新型主体分子试剂的研制及用于生命相关的金属微量元素的荧光分析研究与应用
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摘要
环糊精(CD)具有相当的刚性和良好的疏水性空腔，可作为分子主体识别各种有机、无机和生物分子形成主-客体包合物，因而具有重要的研究价值。通过交联剂可将环糊精单体合成交联聚合物，这种交联聚合物保留CD原有的空腔结构，可以继续与客体分子发生包结反应。同时聚合物中单个CD单元与客体包结过程具有协同作用，使聚合物的包结作用强于CD单体。另外，交联产物具有比单体大得多的水溶性。这为环糊精的单体识别开拓了新领域，目前这方面工作仍然处在发展中，但具有广阔的应用前景。本论文研究工作的主要内容有：用环氧氯丙烷作交联剂制成了环糊精交联聚合物；研究开发了两种新型主体分子腙类试剂，并成功的用于自然界中生命相关的某些微量金属元素的识别分析。
本论文共分六章。
第一章，简单介绍了环糊精及其交联聚合物的现状研究，从中可以发现环糊精及其衍生物用与客体分子的识别是当前研究的热点。
第二章，综述了自然界中生命相关的微量金属元素的荧光分析进展，发现寻找简便迅速、选择性好和灵敏度高的新型荧光试剂，用于测定自然界中的痕量金属元素依然具有很高的理论和实际意义。
第三章，合成了邻羟基—1—萘醛缩8—氨基喹啉、五溴水杨醛水杨酰腙、邻香草醛水杨酰腙、邻羟基—1—萘醛—2—氨基吡啶、邻香草醛缩8—氨基喹啉、邻香草醛苯甲酰腙、邻香草醛呋喃甲酰腙、以及主体试剂交联聚合β-CDP-邻香草醛苯甲酰腙、β-CDP-邻香草醛呋喃甲酰腙。
第四章，交联聚合β-CDP-邻香草醛苯甲酰腙新型主体试剂的应用。利用环糊精聚合物增强的疏水性及其中β-CD单元间的协同作用，设计合成了主体试剂β-CDP-邻香草醛苯甲酰腙，并成功的用于小客体Zn~(2+)、Al~(3+)的选择识别。
第五章，交联聚合β-CDP-邻香草醛呋喃甲酰腙新型主体试剂的研制及应用。利用环糊精聚合物对直线型分子特殊的识别作用，设计合成了主体试剂β-CDP-邻香草醛呋喃甲酰腙，并成功的用于小客体Cd~(2+)、Ga~(3+)的识别检测。
Cyclodextrin and its ramifications possess comparative rigidity and favourable hydraphobic cavum, they can be used as molecular hosts to recognize different kinds of organic, inorganic, biological molecules and to form host and guest complexs, so they are worth studying. The cross-linking complex of p-CD ((3-CDP) can be made by use of cross-linking reagent such as epichlorohydrin. The cross-linking complex reserves the intrinsic cavum structure of CD and can complex with guest molecule continuely. At the same time, the CDs of the (3-CDP can cooperate to fold the guest with each other, which makes it has advantage over P-CD in fold and dissolution. Though the identification of P-CDP is in developing, it has extensive applid foreground. The main content of this article is as following: the synthesis of different kind of hydrazone and the use of determination of metal ion, the synthesis of the cross-linking complex of P-CD (p-CDP) by use of cross-Unking reagent-epichlorohydrin, the research and discovery of two
kinds of novel host reagents and the successful identification determination of some minim amounts of metal element correlative with life in nature.
There are five chapters:
Chapter one: There is a summary review about the character and research development of cyclodextrin and its cross-linking complex, from which, we can see that cyclodextrin and its cross-linking complex used in molecule recognition are the hotspots nowadays.
Chapter two: There is a review about the development of fluorescent analysis of some kinds of metal elements which cooperative with life in nature. It has very highly theoretical and practical meaning to find novel fluorescent reagent to determine these elements simply, rapidly, selectively and sensitively.
Chapter three:The synthesis of o-hydroxy-l-naphaldehydene-8-aminoquinoline, 5-bromine-salicylaldehyde salicyloylohydrazone,o-vanillin-salicyloyhydrazone,
2-hydroxy-l-naphaldehydene-2-aminopyridine.o-vanillin-8-aminoquinoline, o-vanillin benzoylhydrazone, o-vanillin furfuralhydrazone and the synthesis of p-cyclodextrin-o-vanillin benzoylhydrazone , P-cyclodextrin-o-vanillin furfuralhydrazone are showed in this chapter.
Chapter four: The application of the novel host reagent-cross-linking complex of P-cyclodextrin-o-vanillin benzoylhydrazone. The host reagent-cross-linking complex was synthesized on the hydrophobic and cooperative action of the CD and used successfully to identify the small guest such as .
Chapter five: The application of the novel host reagent-cross-Unking complex of p-cyclodextrin-o-vanillin furfuralhydrazone.The host reagent-cross-linking complex was synthesized on the special identification action on linear molecule of P-CDP and used successfully to identify the small guest such as Cd2+ Ga3+.
本论文共分六章。
第一章，简单介绍了环糊精及其交联聚合物的现状研究，从中可以发现环糊精及其衍生物用与客体分子的识别是当前研究的热点。
第二章，综述了自然界中生命相关的微量金属元素的荧光分析进展，发现寻找简便迅速、选择性好和灵敏度高的新型荧光试剂，用于测定自然界中的痕量金属元素依然具有很高的理论和实际意义。
第三章，合成了邻羟基—1—萘醛缩8—氨基喹啉、五溴水杨醛水杨酰腙、邻香草醛水杨酰腙、邻羟基—1—萘醛—2—氨基吡啶、邻香草醛缩8—氨基喹啉、邻香草醛苯甲酰腙、邻香草醛呋喃甲酰腙、以及主体试剂交联聚合β-CDP-邻香草醛苯甲酰腙、β-CDP-邻香草醛呋喃甲酰腙。
第四章，交联聚合β-CDP-邻香草醛苯甲酰腙新型主体试剂的应用。利用环糊精聚合物增强的疏水性及其中β-CD单元间的协同作用，设计合成了主体试剂β-CDP-邻香草醛苯甲酰腙，并成功的用于小客体Zn~(2+)、Al~(3+)的选择识别。
第五章，交联聚合β-CDP-邻香草醛呋喃甲酰腙新型主体试剂的研制及应用。利用环糊精聚合物对直线型分子特殊的识别作用，设计合成了主体试剂β-CDP-邻香草醛呋喃甲酰腙，并成功的用于小客体Cd~(2+)、Ga~(3+)的识别检测。
Cyclodextrin and its ramifications possess comparative rigidity and favourable hydraphobic cavum, they can be used as molecular hosts to recognize different kinds of organic, inorganic, biological molecules and to form host and guest complexs, so they are worth studying. The cross-linking complex of p-CD ((3-CDP) can be made by use of cross-linking reagent such as epichlorohydrin. The cross-linking complex reserves the intrinsic cavum structure of CD and can complex with guest molecule continuely. At the same time, the CDs of the (3-CDP can cooperate to fold the guest with each other, which makes it has advantage over P-CD in fold and dissolution. Though the identification of P-CDP is in developing, it has extensive applid foreground. The main content of this article is as following: the synthesis of different kind of hydrazone and the use of determination of metal ion, the synthesis of the cross-linking complex of P-CD (p-CDP) by use of cross-Unking reagent-epichlorohydrin, the research and discovery of two
kinds of novel host reagents and the successful identification determination of some minim amounts of metal element correlative with life in nature.
There are five chapters:
Chapter one: There is a summary review about the character and research development of cyclodextrin and its cross-linking complex, from which, we can see that cyclodextrin and its cross-linking complex used in molecule recognition are the hotspots nowadays.
Chapter two: There is a review about the development of fluorescent analysis of some kinds of metal elements which cooperative with life in nature. It has very highly theoretical and practical meaning to find novel fluorescent reagent to determine these elements simply, rapidly, selectively and sensitively.
Chapter three:The synthesis of o-hydroxy-l-naphaldehydene-8-aminoquinoline, 5-bromine-salicylaldehyde salicyloylohydrazone,o-vanillin-salicyloyhydrazone,
2-hydroxy-l-naphaldehydene-2-aminopyridine.o-vanillin-8-aminoquinoline, o-vanillin benzoylhydrazone, o-vanillin furfuralhydrazone and the synthesis of p-cyclodextrin-o-vanillin benzoylhydrazone , P-cyclodextrin-o-vanillin furfuralhydrazone are showed in this chapter.
Chapter four: The application of the novel host reagent-cross-linking complex of P-cyclodextrin-o-vanillin benzoylhydrazone. The host reagent-cross-linking complex was synthesized on the hydrophobic and cooperative action of the CD and used successfully to identify the small guest such as .
Chapter five: The application of the novel host reagent-cross-Unking complex of p-cyclodextrin-o-vanillin furfuralhydrazone.The host reagent-cross-linking complex was synthesized on the special identification action on linear molecule of P-CDP and used successfully to identify the small guest such as Cd2+ Ga3+.
引文
[1] 郝爱友，童林荟，金道森．合成化学，1995，3(3)：208．．
[2] 邹红伟，邵宇，郑琦．化学通报，1995，12：12．
[3] Ueno A. Supramol .Sci., 1996, 3(1-3):31.
[4] Szejtli j. Compr. Supramol. Chem., 1996, 3:189.
[5] Shieh W. J., Hedges A.R. J.Macromol. Sci., 1996, A33(5):673.
[6] 谢剑炜．分析化学新进展，1997，A3-20：135．
[7] Fenyvesi E., Szente L., Russell N., Monamara M. Compr. Supramol. Chem., 1996, 3:305.
[8] Chen E.T.Y., Pardue H.L. Anal. Chem., 1994, 66(20):3318.
[9] Hamai S. Bull. Chem. Soc.Jpn., 1996, 69(3):543.
[10] Brochsztain S., Rodrigues M.A., Politi M.J. J.Photochem. Photobiol., 1997,107(1-3):195.
[11] Divakar S., Maheswaran M.M. J.Inclusion. Phenom.Mol. Recognit. Chem., 1997, (2): 113.
[12] Hamada F., Ishikawa K., Tamura I., Ueno K. Anal. Sci., 1995,11(6):935.
[13] Braun T. Fullerene. Sci.Technol., 1997,5(3):615.
[14] Yoskida Z., Takekuma H., Matsubara Y. Angew. Chem., 1994, 106(15/16):1658.
[15] Hacket F., Coteron J.M., Schneider H.J., Kazachenko V.P. Can.J.Chem., 1997,75(1):52.
[16] Imaata H., Takahashi K., Hattori K. Kobunshi ronbunshu., 1995,52(10):637.
[17] Harada A., Kamachi M. New Macromol. Archit. Funct., Proc. Oums'95,2nd, 1995,107.
[18] Harada A. Adv. Polym. Sci., 1997, 133:141.
[19] Amiel C., Sandier A., Sebille B., Valat P., Wintgens V. Int.J.Polym. Anal.Charact.,1995, 1(4):289.
[20] Harada A. Supramol. Sci., 1996, 3(1-3):18.
[21] Duchene D., Wouessidjewe D. Polysaccarides Med. Appl., 1996, 575.
[22] Donze C., Coleman A.W. J.Inclusion Phenom.Mol. Recognit. Chem., 1995,23(1): 11.
[23] Yang H., Bohne C. J.Phys.Chem., 1996, 100(34):14533.
[24] (28)赵瑜，李隆第，童爱军．分析化学，1997，9：1016．
[25] Will A.Y., Schuette-parsous J.M., Agbaria R.A., Warner I.M., Appl. Spectrosc.,1995, 49(12):1762.
[26] Iketa H., Iketa O., Moon H.Y., Yoon C.J., Osa T., Nakamura A., Hamada E, Nakamura M.,Ueno A., Oh I. Shikurodekisutorin.,1995,167.
[27] Jicsinszky L., Fenyvesi E., Hashimoto H, Ueno A. Compr. Supramol.Chem., 1996,3:37.
[28] Easton C.J.,Lincoln S.F. Chem. Aust.,1997,64(4):3.
[29] Hamai S., Mononobe N. J.Photochem. Photobiol., 1995, 91(3):217.
[30] Ahern C., Darcy R., O'keeffe F., Schhwinte P. J.Inclusion Phenom. Mol. Recognit. Chem.,1996, 25(1-3):43.
[31] Maafi M., Mahedero M.C., Aaron J.J. Talanta., 1997,44(12):2193.
[32] Carofiglio T., Fornasier R.,Lucchini V. Rosso C.,Tonellato U. Tetrahedron Lett.,1996,37(44):8019.
[33] 刘育，张毅民，孙世新，张智慧，陈荣悌．化学学报，1997,55(8)：779．
[34] 谢剑炜．分析化学新进展．1997,A3-20：135．
[35] Fenyresi E., szilasi M., Zsadon B., Szejtli J., Tudos E 1-st Inter. Symp.on Cyclodextrin.,Budapest, 1981,345.
[36] 苏小迪，刘六战，沈含熙．化学学报，1996，54(10)：997．
[37] 苏小迪．刘六战，沈含熙．高等学校化学学报，1996，17(7)：1157．
[2] 邹红伟，邵宇，郑琦．化学通报，1995，12：12．
[3] Ueno A. Supramol .Sci., 1996, 3(1-3):31.
[4] Szejtli j. Compr. Supramol. Chem., 1996, 3:189.
[5] Shieh W. J., Hedges A.R. J.Macromol. Sci., 1996, A33(5):673.
[6] 谢剑炜．分析化学新进展，1997，A3-20：135．
[7] Fenyvesi E., Szente L., Russell N., Monamara M. Compr. Supramol. Chem., 1996, 3:305.
[8] Chen E.T.Y., Pardue H.L. Anal. Chem., 1994, 66(20):3318.
[9] Hamai S. Bull. Chem. Soc.Jpn., 1996, 69(3):543.
[10] Brochsztain S., Rodrigues M.A., Politi M.J. J.Photochem. Photobiol., 1997,107(1-3):195.
[11] Divakar S., Maheswaran M.M. J.Inclusion. Phenom.Mol. Recognit. Chem., 1997, (2): 113.
[12] Hamada F., Ishikawa K., Tamura I., Ueno K. Anal. Sci., 1995,11(6):935.
[13] Braun T. Fullerene. Sci.Technol., 1997,5(3):615.
[14] Yoskida Z., Takekuma H., Matsubara Y. Angew. Chem., 1994, 106(15/16):1658.
[15] Hacket F., Coteron J.M., Schneider H.J., Kazachenko V.P. Can.J.Chem., 1997,75(1):52.
[16] Imaata H., Takahashi K., Hattori K. Kobunshi ronbunshu., 1995,52(10):637.
[17] Harada A., Kamachi M. New Macromol. Archit. Funct., Proc. Oums'95,2nd, 1995,107.
[18] Harada A. Adv. Polym. Sci., 1997, 133:141.
[19] Amiel C., Sandier A., Sebille B., Valat P., Wintgens V. Int.J.Polym. Anal.Charact.,1995, 1(4):289.
[20] Harada A. Supramol. Sci., 1996, 3(1-3):18.
[21] Duchene D., Wouessidjewe D. Polysaccarides Med. Appl., 1996, 575.
[22] Donze C., Coleman A.W. J.Inclusion Phenom.Mol. Recognit. Chem., 1995,23(1): 11.
[23] Yang H., Bohne C. J.Phys.Chem., 1996, 100(34):14533.
[24] (28)赵瑜，李隆第，童爱军．分析化学，1997，9：1016．
[25] Will A.Y., Schuette-parsous J.M., Agbaria R.A., Warner I.M., Appl. Spectrosc.,1995, 49(12):1762.
[26] Iketa H., Iketa O., Moon H.Y., Yoon C.J., Osa T., Nakamura A., Hamada E, Nakamura M.,Ueno A., Oh I. Shikurodekisutorin.,1995,167.
[27] Jicsinszky L., Fenyvesi E., Hashimoto H, Ueno A. Compr. Supramol.Chem., 1996,3:37.
[28] Easton C.J.,Lincoln S.F. Chem. Aust.,1997,64(4):3.
[29] Hamai S., Mononobe N. J.Photochem. Photobiol., 1995, 91(3):217.
[30] Ahern C., Darcy R., O'keeffe F., Schhwinte P. J.Inclusion Phenom. Mol. Recognit. Chem.,1996, 25(1-3):43.
[31] Maafi M., Mahedero M.C., Aaron J.J. Talanta., 1997,44(12):2193.
[32] Carofiglio T., Fornasier R.,Lucchini V. Rosso C.,Tonellato U. Tetrahedron Lett.,1996,37(44):8019.
[33] 刘育，张毅民，孙世新，张智慧，陈荣悌．化学学报，1997,55(8)：779．
[34] 谢剑炜．分析化学新进展．1997,A3-20：135．
[35] Fenyresi E., szilasi M., Zsadon B., Szejtli J., Tudos E 1-st Inter. Symp.on Cyclodextrin.,Budapest, 1981,345.
[36] 苏小迪，刘六战，沈含熙．化学学报，1996，54(10)：997．
[37] 苏小迪．刘六战，沈含熙．高等学校化学学报，1996，17(7)：1157．