nature sewage often contain other metal besides lead and cadmium,such as zinc,iron, chromium,etc.The experimental results of differential pulse voltammetry(DPV) reveal that this water soluble cage-type compound shows very high selectivity for Pb~(2+) and Cd~(2+),while appears a masking compound for the other transition metal ions,particularly for the Co~(2+),Fe~(3+),Zn~(2+),Cr~(3+) due to a sharp decrease in the DPV peak current of these metal ions in the presence of TMeQ[6].
3.Studied the kinetic,thermodynamic of the Lead Ion adsorpt on Cucurbit[6]uril using the AAS,the kinetics could described by the Pseudo-second order model effectively, the correlation coefficient(r) more than 0.99.The adsorption isotherms for lead ion follow the Freundlich isotherm model,the correlation coefficient(r) more than 0.97 in the rome Temperature.Studing the adsorption under the condition of pH=1～6,we find the adsorption rate is best in pH=6.0,get a excellent condition for simulation waste water containing Lead 1.00×10~(-2)mol/l is treated by Static method at last,The results show that the absorption rate reach in 98.4%after the addition of the Cucurbit[6]uril 2.0 g/mmol.
首次利用差分脉冲伏安法考察了一种新型的改性瓜环—对称四甲基六元瓜环(TMeQ[6])对铅、镉离子的识别作用。结果表明:TMeQ[6]与铅、镉离子均形成物质的量之比为1:2的超分子配合物,配合物稳定常数分别为K_(TMeQ[6]-Pb)~(2+)=2.12×10~9 L~2·mol~(-2)、K_(TMeQ[6]-Cd)~(2+)=2.10×10~9 L~2·mol~(-2)。利用单晶x-射线衍射法对TMeQ[6]与铅离子作用形成的晶体进行测试,晶体结构分析结果表明TMeQ[6]与铅离子是以1:2的作用比,在瓜环的两端口发生相互作用。两种方法的测定结果相互佐证。
自然界的含铅、镉的污水中往往还会含有其他的金属,如锌、铁、铬等,本文利用差分脉冲伏安法考察了铁、亚钴、锌等过渡金属离子共存的条件下,TMeQ[6]对铅、镉的识别性能,结果表明:TMeQ[6]对铅、镉有明显的选择性识别作用。
利用原子吸收光谱法考察了普通六元瓜环(Q[6])固体粉末对水溶液中铅离子的捕集性能,分别考察了体系pH的影响,捕集动力学、热力学性质。结果表明:当作用体系pH 1.0-6.0时,随着体系pH值的增大,六元瓜环对铅离子的捕集能力逐渐增强;捕集动力学可用Lagergren拟二级速率方程来描述,线性相关系数达到0.99以上;捕集热力学等温线符合Freundlich方程;活性炭对比实验表明,活性炭捕集铅离子符合Langmuir等温模型,瓜环与活性炭对铅的捕集模式不相同;以静态模拟方式考察了Q[6]粉末捕集含铅废水的能力,表明在浓度为1.00×10~(-2) mol/L的含铅离子模拟水样中,加入了2.0 g/mmol Q[6]固体粉末后,Q[6]粉末对铅离子的捕集率可达到98.4%。
All of the heavy metals are harmful to the human body more than a certain concentration.They are the most insidious pollutants beeause of their nonbiodegradable nature and ability to persist for long periods.Benefit Cucurbit[n]urils have two identical portals surrounded by carbonyl groups,they are able to bind metal cations as macrocyclic ligands like as crown ethers,cryptands and calixarenes and create novel supramolecular structures.Therefore,this thesis concentrates reseaches on molecular recognition of the Cucurbit[n]urils with heavy metals,In this paper,a variety of physical and chemical methods of supramolecular investigated Cucurbiturils complex with heavy metals lead and cadmium,preparation to explore Cucurbit[n]urils advantages in medical, food,clinical and enviromental monitoring fields.
1.The complex information ofα,α',δ,δ'-tetramethylcucurbit[6]uril(TMeQ[6]) with the transition metal ions has been studied by differential pulse voltammetry(DPV) and X-ray crystallography.Binding constants were determined from voltammetric data,the Pb~(2+) and Cd~(2+) dications displayed high binding affinity to TMeQ[6](K_(Pb)~(2+)=2.12×10~9 M~(-2) and K_(Cd)~(2+)=2.10×10~9 M~(-2)) and forms 2:1(M~(2+)/TMeQ[6]) complexes.The crystal structure of TMeQ[6]-Pb~(2+) showed a 2:1(pb~(2+)/TMeQ[6]) complex in solid state which was consistent with the result in the solution state.
2.Nature sewage often contain other metal besides lead and cadmium,such as zinc,iron, chromium,etc.The experimental results of differential pulse voltammetry(DPV) reveal that this water soluble cage-type compound shows very high selectivity for Pb~(2+) and Cd~(2+),while appears a masking compound for the other transition metal ions,particularly for the Co~(2+),Fe~(3+),Zn~(2+),Cr~(3+) due to a sharp decrease in the DPV peak current of these metal ions in the presence of TMeQ[6].
3.Studied the kinetic,thermodynamic of the Lead Ion adsorpt on Cucurbit[6]uril using the AAS,the kinetics could described by the Pseudo-second order model effectively, the correlation coefficient(r) more than 0.99.The adsorption isotherms for lead ion follow the Freundlich isotherm model,the correlation coefficient(r) more than 0.97 in the rome Temperature.Studing the adsorption under the condition of pH=1～6,we find the adsorption rate is best in pH=6.0,get a excellent condition for simulation waste water containing Lead 1.00×10~(-2)mol/l is treated by Static method at last,The results show that the absorption rate reach in 98.4%after the addition of the Cucurbit[6]uril 2.0 g/mmol.
引文
1.万军民,胡智文,陈文兴,陈海相,余志成.纤维素纤维接枝β-环糊精的合成及其富集金属离子研究.高分子学报,2004,8(4):566-571.
2.方惠群,于俊生,史坚.仪器分析.北京:科学出版社,2002.
3.王宏镔,束文圣,蓝崇钮.重金属污染生态学研究现状与展望.生态学报,2005,25:596-605.
4.韦进宝,钱沙华.环境分析化学.北京:化学工业出版社,2002.
5.冯全芬,李浙华,刘芬芬.活性炭吸附处理黄磷化工渗滤液研究.环境科学与技术,2008,31(8):99-102.
6.李金英.ICP-MS在环境分析中的应用研究.质谱学报,1996,17:18-24.
7.刘勇,肖丹,郭灵虹,杨文树,李晖.天然蛭石对金属离子的吸附性能研究.四川大学学报(工程科学版),2006,38(3):92-96.
8.朱映川,刘雯,周遗品,雷泽湘.水体重金属污染现状及其治理方法研究进展.广东农业科学,2008,8:143-146.
9.汪尔康.分析化学.北京:北京理工大学出版社,2002.
10.严凤霞,王筱敏.现代光学仪器分析选论.上海:华东师范大学出版社,1992.
11.杜宝中.环境监测中的电化学分析法.北京:化学工业出版社,2003.
12.陈集,饶小桐.仪器分析.重庆:重庆大学出版社,2002.
13.陈怀满.土壤一植物系统中的重金属污染.北京:科学出版社,1996.
14.郑少平,李卫平.活性炭吸附除去重金属研究进展.山西建筑,2007,33(14):153-154.
15.周荣生,侯新生,马英杰.中子活化分析在大气环境及水环境研究中的应用.核技术,1999,22:362-366.
16.邹绍芳,王平.重金属电化学传感器极其在海水检测中的应用.浙江大学博士学位论文,2006.
17.党静霜,范德勇.配合物的组成及稳定常数的测定.河北工业科技,2008.25(2):86-89.
18.胡振琪,杨秀红.重金属污染土壤的粘土矿物与菌根稳定化修复技术.北京:地质出版社,2006.
19.韩宝航,刘育.葫芦脲:分子识别与组装.有机化学,2003,23:139-149.
20.杨自军.镉的污染及危害防治.中国动物保健,2008,5(1):55-60.
21.杨正亮,冯贵颖,呼世斌,郑雪斌.水体重金属污染研究现状及治理技术.干旱地区农业研究,2005,23:219-218.
22.赵振国.吸附作用应用机理.北京:化学工业出版社,2005.
23.黄德培,沈子深.离子选择电极的原理及应用.北京:新时代出版社,1982.
24.葛俊森,梁渠.水中重金属危害现状及处理方法.广州化工,2007,35(5):69-70.
25.GB3097-1997《国家标准海水水质标准》
26.GB5749-85《生活饮用水卫生标准》
27.GB8978-1996《污水综合排放标准》
28.2004-2008年中国国家海洋局《中国海洋环境质量公报》
29.Balzani,V.;Scandols,F.S.Upramolecular-Photochemistry,Ellis Harwood:New York,1990.
30.Buschmann H.J.,Cleve E.,Sccchollyer E.,Cucurbituril as a ligand for the complexation of cations in aqueous solutions.Inorg.Chim.Acta,1992,193(1):93-97.
31.Buschmann H.J.,Jansen K.,Schollmeyer E.,The formation of cucurbituril complexes with amino acids and amino alcohols in aqueous formic acid studied by calorimetric titrations.Thermochim.Acta,1998,317(1):95-98.
32.Buschmann H.J.,Cleve E.,Jansen K.,Wego A.,Schollmeyer E.,Complex formation between cucurbit[n]urils and alkali,alkaline earth and ammonium ions in aqueous solution.J.Inclusion Phenom.Mol.Recognit.,Chem.,2001,40(1～2):117-120.
33.Buschmann H.J.,Cleve E.,Jansen K.,Scholleyer E.,Determination of complex stabilities with nearly insoluble host molecules:cucurbit[5]uril,decamethylcucurbit[5]uril and cucurbit[6]uril as ligands for the complexation of some multicharged cations in aqueous solution.Anal,Chim.Acta,2001,437(1):157-163.
34.Buschmann,H.-J.;Jansen,K.;Schollmeyer,E.Cucurbit[6]uril as ligand for the complexation of lanthanide cations in aqueous solution.Inorg.Chem.Commun. 2003,6,531-534.
35. Cong H., Yang F., Tao Z., Zhang J. X., Synthesis of bi-((N-methyl-N '-benzyl) ethylenediamine) nickel(II) dichloride and studies on interaction of cucurbit[n=6 similar to 8]urils with nickel complex guest. Chinese J. Inorg. Chem., 2005, 21(3):349-356.
36. Day A. I., Blanch R. J., Arnold A P, et al. A cucurbituril-based gyroscane:a new supramolecular form. Angew Chem Int Ed, 2002, 41(2): 275-277
37. Day A. I., Arnold A. P., Blanch R. J., A method for synthesizing partially substituted cucurbit[n]uril. Molecules, 2003, 8 (1): 74-84.
38. El Haouaj, M.; Young, H. K.; Luhmer, M.; Kim, K.; Bartik, K. NMR Invest-igation of the complexation of neutral guests by cucurbitunl. J.Chem. Soc, Perkin Tran.2001, (11), 2104-2107.
39. Freeman W. A., Mock W. L., Shih N.Y., Cucurbituril. J. Am.. Chem. Soc., 1981,103(24): 7367-7368.
40. Flinn A., Hough G.C., Stoddart J.F., Williams D.J., Decamethylcucubit[5]uril ,Angew. Chem. Int. Ed. 1992, (31): 1475.
41. Fedin, V. P.; Gramlich, V.; Woerle, M.; Weber, T. Supramolecular Assemblies Based on Cucurbituril Adducts of Hydrogen-Bonded Cubane-Type Molybdenum-Nickel Sulfide Aqua Complexes. Inorg. Chem. 2001,40(5), 1074-1077.
42. Fedin V. P.; Siberian D., New Lines of Research in Chemistry of Chalcogenide Complexes: From Clusters to Supramolecular Compounds. Russ. J. Coord. Chem.,2004,30, 151-158.
43. Gerasko O. A., Mainicheva E. A., Naumova M. I., Neumaier M., Kappes M.M.,Lebedkin S., Fenske D. and Fedin V. P., Sandwich-Type Tetranuclear Lanthanide Complexes with Cucurbit[6]uril: From Molecular Compounds to Coordination Polymers. Inorg. Chem., 2008, 47, 8869.
44. Gerasko O. A., Mainicheva E. A., Naumova M. I., Yurjeva O. P., Alberola A.,Vicent C, Llusar R. and Fedin V. P., Tetranuclear lanthanide aqua hydroxo complexes with macrocyclic ligand cucurbit[6]uril. Eur. J. Inorg. Chem., 2008, 416.
45. Gerasko O. A., Sokolov M. N. and Fedin V. P., Mono- and polynuclear aqua complexes and cucurbit[6]uril: Versatile building blocks for supramolecular chemistry. Pure App. Chem., 2004,76(9), 1633-1646.
46. Gerasko O. A., Samsonenko D. G. and Fedin V. P., Supramolecular chemistry of cucurbiturils. Russ. Chem. Rev., 2002,71(9): 741-760.
47. He X. Y., Li G, Chen H. L., A new cucurbituril-based metallo-rotaxane. Inorg.Chem. Commun., 2002, 5(9): 633-636.
48. Hoffmann R., Knoche W., Fenn C., et al. Host-guest complexes ofcucurbituril withthe 4-methylbenzylammonium ion, alkali-metal cations and NH4. J. Chem. Soc.,Faraday Trans., 1994, 90(11), 1507.
49. Huang, W. H.; Zavalij, P. Y.; Isaacs, L. J., Cucurbit[n]uril Formation Proceeds by Step-Growth Cyclo-oligomerization. Am. Chem. Soc. 2008,130, 8446-8454.
50. Jon S Y, Selvapalam N, OhD H, et al. Facile Synthesis of Cucurbit[n]uril Derivatives Via Direct Funetionalization: Expanding Utilization of Cucurbit[n]uril,J Am Chem Soc, 2003, 125(34): 10186-10187
51. Jeon, W. S.; Kim, H. J.; Lee, C.; Kim, K.. Control of the stoichiometry in host-guest cmplexation by redox chemistry of guests: Inclusion of methyviologen in cucurbit[8]uril, Chem Commun, 2002, 1826-1829.
52. Kim S. Y., Jung I. S., Lee E., et al., Macrocycles within macrocycles: cyclen,cyclam, and their transition metal complexes encapsulated in cucurbit[8]uril.Angewandte Chemie International Edition, 2001,40(11): 2119-2121.
53. 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 Am Chem Soc, 2000, 122(3): 540-541.
54. Kim K., Jeon W. S., Kang J. K., Lee J. W., Jon S.Y., Kim T., Kim K., A pseudorotaxane on gold: Formation of self-assembled monolayers, reversible dethreading and rethreading of the ring, and ion'gating behavior. Angew. Chem. Int.Ed., 2003, 42(20): 2293-2296.
55. Karcher, S.; Kornmuller, A.; Jekel, M. Cucurbituril for water treatment. Part I:Solubility of cucurbituril and sorption of reactive dyes. Water Research, 2001,35(14), 3309-3316.
56. Kang, J.-K.; Hwang, I.; Ko, Y. H.; Jeon, W. S.; Kim, H.-J.; Kim, K.,Electrochemically Controllable Reversible Formation of Cucurbit[8]uril-Stabilized Charge-Transfer Complex on Surface. Supramol. Chem. 2008,20,149-155.
57. Lehn J. M., Williams A. F., Floriani C, Merbach A. S. Perspectives in Coordination Chemistry. VCH, New York, 1992.
58. Lehn, J. M. Supramolecular-chemistry concepts and perspectives, VCH, Weiheim,1995.
59. Lehn, L. M.; Atwood, J. L.; Davies, L. E. D.; Macnicol, D. D.; Vogtle, F.Comprehensive supramolecular chemistry, Pergamon: New York, 1996.
60. Liu J. X., Tao Z., Xue S. F., Zhu Q. J., Zhang J. X., Investigation of host-guest compounds of cucurbit[n=5.apprx.8]uril with some piperazine derivatives.Chinese J.Inorg. Chem., 2004, 20(2): 139-146.
61. Ma P. H., Dong J., Xiang S. C., Xue S. F., Zhu Q. J., Tao Z., Zhang J. X.,Zhou X.,Interaction of host-guest complexes of cucurbit[n]urils with double probe guests.Sci. in Chin. Ser. B: Chemistry, 2004,47(4): 301-310.
62. Mitkina, T. V.; Zakharchuk, N. F.; Naumov, D. Y.; Gerasko, O. A.; Fenske,D.;Fedin, V. P., Syntheses, structures, and electrochemical properties of inclusion compounds of cucurbit[8]uril with cobalt(III) and nickel(II) complexes. Inorg.Chem. 2008, 47, 6748-6755.
63. Mock, W. L.; Shih, N. Y. Dynamics of molecular recognition involving cucurbituril.J. Am. Chem. Soc, 1989, 111(7): 2697-2699.
64. Mock W. L., Irra T A, Wepsiec J. P, Adhya M., Catalysis by cucurbituril. The significance of bound-substrate destabilization for induced triazole formation. J.Org. Chem., 1989, 54(22): 5302-5308.
65. Motohiro N.; Yoji U.; Minoru H.; Takeuchi Y. The CH/π Interaction: Significance in molecular recognition. Tetrahedron, 1995, 51, 8665.
66. Neugebauer R., Knoche W., Host-guest complexes of cucurbituril with 4-amino-4'-nitroazobenzene and 4, 4'-diaminoazobenzene in acidic aqueous solutions. J.Chem. Soc. Perkin Trans. , 1998, (3): 529-534.
67. Ni X. L., Lin J. X., Zheng Y. Y., Wu W. S., Zhang Y. Q., S. F. Xue S. F., Zhu Q. J., Tao Z. and. Day A. I, Supramolecular Bracelets and Interlocking Rings Elaborated Through the Interrelationship of Neighboring Chemical Environments of Alkyl-Substitution on Cucurbit[5]uril. Cryst. Growth Des., 2008, 8, 3446.
68. Ong W., Kaifer A. E., Molecular encapsulation by cucurbit[7]uril of the apical 4,4'-bipyridinium residuein newkome-type dendrime. Angew. Chem. Inter. Ed.,2003,42:2164-2167.
69. Shen Y. Q., Xue S. F., Zhao Y. J., Zhu Q. J., Tao Z., NMR study on self-assembled cage complex of hexamethylenetetramine and cucurbit[n]urils. Chin.Sci. Bull.,2003, 48(24): 2694-2697.
70. Sobransingh, D.; Kaifer, A. E. New Dendrimers Containing a Single Cobaltocenium Unit Covalently Attached to the Apical Position of Newkome Dendrons: Electrochemistry and Guest Binding Interactions with Cucurbit[7]uril.Langmuir, 2006, 22, 10540-10544
71. Sokolov M. N., Dybtsev D. N. and Fedin V. P., Supramolecular compounds of cucurbituril with molybdenum and tungsten chalcogenide cluster aqua complexes.Russ. Chem. Bull., 2003, 52, 1041-1060.
72. Trabolsi, A.; Hmadeh, M.; Khashab, N. M.; Friedman, D. C.; Belowich, M. E.;Humbert, N.; Elhabiri, M.; Khatib, H. A.; Albrecht-Gary, A.-M.; Stoddart,J. F.Redox-driven switching in pseudorotaxanes. New J. Chem. 2009, 33, 254-263.
73. W. S. Jeon, K. Moon, S. H. Park, H. Chun, Y. H. Ko, J. Y. Lee, E. S. Lee, S. Samal,N. Selvapalam, M. V. Rekharsky,. V. Sindelar, D. Sobransingh, Y. Inoue, A. E.Kaifer, K. Kim, Complexation of Ferrocene Derivatives by the Cucurbit[7]uril Host:A Comparative Study of the Cucurbituril and Cyclodextrin Host Families. J. Am.Chem. Soc. 2005, 127, 12984-12989.
74. Xu Z.Q., Yao X.Q., Xue S. F., Zhu Q. J., Tao Z., Zhang J. X., Wei Z. B., Long L. S.,Investigation of structures of the self-assembled pseudorotaxane of cucurbiturils with some alkyldiamines. Acta Chim. Sinica, 2004, 62(19): 1927-1934.
75. Zhao, J. Z.; Kim, H. J.; Oh, J. H.; Kim, S. Y; Lee, J. W.; Sakamoto, S.; Yamaguchi,K.; Kim, K. Cucurbit[n]uril derivatives soluble in water and organic solvents.Angew. Chem., Int. Ed. 2001, 40(22), 4233-4235.
76. Zhao Y. J., Xue S. F., Zhu Q. J., Tao Z., Zhang J. X., Wei Z. B., Long L.S., Hu M.L., Xiao H. P. and Day A. I.. Synthesis of tetramethylcucurbit[6]uril and study the host-guest inclusion complexe with 2,2'-bipyridine. Chin. Sci. Bull., 2004, 49,1047-1051
2.方惠群,于俊生,史坚.仪器分析.北京:科学出版社,2002.
3.王宏镔,束文圣,蓝崇钮.重金属污染生态学研究现状与展望.生态学报,2005,25:596-605.
4.韦进宝,钱沙华.环境分析化学.北京:化学工业出版社,2002.
5.冯全芬,李浙华,刘芬芬.活性炭吸附处理黄磷化工渗滤液研究.环境科学与技术,2008,31(8):99-102.
6.李金英.ICP-MS在环境分析中的应用研究.质谱学报,1996,17:18-24.
7.刘勇,肖丹,郭灵虹,杨文树,李晖.天然蛭石对金属离子的吸附性能研究.四川大学学报(工程科学版),2006,38(3):92-96.
8.朱映川,刘雯,周遗品,雷泽湘.水体重金属污染现状及其治理方法研究进展.广东农业科学,2008,8:143-146.
9.汪尔康.分析化学.北京:北京理工大学出版社,2002.
10.严凤霞,王筱敏.现代光学仪器分析选论.上海:华东师范大学出版社,1992.
11.杜宝中.环境监测中的电化学分析法.北京:化学工业出版社,2003.
12.陈集,饶小桐.仪器分析.重庆:重庆大学出版社,2002.
13.陈怀满.土壤一植物系统中的重金属污染.北京:科学出版社,1996.
14.郑少平,李卫平.活性炭吸附除去重金属研究进展.山西建筑,2007,33(14):153-154.
15.周荣生,侯新生,马英杰.中子活化分析在大气环境及水环境研究中的应用.核技术,1999,22:362-366.
16.邹绍芳,王平.重金属电化学传感器极其在海水检测中的应用.浙江大学博士学位论文,2006.
17.党静霜,范德勇.配合物的组成及稳定常数的测定.河北工业科技,2008.25(2):86-89.
18.胡振琪,杨秀红.重金属污染土壤的粘土矿物与菌根稳定化修复技术.北京:地质出版社,2006.
19.韩宝航,刘育.葫芦脲:分子识别与组装.有机化学,2003,23:139-149.
20.杨自军.镉的污染及危害防治.中国动物保健,2008,5(1):55-60.
21.杨正亮,冯贵颖,呼世斌,郑雪斌.水体重金属污染研究现状及治理技术.干旱地区农业研究,2005,23:219-218.
22.赵振国.吸附作用应用机理.北京:化学工业出版社,2005.
23.黄德培,沈子深.离子选择电极的原理及应用.北京:新时代出版社,1982.
24.葛俊森,梁渠.水中重金属危害现状及处理方法.广州化工,2007,35(5):69-70.
25.GB3097-1997《国家标准海水水质标准》
26.GB5749-85《生活饮用水卫生标准》
27.GB8978-1996《污水综合排放标准》
28.2004-2008年中国国家海洋局《中国海洋环境质量公报》
29.Balzani,V.;Scandols,F.S.Upramolecular-Photochemistry,Ellis Harwood:New York,1990.
30.Buschmann H.J.,Cleve E.,Sccchollyer E.,Cucurbituril as a ligand for the complexation of cations in aqueous solutions.Inorg.Chim.Acta,1992,193(1):93-97.
31.Buschmann H.J.,Jansen K.,Schollmeyer E.,The formation of cucurbituril complexes with amino acids and amino alcohols in aqueous formic acid studied by calorimetric titrations.Thermochim.Acta,1998,317(1):95-98.
32.Buschmann H.J.,Cleve E.,Jansen K.,Wego A.,Schollmeyer E.,Complex formation between cucurbit[n]urils and alkali,alkaline earth and ammonium ions in aqueous solution.J.Inclusion Phenom.Mol.Recognit.,Chem.,2001,40(1～2):117-120.
33.Buschmann H.J.,Cleve E.,Jansen K.,Scholleyer E.,Determination of complex stabilities with nearly insoluble host molecules:cucurbit[5]uril,decamethylcucurbit[5]uril and cucurbit[6]uril as ligands for the complexation of some multicharged cations in aqueous solution.Anal,Chim.Acta,2001,437(1):157-163.
34.Buschmann,H.-J.;Jansen,K.;Schollmeyer,E.Cucurbit[6]uril as ligand for the complexation of lanthanide cations in aqueous solution.Inorg.Chem.Commun. 2003,6,531-534.
35. Cong H., Yang F., Tao Z., Zhang J. X., Synthesis of bi-((N-methyl-N '-benzyl) ethylenediamine) nickel(II) dichloride and studies on interaction of cucurbit[n=6 similar to 8]urils with nickel complex guest. Chinese J. Inorg. Chem., 2005, 21(3):349-356.
36. Day A. I., Blanch R. J., Arnold A P, et al. A cucurbituril-based gyroscane:a new supramolecular form. Angew Chem Int Ed, 2002, 41(2): 275-277
37. Day A. I., Arnold A. P., Blanch R. J., A method for synthesizing partially substituted cucurbit[n]uril. Molecules, 2003, 8 (1): 74-84.
38. El Haouaj, M.; Young, H. K.; Luhmer, M.; Kim, K.; Bartik, K. NMR Invest-igation of the complexation of neutral guests by cucurbitunl. J.Chem. Soc, Perkin Tran.2001, (11), 2104-2107.
39. Freeman W. A., Mock W. L., Shih N.Y., Cucurbituril. J. Am.. Chem. Soc., 1981,103(24): 7367-7368.
40. Flinn A., Hough G.C., Stoddart J.F., Williams D.J., Decamethylcucubit[5]uril ,Angew. Chem. Int. Ed. 1992, (31): 1475.
41. Fedin, V. P.; Gramlich, V.; Woerle, M.; Weber, T. Supramolecular Assemblies Based on Cucurbituril Adducts of Hydrogen-Bonded Cubane-Type Molybdenum-Nickel Sulfide Aqua Complexes. Inorg. Chem. 2001,40(5), 1074-1077.
42. Fedin V. P.; Siberian D., New Lines of Research in Chemistry of Chalcogenide Complexes: From Clusters to Supramolecular Compounds. Russ. J. Coord. Chem.,2004,30, 151-158.
43. Gerasko O. A., Mainicheva E. A., Naumova M. I., Neumaier M., Kappes M.M.,Lebedkin S., Fenske D. and Fedin V. P., Sandwich-Type Tetranuclear Lanthanide Complexes with Cucurbit[6]uril: From Molecular Compounds to Coordination Polymers. Inorg. Chem., 2008, 47, 8869.
44. Gerasko O. A., Mainicheva E. A., Naumova M. I., Yurjeva O. P., Alberola A.,Vicent C, Llusar R. and Fedin V. P., Tetranuclear lanthanide aqua hydroxo complexes with macrocyclic ligand cucurbit[6]uril. Eur. J. Inorg. Chem., 2008, 416.
45. Gerasko O. A., Sokolov M. N. and Fedin V. P., Mono- and polynuclear aqua complexes and cucurbit[6]uril: Versatile building blocks for supramolecular chemistry. Pure App. Chem., 2004,76(9), 1633-1646.
46. Gerasko O. A., Samsonenko D. G. and Fedin V. P., Supramolecular chemistry of cucurbiturils. Russ. Chem. Rev., 2002,71(9): 741-760.
47. He X. Y., Li G, Chen H. L., A new cucurbituril-based metallo-rotaxane. Inorg.Chem. Commun., 2002, 5(9): 633-636.
48. Hoffmann R., Knoche W., Fenn C., et al. Host-guest complexes ofcucurbituril withthe 4-methylbenzylammonium ion, alkali-metal cations and NH4. J. Chem. Soc.,Faraday Trans., 1994, 90(11), 1507.
49. Huang, W. H.; Zavalij, P. Y.; Isaacs, L. J., Cucurbit[n]uril Formation Proceeds by Step-Growth Cyclo-oligomerization. Am. Chem. Soc. 2008,130, 8446-8454.
50. Jon S Y, Selvapalam N, OhD H, et al. Facile Synthesis of Cucurbit[n]uril Derivatives Via Direct Funetionalization: Expanding Utilization of Cucurbit[n]uril,J Am Chem Soc, 2003, 125(34): 10186-10187
51. Jeon, W. S.; Kim, H. J.; Lee, C.; Kim, K.. Control of the stoichiometry in host-guest cmplexation by redox chemistry of guests: Inclusion of methyviologen in cucurbit[8]uril, Chem Commun, 2002, 1826-1829.
52. Kim S. Y., Jung I. S., Lee E., et al., Macrocycles within macrocycles: cyclen,cyclam, and their transition metal complexes encapsulated in cucurbit[8]uril.Angewandte Chemie International Edition, 2001,40(11): 2119-2121.
53. 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 Am Chem Soc, 2000, 122(3): 540-541.
54. Kim K., Jeon W. S., Kang J. K., Lee J. W., Jon S.Y., Kim T., Kim K., A pseudorotaxane on gold: Formation of self-assembled monolayers, reversible dethreading and rethreading of the ring, and ion'gating behavior. Angew. Chem. Int.Ed., 2003, 42(20): 2293-2296.
55. Karcher, S.; Kornmuller, A.; Jekel, M. Cucurbituril for water treatment. Part I:Solubility of cucurbituril and sorption of reactive dyes. Water Research, 2001,35(14), 3309-3316.
56. Kang, J.-K.; Hwang, I.; Ko, Y. H.; Jeon, W. S.; Kim, H.-J.; Kim, K.,Electrochemically Controllable Reversible Formation of Cucurbit[8]uril-Stabilized Charge-Transfer Complex on Surface. Supramol. Chem. 2008,20,149-155.
57. Lehn J. M., Williams A. F., Floriani C, Merbach A. S. Perspectives in Coordination Chemistry. VCH, New York, 1992.
58. Lehn, J. M. Supramolecular-chemistry concepts and perspectives, VCH, Weiheim,1995.
59. Lehn, L. M.; Atwood, J. L.; Davies, L. E. D.; Macnicol, D. D.; Vogtle, F.Comprehensive supramolecular chemistry, Pergamon: New York, 1996.
60. Liu J. X., Tao Z., Xue S. F., Zhu Q. J., Zhang J. X., Investigation of host-guest compounds of cucurbit[n=5.apprx.8]uril with some piperazine derivatives.Chinese J.Inorg. Chem., 2004, 20(2): 139-146.
61. Ma P. H., Dong J., Xiang S. C., Xue S. F., Zhu Q. J., Tao Z., Zhang J. X.,Zhou X.,Interaction of host-guest complexes of cucurbit[n]urils with double probe guests.Sci. in Chin. Ser. B: Chemistry, 2004,47(4): 301-310.
62. Mitkina, T. V.; Zakharchuk, N. F.; Naumov, D. Y.; Gerasko, O. A.; Fenske,D.;Fedin, V. P., Syntheses, structures, and electrochemical properties of inclusion compounds of cucurbit[8]uril with cobalt(III) and nickel(II) complexes. Inorg.Chem. 2008, 47, 6748-6755.
63. Mock, W. L.; Shih, N. Y. Dynamics of molecular recognition involving cucurbituril.J. Am. Chem. Soc, 1989, 111(7): 2697-2699.
64. Mock W. L., Irra T A, Wepsiec J. P, Adhya M., Catalysis by cucurbituril. The significance of bound-substrate destabilization for induced triazole formation. J.Org. Chem., 1989, 54(22): 5302-5308.
65. Motohiro N.; Yoji U.; Minoru H.; Takeuchi Y. The CH/π Interaction: Significance in molecular recognition. Tetrahedron, 1995, 51, 8665.
66. Neugebauer R., Knoche W., Host-guest complexes of cucurbituril with 4-amino-4'-nitroazobenzene and 4, 4'-diaminoazobenzene in acidic aqueous solutions. J.Chem. Soc. Perkin Trans. , 1998, (3): 529-534.
67. Ni X. L., Lin J. X., Zheng Y. Y., Wu W. S., Zhang Y. Q., S. F. Xue S. F., Zhu Q. J., Tao Z. and. Day A. I, Supramolecular Bracelets and Interlocking Rings Elaborated Through the Interrelationship of Neighboring Chemical Environments of Alkyl-Substitution on Cucurbit[5]uril. Cryst. Growth Des., 2008, 8, 3446.
68. Ong W., Kaifer A. E., Molecular encapsulation by cucurbit[7]uril of the apical 4,4'-bipyridinium residuein newkome-type dendrime. Angew. Chem. Inter. Ed.,2003,42:2164-2167.
69. Shen Y. Q., Xue S. F., Zhao Y. J., Zhu Q. J., Tao Z., NMR study on self-assembled cage complex of hexamethylenetetramine and cucurbit[n]urils. Chin.Sci. Bull.,2003, 48(24): 2694-2697.
70. Sobransingh, D.; Kaifer, A. E. New Dendrimers Containing a Single Cobaltocenium Unit Covalently Attached to the Apical Position of Newkome Dendrons: Electrochemistry and Guest Binding Interactions with Cucurbit[7]uril.Langmuir, 2006, 22, 10540-10544
71. Sokolov M. N., Dybtsev D. N. and Fedin V. P., Supramolecular compounds of cucurbituril with molybdenum and tungsten chalcogenide cluster aqua complexes.Russ. Chem. Bull., 2003, 52, 1041-1060.
72. Trabolsi, A.; Hmadeh, M.; Khashab, N. M.; Friedman, D. C.; Belowich, M. E.;Humbert, N.; Elhabiri, M.; Khatib, H. A.; Albrecht-Gary, A.-M.; Stoddart,J. F.Redox-driven switching in pseudorotaxanes. New J. Chem. 2009, 33, 254-263.
73. W. S. Jeon, K. Moon, S. H. Park, H. Chun, Y. H. Ko, J. Y. Lee, E. S. Lee, S. Samal,N. Selvapalam, M. V. Rekharsky,. V. Sindelar, D. Sobransingh, Y. Inoue, A. E.Kaifer, K. Kim, Complexation of Ferrocene Derivatives by the Cucurbit[7]uril Host:A Comparative Study of the Cucurbituril and Cyclodextrin Host Families. J. Am.Chem. Soc. 2005, 127, 12984-12989.
74. Xu Z.Q., Yao X.Q., Xue S. F., Zhu Q. J., Tao Z., Zhang J. X., Wei Z. B., Long L. S.,Investigation of structures of the self-assembled pseudorotaxane of cucurbiturils with some alkyldiamines. Acta Chim. Sinica, 2004, 62(19): 1927-1934.
75. Zhao, J. Z.; Kim, H. J.; Oh, J. H.; Kim, S. Y; Lee, J. W.; Sakamoto, S.; Yamaguchi,K.; Kim, K. Cucurbit[n]uril derivatives soluble in water and organic solvents.Angew. Chem., Int. Ed. 2001, 40(22), 4233-4235.
76. Zhao Y. J., Xue S. F., Zhu Q. J., Tao Z., Zhang J. X., Wei Z. B., Long L.S., Hu M.L., Xiao H. P. and Day A. I.. Synthesis of tetramethylcucurbit[6]uril and study the host-guest inclusion complexe with 2,2'-bipyridine. Chin. Sci. Bull., 2004, 49,1047-1051