基于氢键和两亲性组装的光开关超分子的设计合成及应用
|
摘要
由功能性小分子组装成具有超分子结构的软材料和纳米器件是一种有效的发展新材料的方法,近些年来新型的超分子自组装材料构筑模块已经越来越引起人们的注意。因为它们可以通过特殊的非化学键分子相互作用如氢键,疏水作用,π-π堆积作用及范德华力来形成具有稳定均一结构的纳米级器件。本文中,我们采用光致变色二芳乙烯分子通过接有萘啶的衍生物来达到识别含有萘酰亚胺的鸟嘌呤衍生物的作用,对形成组装的机理,组装的形貌,以及堆积形式加以研究,同时将该材料应用于生物成像,发现其在不同比例组装下对KB细胞有特别的作用,同时还设计合成了一些预期小分子凝胶中间体,本文结构如下:
1.设计了含有萘啶的二芳烯衍生物,通过强的三重氢键作用与含有萘酰亚胺荧光团的鸟嘌呤衍生物进行氢键组装,通过核磁滴定和光谱数据证实了组装行为,通过扫描电镜观察了组装后的形貌。组装体含有特殊的光物理光化学性质,以及相应的光致变色行为,不同比例的组装体对于KB细胞有特殊的作用,与HeLa细胞进行了比对试验
2.设计合成了含有胆甾酸的的伞形分子,没有获得预期的凝胶效果,发现胆甾酸衍生物几乎不能形成有机凝胶,合成了含有没食子酸长烷基链衍生物的预期小分子凝胶中间体,对比分子进行了合成设计表征。
The self-assembling of small functional molecules into supramolecular structures is a powerful approach towards the development of soft materials and nanoscale devices. As a novel class of self-assembled materials, new supramolecular building block have received considerable attention in recent years because they can organize into regular nanoarchitectures through specific non-covalent interactions including hydrogen-bonding, hydrophobic interactions,π-πinteractions and Van der Waals forces. In this masters thesis, photochromic diarylethene moiety contained naphthyridine and the derivative of guanine were designed and synthesized. The morphology, mechanism of the assembly formation and the packing fashion were studied in details, and the assembly materials were applied in bio-imaging,and respond to KB cell. Meanwhile, some low weight molecular gelator synthetized. The research contains two parts as following
1. strong intermolecular hydrogen-bonds are designed through naphthyridine and guanine base on diarylethene, which are verified by NMR,UV-VIS,IR, The self-assembly complex gives special photophysical and photochemical properties and these properties could be well controlled by light.The complex can imagine in KB cell ,different proportions can get different results.
2. We synthesized derivatives of cholic acid with naphthalimide and found that the small amount of low weight molecules can not gel any organic solvents. Designed and synthesized two derivatives of trihydroxybenzoic with three hydrophobic alkyl chains , which have the ability for gelating some organic solvents.
1.设计了含有萘啶的二芳烯衍生物,通过强的三重氢键作用与含有萘酰亚胺荧光团的鸟嘌呤衍生物进行氢键组装,通过核磁滴定和光谱数据证实了组装行为,通过扫描电镜观察了组装后的形貌。组装体含有特殊的光物理光化学性质,以及相应的光致变色行为,不同比例的组装体对于KB细胞有特殊的作用,与HeLa细胞进行了比对试验
2.设计合成了含有胆甾酸的的伞形分子,没有获得预期的凝胶效果,发现胆甾酸衍生物几乎不能形成有机凝胶,合成了含有没食子酸长烷基链衍生物的预期小分子凝胶中间体,对比分子进行了合成设计表征。
The self-assembling of small functional molecules into supramolecular structures is a powerful approach towards the development of soft materials and nanoscale devices. As a novel class of self-assembled materials, new supramolecular building block have received considerable attention in recent years because they can organize into regular nanoarchitectures through specific non-covalent interactions including hydrogen-bonding, hydrophobic interactions,π-πinteractions and Van der Waals forces. In this masters thesis, photochromic diarylethene moiety contained naphthyridine and the derivative of guanine were designed and synthesized. The morphology, mechanism of the assembly formation and the packing fashion were studied in details, and the assembly materials were applied in bio-imaging,and respond to KB cell. Meanwhile, some low weight molecular gelator synthetized. The research contains two parts as following
1. strong intermolecular hydrogen-bonds are designed through naphthyridine and guanine base on diarylethene, which are verified by NMR,UV-VIS,IR, The self-assembly complex gives special photophysical and photochemical properties and these properties could be well controlled by light.The complex can imagine in KB cell ,different proportions can get different results.
2. We synthesized derivatives of cholic acid with naphthalimide and found that the small amount of low weight molecules can not gel any organic solvents. Designed and synthesized two derivatives of trihydroxybenzoic with three hydrophobic alkyl chains , which have the ability for gelating some organic solvents.
引文
1．J．w斯蒂德，J．L阿特伍德，赵耀鹏，孙震译．超分子化学[M]北京：化学工业出版社，2006．
2．Robert F．Service．How far can we Push chemical self-assembly[J]l Science．2005，309，573 1-5795．
3．Lehn J．M．沈兴海等译．超分子化学一概念和展望[M]．北京大学出版社，2002．
4．Terech PI Weiss R．G Low molecular mass gelators of organic liquids and the properties oftheir gels[J]l Chem．Rev．1997，97，3 133—3 160．
5．W．Nernst．Distribution of a substance between two solvents，etc[J]l Z．Phys．Chem．1892，8，1 10—139．
6．Werner．Liebigs Ueber Haupt—und Nebenvalenzen und die Constitution der Ammoniumverbindungen[J]l Ann．Chem．1902，322，261-269．
7．M．L．Huggins．Hydrogen bridges in organic compounds[J]l J．Org．Chem．1936，1，407—456．
8．Leonard J．Prins，David N．Reinhou~，and Peter Timmermam，Noncovalent Synthesis Using Hydrogen Bonding[J]l Angew．Chem．Int．Ed．2001，40，2382—2426．
9．D．Hadzi．W．J．Orville—Thomas．J．Tomasi．Theoretical Treatments of Hydrogen Bonding[M]．Wiley，Chichester，1997．
10．邢其毅，裴伟伟，徐瑞秋，裴坚，基础有机化学．第三版[M]．北京：高等教育出版社，2005．
11．Stefamo Lena，Stefano Masiero，Silvia Pieraccini，and Gian Piero Spada．Guanosine Hydrogen—Bonded Scaffolds：A New Way to Control the Bottom-Up ealisation of Well—Defined Nanoarchitecmres[J]lChem．Eur．J．2009，15，7792—7806．
12．J．T．Davis．G—Quartets 40 Years Later：From 5’一GMP to Molecular Biology and Supramolecular Chemistry[J]lAngew．Chem．2004，1 16，668—698．
13. Davis J. T., Spada G.P. Supramolecular architectures generated by self-assembly of guanosine derivatives [J]. Chem. Soc. Rev. 2007, 36, 296-313.
14. S Lena, P Neviani, S Masiero, S Pieraccini, and G.P. Spada. Triggering of Guanosine Self-Assembly by Light [J].Angew. Chem. Int. Ed. 2010, 49, 3657-3660.
15. Xi Zhang and Chao Wang. Supramolecular amphiphiles [J]. Chem. Soc. Rev. 2011, 40, 94-101.
16. Chao Wang, Qishui Chen, Huaping Xu, Zhiqiang Wang, and Xi Zhang. Photoresponsive Supramolecular Amphiphiles for Controlled Self-Assembly of Nanofibers and Vesicles [J]. Adv. Mater. 2010, 22, 2553-2555.
17. J. F. Gohy, B. G. G. Lohmeijer and U. S. Schuber. Metallo-Supramolecular Block Copolymer Micelles [J]. Macromolecule. 2002, 35, 4560-4563.
18. A. O. Moughton and R. K. O’Reilly. Noncovalently Connected Micelles, Nanoparticles, and Metal-Functionalized Nanocages Using Supramolecular Self-Assembly [J]. J. Am. Chem. Soc. 2008, 130,8714.
19. Kiyonaka Sada, K.Yoshimura, I, Shinkai, S, Kato, N, Hamaehi, I. Semi- wet PePtide/Proten array using supermolecular hydroge [J]. Nature Materals2004, 3, 58-64.
20. Mukkamala R, Weiss R G. Physical gelation of organic fluids by anthraquinone-steroid-based molecules. Structural features influencing the properties of gels [J]. Langmuir, 1996, 12, 1474-1482.
21. Huang X, Terech P, Raghavan S R, Weiss R. G. Kinetics of 5 -cholestan-3 -yl-N-(2-Naphthyl)carbamate n-alkane organogel formation and its influence on the fibrillar networks [J]. J. Am. Chem. Soc. 2005, 127, 4336-4344.
22. Ono Y., Nakashima K., Sano M., Hojo J., Shinkai S., Organogels are useful as a template for the preparation of novel helical silica fibers [J]. J. Mater. Chem. 2001, 11, 2412-2419.
23. Wu Junchen, Yi Tao, Shu Tianmin, Yu Mengxiao, Zhou Zhiguo , Xu Miao,Zhou Yifeng，Zhang Huijun，Hart Jiaxltao，Li Fuyou,Huang Chunhui．Ultrasound switch and thermal self-repair of morphology and surfacewettability in a cholesterol—base self-assembly system[J]. Angew．Chem．Int．Ed．2007，47，1063—1067．
24．Xudong Yu，Qian Liu，Junchen Wu，Mingming Zhang，Xinhua Cao，SongZhang，ei Wang，Liming Chen，and Tao Yi，Sonication—TriggeredInstantaneous Gel—to—Gel Transformation[J]l Chem．Eur．J．2010，16，9099—9106．
25．左伯莉，刘国宏化学传感器原理及应用[M]北京：清华大学出版社，2006．
26．樊美公光化学基本原理与光子材料[M]北京：科学出版社，2001．
27．Hishberg Y，Fischer E．，Low—temperature phtochromism and its relation tothermo—chromism[J]l J．Chem．Soc．，1953，629—636．
28．Irie M，Diarylethenes for Memories and Switches[J]l Chem．Rev．2000，100，1685—1716．
29．Labsky J．Mikes F and Kalal J Effect of spacer on the isomerization ofbound azobenzene in soluble polymers[J] Polym．Bull．，1981，4，711-715．
30．Y．P．Wang．N．Ma,Z．e．Wang and X．Zhang．Photocontrolled ReversibleSupramoleculax Assemblies of a2"1 Azobenzene—Containing Surfactant witha—Cyclodextrin[J]l Angew．Chem．Int．Ed．2007，46，2823—2826．
31．Ron Siewertsen，Hendrikje Neumann，Bengt Buchheim-Stehn，Rainer Herges，Christian Nather,Falk Renth，and Friedrich Temps，Highly EfficientReversible Z—E Photoisomerization of a Bridged Azobenzene with VisibleLight through Resolved Sl(na*)Absorption Brands[J]l J．Am．Chem．Soc．2009，131，15594—15595．
32．Berkovic G KrongauzV and Weiss V Spiropyrans and spirooxazines formemories and switches[J] Chem．Rev．2000，100，1741-1754．
33．In Sung Park, Young—Sik Jung．Kee—Jung Leeand Jong—Man KimPhotoswitching and sensor applications of aspiropyram-polythiopheneconjugate[J] Chem．Commun．，2010，46，2859–2861.
34. Zhihong Bao, Ka-yuen Ng, Vivian Wing-Wah Yam, Chi-Chlu Ko, Nianyong Zhu, Lixin Wu, Syntheses, Characterization, and Photochromic Studies of Spirooxazine-Containing 2,2 -Bipyridine Ligands and Their Zinc(II) Thiolate Complexes [J]. Inorg. Chem., 2008, 47 , 8912-8920.
35. Yokoyama Y, Fulgides for Memories and Switches [J]. Chem. Rev. 2000, 100, 1717-1739.
36. Morimoto, M, Kobatake, S, Irie, M, Crystal engineering of phtochromic diarylethene single crystals [J]. Chem. Record. 2004, 4, 23-38.
37. Wigglesorth T J, Myles A J, Branda N R, High-content photochromic polymers based on dithienylethenes [J]. Eur. J. Org. Chem. 2005, 1233-1238.
38. Lucas L N, Jong J. J. D, Van Esch J. H, Kellog R. M., B. L, Synthesis of dithienylcyclopentene optical molecular switches [J]. Eur. J. Org. Chem., 2003, 155-166.
39. Bing Qin, Rongxia Yao, Xueli Zhao, He Tian, Enhanced photochromism of 1,2-Dithie-nylcyclopentene complexes with metal ion [J]. Org. Biomol. Chem., 2003, 1, 2187-2191.
40. Bing Qin, Rongxia Yao, He Tian, One-dimensional structure of a photochromic polymer composed of 1,2-bis[2-methyl-5-(4-pyridyl)-3-thienyl] cyclopentene and Zn(II) chloride [J]. Inorganica Chimica Acta, 2004, 357, 3382-3384.
41. Megumu Munakata, Jing Han, Masahiko Maekawa, Yusaku Suenaga, Takayoshi Kuroda-Sowa, Atsuhiro Nabei, Hideaki Ebisu, A MLCT-switched photochromic copper(II) coordination polymer with 1,2-bis(2-methyl-5-(4-pyridyl)-3-thienyl)perfluo-rocyclopentene in crystalline phase [J]. Inorgnica Chimica Acta, 2007, 360, 2792-2796.
42. Wenjuan Tan, Qiong Zhang, Junji Zhang, He Tian, Near-infrared photochromic diaryl-etnene Iridium(III) complex [J]. Org. Lett. 2009, 11. 161-164.
43. Liu H.H, Chen Y, A bifunctional metel probe with independent signaloutputs and regulable detection limits [J]. Eur. J. Org. Chem. 2009, 5261-5265.
44. S. Fraysse, C Coudret, Jean-Pierre Launay, Synthesis and properties of dinuclear complex with a photochromic bridge: an intervalence electron transfer switching“On”and“Off”[J]. Eur. J. Inorg. Chem., 2000, 39, 1581-1590.
45. Kenji Matsuda Kohsuke Takayama, Kohsuke Takayama, Masahiro Irie, Photochromism of metal complexes composed of diarylethene ligands and Zn, Mn, and Cu(II) hexafluoroacetylacetonates [J]. Inorg. Chem., 2004, 43: 482-489.
46. Kenji Matsuda, Yoshihiro Shinkai, Masahiro Irie, Photochromism of metal complexes composed of diaryletnene ligands and ZnCl2 [J]. Inorg. Chem. 2004, 43, 3774-3776.
47. Sheng Wang, Wei Shen, Yanli Feng and He Tian. A multiple switching bisthienylethene and its photochromic fluorescent organogelator [J]. Chem. Commun., 2006, 1497–1499.
48. Xiao Shuzhang, Zou Ying, Yu Mengxiao, Yi Tao, Zhou Yifeng, Li Fuyou, Huang Chunhui. A photochromic fluorescent switch in an organogel system with nondestructive readout ability [J]. Chem. Commun. 2007, 4758–4760.
49. de Jong J J D, Tiemersma-Wegman T D, van Esch J H, Feringa B L. Dynamic chiral selection and amplification using photoresponsive organogelators [J]. J. Am. Chem. Soc. 2005, 127, 13804-13805.
50. de Jong J J D, Lucas L N, Kellogg R M, van Esch J H, Feringa B L. Reversible Optical Transcription of Supramolecular Chirality into Molecular Chirality [J]. Science, 2004, 304, 278-281.
51. de Jong J J D, Feringa B L, Van Esch J H. Light-driven dynamic pattern formation [J]. Angew. Chem. Int. Ed. 2005, 44, 2373-2376.
52. Ying Zou, Tao Yi, Shuzhang Xiao, Fuyou Li, Chunyan Li,Xia Gao, Junchen Wu, Mengxiao Yu, and Chunhui Huang. Amphiphilic Diarylethene as a Photoswitchable Probe for Imaging Living Cells [J]. J. Am. Chem. Soc. 2008,130, 15750–15751.
53. Nobuaki Soh, Kenji Yoshida, Hizuru Nakajima, Koji Nakano, Toshihiko Imato, Tuyoshi Fukaminato and Masahiro Irie. A fluorescent photochromic compound for labeling biomolecules [J]. Chem. Commun. 2007, 5206-5208.
54. Usama Al-Atar, Rylan Fernandes, Bob Johnsen,David Baillie and Neil R Branda. A Photocontrolled Molecular Switch Regulates Paralysis in a Living Organism [J]. J. Am. Chem. Soc. 2009, 131, 15966–15967.
55. Weiss, Naphthyridine Heterocyclic Compounds [J].1961, 7, 198-236.
56. W W Paudler, R M Sheets, Recent developments in naphthyridine chemistry [J]. Adv. Heterocycl. Chem. 1983, 33, 147-184.
57. Nakatani, Sando, Saito, Improved selectivity for the binding of naphthyridine dimer to guanine-guanine mismatch [J]. Bioorganic & Medicinal Chemistry, 2001, 9, 2381-2385.
58. Yong Chen, Xi-Juan Zhao, Xin Gan, Wen-Fu Fu. Zinc(II) complexes with 1,8-naphthyridine-based ligand: Crystal structures and luminescent properties Inorganica. Chimica. Acta. [J]. 361 (2008) 2335–2342.
59. Wen-Fu Fu, Huifang-Jie Li, De-Hui Wang, Liang-Jun Zhou, Li Li, Xin Gan, Quan-Qing Xu and Hai-Bin Song. A novel Kolbe reaction pathway for a selective one- and two-electron reduction of azo compounds [J]. Chem. Commun. 2009, 5524-5526.
60. Nabanita Sadhukhan and Jitendra K. Bera. Mixed-Metal Assemblies Involving Ferrocene Naphthyridine Hybrids [J]. Inorg. Chem. 2009, 48, 978–990.
61. Ming-Ming Yu, Zhan-Xian Li, Liu-He Wei, Dong-Hui Wei and Ming-Sheng Tang. A 1,8-Naphthyridine-Based Fluorescent Chemodosimeter for the Rapid Detection of Zn2+ and Cu2+ [J]. Org. Lett. 2008, 10, 5115–5118.
62. R Singh, R Fathi-Afshar, G. Thomas, et al., Synthesis and antibacterial activity of 7-hydrazinoquinolones [J]. Eur. J. Med. Chem. 1998, 33, 697-703.
63. Ferrarini, Mori, adawneh. Synthesis and -blocking activity of (R,S)-(E)-oximeethers of 2,3-dihydro-1,8-naphthyridine and2,3-dihydrothiopyrano[2,3-bipyridine]: potential antihypertensive agents-Part IX [J]. Eur. J. Med. Chem., 2000, 35, 815-826.
64. Fang, S. Selvi, J Liao, Z. Slanina, C. Chen, Pitai. Chou. Fluorescent and Circular Dichroic Detection of Monosaccharides by Molecular Sensors: Bis[(Pyrrolyl)-ethynyl]-naphthyridine and Bis[(Indolyl)-ethynyl] naphthyridine [J]. J. Am. Chem. Soc. 2004, 126, 3559-3566.
65. Kazuhiko Nakatani, Souta Horie, and Isao Saito.Affinity Labeling of a Single Guanine Bulge [J]. J. Am. Chem. Soc. 2003, 125 ,8972–8973.
66. Kazuhiko Nakatani, Shinsuke Sando, and Isao Saito. Recognition of a Single Guanine Bulge by 2-Acylamino-1,8-naphthyridine [J]. J. Am. Chem. Soc.2000, 122, 2172-2177.
67. Chikara Dohno, Shin-nosuke Uno, and Kazuhiko Nakatani. Photoswitchable Molecular Glue for DNA [J]. J. Am. Chem. Soc. 2007, 129,11898-11899.
1．余梦晓生物成像用新型发光探针的研究[D]上海：复旦大学，2009
2．左伯莉，刘国宏化学传感器原理及应用[M]北京：清华大学出版社，2006．
3．Xi Zhang and Chao Wang．Supramoleculax amphiphiles[J]l Chem．Soc．Rev．2011，40，94—101．
4．Leonard J Prins，David N Reinhoudt，and Peter Timmerman．NoncovNent Synthesis Using Hydrogen Bonding[J]l Angew．Chem．Int．Ed．2001，40，2382—2426．
5．J．w斯蒂德，J．L阿特伍德，赵耀鹏，孙震译超分子化学[M]北京：化学工业出版社，2006．
6．Amlr Ciesielski，Stefano Lena，Stefaxm Masiero，Gian Piero Spada，and Paolo Samor．Dynamers at the Solid-Liquid Interface：Controlling the Reversible Assembly／Reassembly Process between Two Highly Ordered Supramolecular Guanine Motifs[J]l Angew．Chem．Int．Ed．2010，49，1963—1966．
7．Na2atani，Sando，Saito．Improved selectivity for the binding of naphthyridine dimer to guanine—guanine mismatch[J]l Bioorganic&Medicinal Chemistry，2001，9，2381-2385．
8．Li Aixiao，，Maurel Francois，Barbault Florent，Delamax Michel，Wang Baoshan，Zhou Xiang，Wang Ping Molecular modeling study ofbinding site selectivity of TQMP to G—quadruplex DNA[J]l European Journal of Medicinal Chemistry．2010，45，983-991．
9．Kazuhiko Na2atani，Souta Horie，and Isao Saito．Affinity Labeling of a Single Guanine Bulge[J]l J．Am．Chem．Soc．2003，125，8972—8973．
10．Chikara Dohno，Shin—nosuke Uno，and Kazuhiko Nakatani．Photoswitchable Molecular GlueforDNA[J]l J．Am．Chem．Soc．2007，129，11898—11899．
11．王海霞基于花二酰亚胺和萘酰亚胺的新型荧光分子探针的设计、合成和性质研究[D]山东：山东大学，2010．
12．Lucas L，N，Jong J．J．D，Van Esch J．H，Kellog R．M．，B．L，Synthesis ofdithienylcyclopentene optical molecular switches[J]l Eur．J．Org．Chem．2003，155—166．
13．吴君臣功能性胆甾化合物的设计合成分子组装及对环境的响应能力[D]上海：复旦大学，2009．
1．Kiyonaka，Sugiyasu Shinkai S．Hamachi First Thermally Responsive Supramolecular Polymer Based on Glycosylated Amino Acid[J]l J．Am．Chem．Soc．，2002，24，10954—10955．
2．Couffin—Hoaxau．，Motulsky,Delmas，Leroux，In situ-Forming Pharmaceutical Organogels Based on the Self-Assembly of L—Alanine Derivatives[J]l Phaxm．Res．2004，2 1，454—457．
3．Terazzi，Torelli，Bernardinelli，Rivera，Benech，Bourgogne，Donnio B，Guillon D，Imbe~D，Bunzli，Pinto A．，Jeannerat D，Piguet C．Molecular Control of Macroscopic Cubic，Columnar,and Lamellar OrgaMzations in Luminescent Lanthamide—Containing Thermotropic Liquid Crystals[J]l J．Am．Chem．Soc．2005，127，888—903．
4．Shome Debnath S，Das．Head Group Modulated pH—Responsive Hydrogel of Amino Acid—Based Amphiphiles：Entrapment and Release of Cytochrome C and Vitamin B12[J]l Langmuir,2008，24，4280—4288．
5．Naota T，Koori H．，Molecules．ThatAssemble by Sound：AnApplication to the Instant Gelation of Stable Organic Fluids[J]l J．Am．Chem．Soc．2005，127，9324—9325．
6．葛春华以含酰胺基的吡啶类配体组装配位超分子结构的研究[D]长春：东北师范大学2004．
7．钟慧萍含氮硫杂环化合物的合成及其超分子化学研究[D]厦门：厦门大学2004．
8．李研基于胆甾酸衍生物的超分子化学研究[D]北京：清华大学2009
9．吴君臣功能性胆甾化合物的设计合成分子组装及对环境的响应能力[D]上海：复旦大学，2009．
10．Mukkamala R，Weiss R G Physical gelation oforganic fluids by anthraquinone—steroid—based molecules．Structural features influencing theproperties of gels [J]. Langmuir, 1996, 12, 1474-1482.
11. Furman I., Weiss, Factors influencing the formation of thermally reversible gels comprised of cholesteryl 4-(2-anthryloxy)butanoate in hexadecane, 1-octanol, or their mixtures [J]. Langmuir, 1993, 9, 2084-2088.
12. Fernando Herranz, M. Dolores Santa Mar??a, and Rosa M. Claramunt [J]. J. Org. Chem. 2006, 71, 2944-2951.
13 Ellis V. Brown. 1,8-Naphthyridines. I. Derivatives of 2- and 4-Methyl-1,8-naphthyridines [J]. J. Org. Chem. 1965, 30 , 1607-1610.
2．Robert F．Service．How far can we Push chemical self-assembly[J]l Science．2005，309，573 1-5795．
3．Lehn J．M．沈兴海等译．超分子化学一概念和展望[M]．北京大学出版社，2002．
4．Terech PI Weiss R．G Low molecular mass gelators of organic liquids and the properties oftheir gels[J]l Chem．Rev．1997，97，3 133—3 160．
5．W．Nernst．Distribution of a substance between two solvents，etc[J]l Z．Phys．Chem．1892，8，1 10—139．
6．Werner．Liebigs Ueber Haupt—und Nebenvalenzen und die Constitution der Ammoniumverbindungen[J]l Ann．Chem．1902，322，261-269．
7．M．L．Huggins．Hydrogen bridges in organic compounds[J]l J．Org．Chem．1936，1，407—456．
8．Leonard J．Prins，David N．Reinhou~，and Peter Timmermam，Noncovalent Synthesis Using Hydrogen Bonding[J]l Angew．Chem．Int．Ed．2001，40，2382—2426．
9．D．Hadzi．W．J．Orville—Thomas．J．Tomasi．Theoretical Treatments of Hydrogen Bonding[M]．Wiley，Chichester，1997．
10．邢其毅，裴伟伟，徐瑞秋，裴坚，基础有机化学．第三版[M]．北京：高等教育出版社，2005．
11．Stefamo Lena，Stefano Masiero，Silvia Pieraccini，and Gian Piero Spada．Guanosine Hydrogen—Bonded Scaffolds：A New Way to Control the Bottom-Up ealisation of Well—Defined Nanoarchitecmres[J]lChem．Eur．J．2009，15，7792—7806．
12．J．T．Davis．G—Quartets 40 Years Later：From 5’一GMP to Molecular Biology and Supramolecular Chemistry[J]lAngew．Chem．2004，1 16，668—698．
13. Davis J. T., Spada G.P. Supramolecular architectures generated by self-assembly of guanosine derivatives [J]. Chem. Soc. Rev. 2007, 36, 296-313.
14. S Lena, P Neviani, S Masiero, S Pieraccini, and G.P. Spada. Triggering of Guanosine Self-Assembly by Light [J].Angew. Chem. Int. Ed. 2010, 49, 3657-3660.
15. Xi Zhang and Chao Wang. Supramolecular amphiphiles [J]. Chem. Soc. Rev. 2011, 40, 94-101.
16. Chao Wang, Qishui Chen, Huaping Xu, Zhiqiang Wang, and Xi Zhang. Photoresponsive Supramolecular Amphiphiles for Controlled Self-Assembly of Nanofibers and Vesicles [J]. Adv. Mater. 2010, 22, 2553-2555.
17. J. F. Gohy, B. G. G. Lohmeijer and U. S. Schuber. Metallo-Supramolecular Block Copolymer Micelles [J]. Macromolecule. 2002, 35, 4560-4563.
18. A. O. Moughton and R. K. O’Reilly. Noncovalently Connected Micelles, Nanoparticles, and Metal-Functionalized Nanocages Using Supramolecular Self-Assembly [J]. J. Am. Chem. Soc. 2008, 130,8714.
19. Kiyonaka Sada, K.Yoshimura, I, Shinkai, S, Kato, N, Hamaehi, I. Semi- wet PePtide/Proten array using supermolecular hydroge [J]. Nature Materals2004, 3, 58-64.
20. Mukkamala R, Weiss R G. Physical gelation of organic fluids by anthraquinone-steroid-based molecules. Structural features influencing the properties of gels [J]. Langmuir, 1996, 12, 1474-1482.
21. Huang X, Terech P, Raghavan S R, Weiss R. G. Kinetics of 5 -cholestan-3 -yl-N-(2-Naphthyl)carbamate n-alkane organogel formation and its influence on the fibrillar networks [J]. J. Am. Chem. Soc. 2005, 127, 4336-4344.
22. Ono Y., Nakashima K., Sano M., Hojo J., Shinkai S., Organogels are useful as a template for the preparation of novel helical silica fibers [J]. J. Mater. Chem. 2001, 11, 2412-2419.
23. Wu Junchen, Yi Tao, Shu Tianmin, Yu Mengxiao, Zhou Zhiguo , Xu Miao,Zhou Yifeng，Zhang Huijun，Hart Jiaxltao，Li Fuyou,Huang Chunhui．Ultrasound switch and thermal self-repair of morphology and surfacewettability in a cholesterol—base self-assembly system[J]. Angew．Chem．Int．Ed．2007，47，1063—1067．
24．Xudong Yu，Qian Liu，Junchen Wu，Mingming Zhang，Xinhua Cao，SongZhang，ei Wang，Liming Chen，and Tao Yi，Sonication—TriggeredInstantaneous Gel—to—Gel Transformation[J]l Chem．Eur．J．2010，16，9099—9106．
25．左伯莉，刘国宏化学传感器原理及应用[M]北京：清华大学出版社，2006．
26．樊美公光化学基本原理与光子材料[M]北京：科学出版社，2001．
27．Hishberg Y，Fischer E．，Low—temperature phtochromism and its relation tothermo—chromism[J]l J．Chem．Soc．，1953，629—636．
28．Irie M，Diarylethenes for Memories and Switches[J]l Chem．Rev．2000，100，1685—1716．
29．Labsky J．Mikes F and Kalal J Effect of spacer on the isomerization ofbound azobenzene in soluble polymers[J] Polym．Bull．，1981，4，711-715．
30．Y．P．Wang．N．Ma,Z．e．Wang and X．Zhang．Photocontrolled ReversibleSupramoleculax Assemblies of a2"1 Azobenzene—Containing Surfactant witha—Cyclodextrin[J]l Angew．Chem．Int．Ed．2007，46，2823—2826．
31．Ron Siewertsen，Hendrikje Neumann，Bengt Buchheim-Stehn，Rainer Herges，Christian Nather,Falk Renth，and Friedrich Temps，Highly EfficientReversible Z—E Photoisomerization of a Bridged Azobenzene with VisibleLight through Resolved Sl(na*)Absorption Brands[J]l J．Am．Chem．Soc．2009，131，15594—15595．
32．Berkovic G KrongauzV and Weiss V Spiropyrans and spirooxazines formemories and switches[J] Chem．Rev．2000，100，1741-1754．
33．In Sung Park, Young—Sik Jung．Kee—Jung Leeand Jong—Man KimPhotoswitching and sensor applications of aspiropyram-polythiopheneconjugate[J] Chem．Commun．，2010，46，2859–2861.
34. Zhihong Bao, Ka-yuen Ng, Vivian Wing-Wah Yam, Chi-Chlu Ko, Nianyong Zhu, Lixin Wu, Syntheses, Characterization, and Photochromic Studies of Spirooxazine-Containing 2,2 -Bipyridine Ligands and Their Zinc(II) Thiolate Complexes [J]. Inorg. Chem., 2008, 47 , 8912-8920.
35. Yokoyama Y, Fulgides for Memories and Switches [J]. Chem. Rev. 2000, 100, 1717-1739.
36. Morimoto, M, Kobatake, S, Irie, M, Crystal engineering of phtochromic diarylethene single crystals [J]. Chem. Record. 2004, 4, 23-38.
37. Wigglesorth T J, Myles A J, Branda N R, High-content photochromic polymers based on dithienylethenes [J]. Eur. J. Org. Chem. 2005, 1233-1238.
38. Lucas L N, Jong J. J. D, Van Esch J. H, Kellog R. M., B. L, Synthesis of dithienylcyclopentene optical molecular switches [J]. Eur. J. Org. Chem., 2003, 155-166.
39. Bing Qin, Rongxia Yao, Xueli Zhao, He Tian, Enhanced photochromism of 1,2-Dithie-nylcyclopentene complexes with metal ion [J]. Org. Biomol. Chem., 2003, 1, 2187-2191.
40. Bing Qin, Rongxia Yao, He Tian, One-dimensional structure of a photochromic polymer composed of 1,2-bis[2-methyl-5-(4-pyridyl)-3-thienyl] cyclopentene and Zn(II) chloride [J]. Inorganica Chimica Acta, 2004, 357, 3382-3384.
41. Megumu Munakata, Jing Han, Masahiko Maekawa, Yusaku Suenaga, Takayoshi Kuroda-Sowa, Atsuhiro Nabei, Hideaki Ebisu, A MLCT-switched photochromic copper(II) coordination polymer with 1,2-bis(2-methyl-5-(4-pyridyl)-3-thienyl)perfluo-rocyclopentene in crystalline phase [J]. Inorgnica Chimica Acta, 2007, 360, 2792-2796.
42. Wenjuan Tan, Qiong Zhang, Junji Zhang, He Tian, Near-infrared photochromic diaryl-etnene Iridium(III) complex [J]. Org. Lett. 2009, 11. 161-164.
43. Liu H.H, Chen Y, A bifunctional metel probe with independent signaloutputs and regulable detection limits [J]. Eur. J. Org. Chem. 2009, 5261-5265.
44. S. Fraysse, C Coudret, Jean-Pierre Launay, Synthesis and properties of dinuclear complex with a photochromic bridge: an intervalence electron transfer switching“On”and“Off”[J]. Eur. J. Inorg. Chem., 2000, 39, 1581-1590.
45. Kenji Matsuda Kohsuke Takayama, Kohsuke Takayama, Masahiro Irie, Photochromism of metal complexes composed of diarylethene ligands and Zn, Mn, and Cu(II) hexafluoroacetylacetonates [J]. Inorg. Chem., 2004, 43: 482-489.
46. Kenji Matsuda, Yoshihiro Shinkai, Masahiro Irie, Photochromism of metal complexes composed of diaryletnene ligands and ZnCl2 [J]. Inorg. Chem. 2004, 43, 3774-3776.
47. Sheng Wang, Wei Shen, Yanli Feng and He Tian. A multiple switching bisthienylethene and its photochromic fluorescent organogelator [J]. Chem. Commun., 2006, 1497–1499.
48. Xiao Shuzhang, Zou Ying, Yu Mengxiao, Yi Tao, Zhou Yifeng, Li Fuyou, Huang Chunhui. A photochromic fluorescent switch in an organogel system with nondestructive readout ability [J]. Chem. Commun. 2007, 4758–4760.
49. de Jong J J D, Tiemersma-Wegman T D, van Esch J H, Feringa B L. Dynamic chiral selection and amplification using photoresponsive organogelators [J]. J. Am. Chem. Soc. 2005, 127, 13804-13805.
50. de Jong J J D, Lucas L N, Kellogg R M, van Esch J H, Feringa B L. Reversible Optical Transcription of Supramolecular Chirality into Molecular Chirality [J]. Science, 2004, 304, 278-281.
51. de Jong J J D, Feringa B L, Van Esch J H. Light-driven dynamic pattern formation [J]. Angew. Chem. Int. Ed. 2005, 44, 2373-2376.
52. Ying Zou, Tao Yi, Shuzhang Xiao, Fuyou Li, Chunyan Li,Xia Gao, Junchen Wu, Mengxiao Yu, and Chunhui Huang. Amphiphilic Diarylethene as a Photoswitchable Probe for Imaging Living Cells [J]. J. Am. Chem. Soc. 2008,130, 15750–15751.
53. Nobuaki Soh, Kenji Yoshida, Hizuru Nakajima, Koji Nakano, Toshihiko Imato, Tuyoshi Fukaminato and Masahiro Irie. A fluorescent photochromic compound for labeling biomolecules [J]. Chem. Commun. 2007, 5206-5208.
54. Usama Al-Atar, Rylan Fernandes, Bob Johnsen,David Baillie and Neil R Branda. A Photocontrolled Molecular Switch Regulates Paralysis in a Living Organism [J]. J. Am. Chem. Soc. 2009, 131, 15966–15967.
55. Weiss, Naphthyridine Heterocyclic Compounds [J].1961, 7, 198-236.
56. W W Paudler, R M Sheets, Recent developments in naphthyridine chemistry [J]. Adv. Heterocycl. Chem. 1983, 33, 147-184.
57. Nakatani, Sando, Saito, Improved selectivity for the binding of naphthyridine dimer to guanine-guanine mismatch [J]. Bioorganic & Medicinal Chemistry, 2001, 9, 2381-2385.
58. Yong Chen, Xi-Juan Zhao, Xin Gan, Wen-Fu Fu. Zinc(II) complexes with 1,8-naphthyridine-based ligand: Crystal structures and luminescent properties Inorganica. Chimica. Acta. [J]. 361 (2008) 2335–2342.
59. Wen-Fu Fu, Huifang-Jie Li, De-Hui Wang, Liang-Jun Zhou, Li Li, Xin Gan, Quan-Qing Xu and Hai-Bin Song. A novel Kolbe reaction pathway for a selective one- and two-electron reduction of azo compounds [J]. Chem. Commun. 2009, 5524-5526.
60. Nabanita Sadhukhan and Jitendra K. Bera. Mixed-Metal Assemblies Involving Ferrocene Naphthyridine Hybrids [J]. Inorg. Chem. 2009, 48, 978–990.
61. Ming-Ming Yu, Zhan-Xian Li, Liu-He Wei, Dong-Hui Wei and Ming-Sheng Tang. A 1,8-Naphthyridine-Based Fluorescent Chemodosimeter for the Rapid Detection of Zn2+ and Cu2+ [J]. Org. Lett. 2008, 10, 5115–5118.
62. R Singh, R Fathi-Afshar, G. Thomas, et al., Synthesis and antibacterial activity of 7-hydrazinoquinolones [J]. Eur. J. Med. Chem. 1998, 33, 697-703.
63. Ferrarini, Mori, adawneh. Synthesis and -blocking activity of (R,S)-(E)-oximeethers of 2,3-dihydro-1,8-naphthyridine and2,3-dihydrothiopyrano[2,3-bipyridine]: potential antihypertensive agents-Part IX [J]. Eur. J. Med. Chem., 2000, 35, 815-826.
64. Fang, S. Selvi, J Liao, Z. Slanina, C. Chen, Pitai. Chou. Fluorescent and Circular Dichroic Detection of Monosaccharides by Molecular Sensors: Bis[(Pyrrolyl)-ethynyl]-naphthyridine and Bis[(Indolyl)-ethynyl] naphthyridine [J]. J. Am. Chem. Soc. 2004, 126, 3559-3566.
65. Kazuhiko Nakatani, Souta Horie, and Isao Saito.Affinity Labeling of a Single Guanine Bulge [J]. J. Am. Chem. Soc. 2003, 125 ,8972–8973.
66. Kazuhiko Nakatani, Shinsuke Sando, and Isao Saito. Recognition of a Single Guanine Bulge by 2-Acylamino-1,8-naphthyridine [J]. J. Am. Chem. Soc.2000, 122, 2172-2177.
67. Chikara Dohno, Shin-nosuke Uno, and Kazuhiko Nakatani. Photoswitchable Molecular Glue for DNA [J]. J. Am. Chem. Soc. 2007, 129,11898-11899.
1．余梦晓生物成像用新型发光探针的研究[D]上海：复旦大学，2009
2．左伯莉，刘国宏化学传感器原理及应用[M]北京：清华大学出版社，2006．
3．Xi Zhang and Chao Wang．Supramoleculax amphiphiles[J]l Chem．Soc．Rev．2011，40，94—101．
4．Leonard J Prins，David N Reinhoudt，and Peter Timmerman．NoncovNent Synthesis Using Hydrogen Bonding[J]l Angew．Chem．Int．Ed．2001，40，2382—2426．
5．J．w斯蒂德，J．L阿特伍德，赵耀鹏，孙震译超分子化学[M]北京：化学工业出版社，2006．
6．Amlr Ciesielski，Stefano Lena，Stefaxm Masiero，Gian Piero Spada，and Paolo Samor．Dynamers at the Solid-Liquid Interface：Controlling the Reversible Assembly／Reassembly Process between Two Highly Ordered Supramolecular Guanine Motifs[J]l Angew．Chem．Int．Ed．2010，49，1963—1966．
7．Na2atani，Sando，Saito．Improved selectivity for the binding of naphthyridine dimer to guanine—guanine mismatch[J]l Bioorganic&Medicinal Chemistry，2001，9，2381-2385．
8．Li Aixiao，，Maurel Francois，Barbault Florent，Delamax Michel，Wang Baoshan，Zhou Xiang，Wang Ping Molecular modeling study ofbinding site selectivity of TQMP to G—quadruplex DNA[J]l European Journal of Medicinal Chemistry．2010，45，983-991．
9．Kazuhiko Na2atani，Souta Horie，and Isao Saito．Affinity Labeling of a Single Guanine Bulge[J]l J．Am．Chem．Soc．2003，125，8972—8973．
10．Chikara Dohno，Shin—nosuke Uno，and Kazuhiko Nakatani．Photoswitchable Molecular GlueforDNA[J]l J．Am．Chem．Soc．2007，129，11898—11899．
11．王海霞基于花二酰亚胺和萘酰亚胺的新型荧光分子探针的设计、合成和性质研究[D]山东：山东大学，2010．
12．Lucas L，N，Jong J．J．D，Van Esch J．H，Kellog R．M．，B．L，Synthesis ofdithienylcyclopentene optical molecular switches[J]l Eur．J．Org．Chem．2003，155—166．
13．吴君臣功能性胆甾化合物的设计合成分子组装及对环境的响应能力[D]上海：复旦大学，2009．
1．Kiyonaka，Sugiyasu Shinkai S．Hamachi First Thermally Responsive Supramolecular Polymer Based on Glycosylated Amino Acid[J]l J．Am．Chem．Soc．，2002，24，10954—10955．
2．Couffin—Hoaxau．，Motulsky,Delmas，Leroux，In situ-Forming Pharmaceutical Organogels Based on the Self-Assembly of L—Alanine Derivatives[J]l Phaxm．Res．2004，2 1，454—457．
3．Terazzi，Torelli，Bernardinelli，Rivera，Benech，Bourgogne，Donnio B，Guillon D，Imbe~D，Bunzli，Pinto A．，Jeannerat D，Piguet C．Molecular Control of Macroscopic Cubic，Columnar,and Lamellar OrgaMzations in Luminescent Lanthamide—Containing Thermotropic Liquid Crystals[J]l J．Am．Chem．Soc．2005，127，888—903．
4．Shome Debnath S，Das．Head Group Modulated pH—Responsive Hydrogel of Amino Acid—Based Amphiphiles：Entrapment and Release of Cytochrome C and Vitamin B12[J]l Langmuir,2008，24，4280—4288．
5．Naota T，Koori H．，Molecules．ThatAssemble by Sound：AnApplication to the Instant Gelation of Stable Organic Fluids[J]l J．Am．Chem．Soc．2005，127，9324—9325．
6．葛春华以含酰胺基的吡啶类配体组装配位超分子结构的研究[D]长春：东北师范大学2004．
7．钟慧萍含氮硫杂环化合物的合成及其超分子化学研究[D]厦门：厦门大学2004．
8．李研基于胆甾酸衍生物的超分子化学研究[D]北京：清华大学2009
9．吴君臣功能性胆甾化合物的设计合成分子组装及对环境的响应能力[D]上海：复旦大学，2009．
10．Mukkamala R，Weiss R G Physical gelation oforganic fluids by anthraquinone—steroid—based molecules．Structural features influencing theproperties of gels [J]. Langmuir, 1996, 12, 1474-1482.
11. Furman I., Weiss, Factors influencing the formation of thermally reversible gels comprised of cholesteryl 4-(2-anthryloxy)butanoate in hexadecane, 1-octanol, or their mixtures [J]. Langmuir, 1993, 9, 2084-2088.
12. Fernando Herranz, M. Dolores Santa Mar??a, and Rosa M. Claramunt [J]. J. Org. Chem. 2006, 71, 2944-2951.
13 Ellis V. Brown. 1,8-Naphthyridines. I. Derivatives of 2- and 4-Methyl-1,8-naphthyridines [J]. J. Org. Chem. 1965, 30 , 1607-1610.