摘要
本文合成了六种含有偶氮或亚胺基团的羟基喹啉、萘酚和间苯二酚的两亲性衍生物。长链烷氧基苯胺重氮化反应后,与8-羟基喹啉、1-萘酚、和间苯二酚进行偶合反应,得到了5-(4′-十八烷氧基苯偶氮基)-8-羟基喹啉(C18AzoHq)、5-(4′-十六烷氧基苯偶氮基)-8-羟基喹啉(C16AzoHq)、4-(4′-十八烷氧基苯偶氮基)-1-萘酚(C18AzoNp)、 4-(4′-十六烷氧基苯偶氮基)-1-萘酚(C16AzoNp)和4-(4′-十六烷氧基苯偶氮基)-1,3-苯二酚(C16AzoBdiol),十八烷氧基苯胺与8-羟基-5-喹啉甲醛进行缩合反应得到了5-(4′-十八烷氧基苯基亚胺甲基)-8-羟基喹啉(C18ImiHq),结构通过元素分析、核磁共振氢谱和红外光谱得到了表征。其中化合物C18AzoHq、C16AzoHq、C18ImiHq和C16AzoBdiol是新的化合物,未见文献报道。这些化合物可以在不同的亚相表面形成稳定的单分子膜,进而沉积在固体载体表面形成稳定的LB膜。
本文研究了化合物C16AzoHq、C18AzoNp和C18ImiHq在溶液及LB膜中的性质:化合物C16AzoHq和C18AzoNp可发生LB膜中的酸致变色反应,该反应是可逆的,可用碱性物质NH3·H2O使其恢复;采用UV-Vis光谱和FT-IR光谱对化合物C16AzoHq和C18ImiHq与金属离子络合进行了研究,结果表明,它们可以和一系列金属离子发生原位络合,化合物C16AzoHq的单层LB膜还可以和溶液中的金属离子发生膜表面的络合;不同的金属离子,对C16AzoHq和C18ImiHq分子的成膜性能产生不同的影响;首次用原子力显微镜对C18ImiHq单分子膜在云母片(mica)表面上的分子膜形态进行了研究,结果发现当亚相金属离子不同时,LB膜表现出不同的微观结构,高度曲线表明C18ImiHq在金属离子的亚相上形成双层膜结构;化合物C18ImiHq在LB膜中具有很强的荧光特性,但是当化合物C18ImiHq与Cu2+络合后,其荧光强度则大为减弱。
In this dissertation, six compounds containing quinolinol and naphthol and resorcinol connected by azo- or imino- group have been synthesized. The coupling reaction between long chain diazonium salt of alkyloxy benzenamine and 8-hydroxyquinoline , 1-hydroxynaphthalene , resorcinol can obtain 8-hydroxy-5-[[(4′-octadecyloxy)phenyl]azo]quinoli-ne(C18AzoHq), 8-hydroxy-5-[[(4′-hexadecyloxy)phenyl]azo]quinoline(C16AzoHq), 1-hydroxy-4-[[(4′-octadecyloxy)phenyl]azo]naphthalene(C18AzoNp),1-hydroxy-4-[[(4-hexadecyloxy)phenyl]azo]naphthalene(C16AzoNp),4-[[(4-octadecyloxy)phenyl]azo]-1,3-benzenediol (C16AzoBdiol).The condensation reaction between 4-octdecyloxybenzenamine and 5-formyl-8-hydroxyquinoline produces 8-hydroxy-5-[[[(4′-octadecyloxy)phenyl]imino]methyl]qui-noline(C18ImiHq).The structure has been characterized by elemental analysis, IR, 1H-NMRAmong these compounds, C18AzoHq, C16AzoHq, C18ImiHq and C16AzoBdiol are new compounds.These compounds can form stable monolayers on different subphases interface and the monolayers can be deposited onto solid substrates to form stable LB films.
The properties of C16AzoHq, C18AzoNp and C18ImiHq in solutions and LB films have been investigated. C16AzoHq and C18AzoNp show acidichromism in LB films. And the color change is reversible. It can be recovered by using NH3 gas. Studies on the complex reaction by UV-Vis absorption and FT-IR spectroscopy show that there exits in situ complex reaction between C16AzoHq , C18ImiHq and a series of metal ions. The complex formation between the LB monolayer of C16AzoHq and the metal ions in solution at the air/water interface can be obtained. Different metal ions have different effect on the film properties of C16AzoHq and C18ImiHq. Studies on the surface configuration of C18ImiHq monolayer on the mica surface show that microstructure varies with subphase of metal ions. It can be seen that bilayers form on the surface of subphase from the high curve. C18ImiHq in LB films has strong fluorescence character. But it weaken greatly after C18ImiHq combines with Cu2+ ion.
引文
[1] 欧阳健明,LB膜原理与应用,第一版,广州,暨南大学出版社,1999
[2] Kuhn H,Mobins D,Bucher H,Physical Methods of Chemistry,Vol.1,ParⅢB,New york,Wiley-Intersci,1972,577~701
[3] 崔大付,LB膜的物理性能与应用,物理,1996,25(1),54~61
[4] 江龙,化学进展,1994,6(13),195
[5] 孙祥贵,刘益春,鄂书林,CuPc/InP(OI)异质结构的电学性及其引起的Raman效应,化学物理学报,1995,8(1),41~45
[6] 李加,徐叙容,王永生,侯延冰,王劲伯,赵福潭,张光演,张春平,田建国,不同表面压下芪盐单层LB膜二次谐波的研究,发光学报,1996,17(1),74~78
[7] Kuniharu Ijiro,Helmut Ringsdorf,Eckhard Birch-Hirschfeld,Siegfried Hoffmann,Ute Schilken and Michael Strube, Protein-DNA Double and Trriple L:Interaction of Biotinylated DNA Fragments with Solid Supported Streptavidin Layers,Labngmuir,1998,14,2796~2800
[8] Toshihiro Kondo,Toshihiro Kanai,Kohei Uosaki,Control of the charge-transfer rate at agold electrode modified with a self-assembled monolayer containing ferrocene and azobenzene by electro- and photochemical structural conversion of cis and trans forns of the azobenzene moiety,Langmuir,2001,17,6317~6324
[9] D.S.DOS Santos Jr.,Mendonca C.R.,Balegh D. T.,Dhanablan A.,Giacometti J. A.,Zilio S. C.,O. N. Oliveiva J.,Opitical Storage in Mixed Langmuir-Blodgett(LB) films of disperse Red 19,Synth. Metals,2001,121,1479~1480
[10] 逯乐慧,霍立华,李薇,崔海宁,习时权,LB膜诱导CaF2单晶的生长研究,化学通报,2001,1,33～36
[11] 關 隆広,ポリシランのラングミュアーブロジエト膜,表面,1993,31(12),1~10
[12] 中原弘雄,超薄分子膜の構造制御と機能,日本油化學會志,1996,45(10),155~167
[13] 關 隆広,単分子膜およびLB膜の光応答機能材料への展開,日本油化學會志,1998,47(5),15~22
[14] 赵冰,李小灵,吴玉清,徐蔚青,李国文,李伯符,1-羟基-5-十二烷氧基萘LB膜结构和取向的光谱研究,光谱学与光谱分析,1999,19(5),680~683
[15] Liu Minghua,Kira Akira,NaKaHaRa Hiroo,Complex Formation between Monolayers of a Novel Amphiphilic Thiazolylazo Dye and Transition Metal Ions at the Air/Water Interface,Langmuir,1997,13,779~783
[16] 纪军,辛德瑗,胡真,萘酞菁酮LB膜在气敏传感器中的应用研究,云南大学学报(自然科学版),1997,19(2),231~234
[17] J.H.芬德勒著,江龙译,尖端材料德膜模拟,北京,科学出版社,1999
[18] 柳士忠,张贞文,王俊,杜祖亮,戴树玺,十八胺杂多阴离子杂化LB膜的制备与表征,无机化学学报,2001,17(1),96~100
[19] Du Xuezhong,Ling Yingqiu,Roles of metal complex and Hydrogen Bond in Molecular Structures and Phase Behaveiors of metal N-Octadecanoyl-L-alaninate Langmuir-Blodgett Films,J.Phys.Chem.B,2000,104,10047～10052
[20] 孙睿朋,郭建新,王宗凯,马凯,黄锡民,聚酰亚胺LB膜上液晶表面锚定的研究,物理学报,1996,45(12),2041～2046
[21] 王文军,徐建华,陆兴泽,韩奎,王恭明,王文澄,蔡志刚,杨佩青,周建英,有机分子膜层间相互作用对聚集体的影响,物理化学学报,1999,5,471～475
[22] 钱人元,导电高聚物的分子设计问题,高分子通报,1991,2,65～71
[23] Li Hongqi,Yao Zhongqi,Liu Renhua,Tan Ganzu,Yu Xianda,Study of a New Crowned Azobenzene:Photochromism and Langmuir-Blodgett films,Adv. Colloid. Interface Sci.,2000,87,147～164
[24] 周悦,何平笙,陈昆松,李春婀,洪昆仑,聚酰胺盐酸LB膜的亚胺化研究,中国科学技术大学学报,1995,25(1),21～26
[25] Ng S. C.,Zhou X. C.,Miso P.,Chan H. S. O.,Li S. F. Y.,Fu P.,Quaetz Crystal Microbalance Sensor Deposited With Langmuir-Blodgett Films of
Functionalized Polythiophenes and Application to Heavy Metal Ions Analysis,Langmuir,1998,14,1748～1752
[26] 刘志斌,超分子光化学分子器件的研究进展,液晶与显示,1997,12(2),134～142
[27] Zhan Jin,Huang Chunhui,Wei Tianxin,Yu Anchi,Zhao Xinsheng,The Second harmonic generation and the photoelectric property studies ona new dye,(E)-N-octadecyl-4-[2-(4-dimethylaminophenyl)enamine] pyridinium iodide,Solid State Commun.,1999,109,733～738
[28] 杜玉扣,唐季安,江龙,Paul Boullanger,长碳链正电糖苷和葡萄糖氧化酶混和Langmuir-Blodgett膜的光谱研究,感光材料与光化学,1998,16(1),32～37
[29] Hiroaki Tchibana,FumiyasuSato,Samuel Terrettaz,Reiko Azumi,Tohru Nakamura,Hideki Sakai,Masahiko Abe,Mutsuyoshi Matsumoto,Light-induced J-aggregation in mixed Langmuie-Blodgett films of selenium-containing cyanine and azobenzene,Thin Solid Films,1998,327～329,813～815
[30] Marina Stanescu,Hussein Samba,Jerry Perlstein,David G. Whitten,Unusual Folded Structures for a tethered suqaraine-cholesterol deravative in Langmuir-Blodgett Films,Langmuir,2000,16,275～281
[31] Gail E. Fanucci,Renal Backov,Riqiang Fu,Daniekl R. Talham,Multiple Bilayer Dipalmitoylphisphatidylserine LB film Stabilized with Transition,Langmuir,2001,17,437～440
[32] 黄兰,张东柏,史兵,钱林茂,端羟基PS-PEO嵌段共聚物LB膜微摩擦性能,材料研究学报,1999,13(6),627～631
[33] K. P. Girard,J. S. Quinn,T. K. Vanderlick,The mechanical stability of Langmuir-Blodgett multilayers,Thin Solid Films,2000,371,242～248
[34] Riccardo Ricceri,Alessadro Abbotto,Antonio Facchetti,Giorgio A. Pagani,Gabriella Gabrielli,Information storage based on photochemical effects in mixed Langmuir-Blodgett films,Thin Solid Films,1999,340,218～220
[35] 刘洪国,杨孔章,钱东金,薛庆斌,冯绪胜,卟啉衍生物复合单层膜的结
构特征,化学学报,2001,59,158～162
[36] Liu Minghua,Kiminori Ushida,Akira Kira,Photoaccelerated Complex Formation of a Novel Langmuir-Blodgett Film with Transition Metal Ions and Its Ion Selectivity,J. Phys. Chem. B,1997,101(7),1101～1104
[37] Hiroaki Tachibana,Yasushi Yamaraka,Hidaki Sakai,Masahiko Abe and Mutsuyoshi Matsumoto,J-aggregate Formation in Single-Layer Amphiphilic Spiropyran Langmuir-Blodgett Films,Chem. Lett.,2000,10,1182～1183
[38] Rene P. Nieuwhof,Peter Kimkes,Antonius T. M. Marcelis,Ernst J. R. Sudh?ler,Langmuir and Langmuir-Blodgett Films of Side-Chain Liquid-Crystaline Poly(maleic acid-alt-1-alkene)s,Langmuir,2001,17,78～85
[39] 徐寿昌,有机化学,第二版,北京,高等教育出版社,1993,426,262
[40] 欧阳健明,8-羟基喹啉两亲配体及其配合物的有序分子膜和电致发光的研究,南京大学博士论文,1996
[41] Ouyang Jianming,Zhang Zhiming,Yuan Yuan,Huang Chunxiao,Monolayer and LB Films of Amphiphilic 8-Hydroxyquinoline Derivatives,Mol. Cryst. Liq. Cryst.,2000,338,117~124
[42] Ouyang Jianming,Zhang Zhiming,Langmuir-Blodgett Films and ctroluminescent derivatives of amphiphilic 8-Hydroxyquinoline magnesium,Thin Solid Films,2000,363,134~137
[43] 欧阳健明,LB膜的电致发光及其器件,发光学报,2000,21(4),363~368
[44] Jiang Chaoyang,He Weijiang,Huang Jianguo,Tai Zihou,Ling Yingqiu,FT-IR studies of N-hexadecyl-5-iminomethyl-8-hydroxyquinoline Lingmuir-Blodgett films,Mater. Chem. Phys.,2000,62,236~240
[45] 欧阳健明,邰子厚,钱向平,唐雯霞,亚相酸度及金属离子对2-十六氨基甲酰基-8-羟基喹啉成膜性能的影响,高等学校化学学报,1996,17(3),335~340
[46] Ouyang Jianming,Zheng Wenjie,Huang Ningxing,Tai Zihou,X-ray photoelectron spectroscopy study of Lingmuir-Blodgett films of N-Octadecyl-8-Hydroxy-2-quinoline carboxamide deposited from subphases
containing metal ions,Thin Solid Films,1999,340,257~261
[47] Jang Chaoyang,Tang Ruikang,Tai Zihou,Characterization of N-hexadecyl-5-iminomethyl-8-hydroxyquinoline and orientd crystallization of CuSO4·5H2O,J. Mater. Chem.,1998,8(1),81~84
[48] 欧阳健明,郑文杰,黄宁兴,8-羟基喹啉两亲配合物的LB膜及其电致发光器件研究,化学学报,1999,57,333~338
[49] 邱星屏,张雪蓉,丁马太,荧光法研究含长链烷基聚丙烯酰胺的疏水微区结构,高等学校化学学报,1995,16(8),1321~1323
[50] 巫森怠,郑用熙,荧光法测定β-CD与萘酚负离子包结物的解离常数和β-CD与分子型萘酚包结物的酸式离解常,分析科学学报,1994,10(2),11~15
[51] Schrepp Wolfgang,Ramesh Chandra Ahuja,Budach Wolfgang,Moebius Dietmar,Chemical sensor with a fluorescence compound on a suppout,E. P. 520. 262,1992
[52] Li Guowen,Hu Xuewen,Ding Hong,Ling Yingqiu,Synthesis of a novel amphiphile,4-[4-[4-decyloxyphenylazo]naphthyloxy]butyl trimethylammonium bromide and its self-assembling behavior in dilute aqueous solution,Chin. Chem. Lett.,1991,2(10),817~820
[53] Zhang Aidong,Qin Jingui,The synthesis and photochemical properties of amphiphilic phenylazonaphthalenes,Supramol. Sci,1998,5(5~6),573~576
[54] Abe Kei,Suzuki Sachiko ,Mukai Ikuo,Akimoto Seji,Ohta Nobuhiro,Yamazaki Wao,Dimer Formation of Naphthalene in Langmuir-Blodgett Films Probed by Time-Rrsolved Fluorescence Spectroscopy,Chem. Lett.,1996,2,479~480
[55] Liu Minghua,Ushida Kiminori,Kira Akira,Nakhara Hiroo,Photo-excited hydrogen transfer in the LB films of long-chain anils,Mol. Cryst. Liq. Cryst. Sci. Technol.,sect. A,1997,294,137~140
[56] Pang Shufeng,Ling Yingqiu,Structure Studies on Ion Coordination in 2,4-Dihydroxy-N-octadecylbenzylideneamine LB films by UV-vis Absorption and FTIR Spectroscopy,J. Colloid Interface Sci.,2000,231(1)59~65
[57] S. J. Collins,A.Dhathathreyan,T.Ramasami,H.Mohwald,Langmuir and Langmuir-Blodgett films of N-octadecyldroxysalicylaldimine,Thin Solid Films,2000,358(1,2),229~233
[58] Pang Shufeng,Huang Jianguo,Liang Yingqiu,FTIR Studies on LB films of amphphile with schiff base as headgroup and its copper complex,Spectrosc. Lett.,2000,33(3),301~321
[59] 张淑媛,邓刚,李自法,郑世军,一系列含T-型二维液晶基元的液晶高分子配体的合成,高分子学报,1999,3,266~270
[60] 庹新林,成昊,陈峥,王晓工,侧链型偶氮聚电解质自组装和膜结构研究,高等学校化学学报,2001,22,1581~1586
[61] 梁方珍,江崇球,黄汝骐,新型荧光试剂N-2-噻唑基水杨醛亚胺Schiff碱的合成及荧光性质,合成化学,7(2),170~174
[62] 蔡松传,张章福,刘广鉴,胡良彬,薛忠俊,邻苯二酚单醚的新合成方法,化学试剂,1989,11(4),248~249
[63] By David A.,William H.,Alkylation with long chain p-toluenesulfonates.I.alkylation of phenols with n-octadecyl p-toluenesulfonate,J. Am. Chem. Soc., 1951,73,458~459
[64] 黄涛,王永强,田永驰,梁映秋,羟基卟啉衍生物LB膜的紫外可见光谱表征,光谱学与光谱分析,1999,19(1),1~6