水溶性杯芳烃衍生物的合成及其在生物分析中的应用
|
摘要
本文将具有不同的带电性、良好的水溶性或者光谱活性等不同性质的官能团引入杯芳烃母体上,不仅显著增强了杯芳烃的水溶性,亦拓宽了杯芳烃衍生物在光谱分析以及分子识别等方面的应用范围。本文合成了水溶性以及光谱活性的杯芳烃衍生物,并研究了杯[8]芳烃磺酸钠与喹诺酮类药物以及吩噻嗪类药物之间的相互作用,并进一步研究了杯芳烃衍生物作为药物载体在药物缓释控释中的应用。论文主要包括以下几个方面:
第一部分概述了杯芳烃的研究意义,水溶性杯芳烃以及偶氮杯芳烃衍生物的合成研究进展,杯芳烃及其衍生物的分子识别研究现状以及本论文研究的主要内容。
第二部分采用一步法合成了对叔丁基杯[n]芳烃(n=4,8)以及脱对叔丁基杯[n]芳烃,并将磺酸基以及对磺酸基苯偶氮基引入到脱对叔丁基杯芳烃上,合成了杯[8]芳烃磺酸钠和对磺酸基苯偶氮杯[n]芳烃(n=4,8)。利用红外光谱法、元素分析法等对合成产物的结构进行了表征,同时利用薄层色谱法跟踪反应过程,利用液相色谱法对合成产物的纯度进行了表征,并对实验过程中影响产率的主要因素进行了讨论。
第三部分利用荧光光谱法研究了杯[8]芳烃磺酸钠与诺氟沙星、杯[8]芳烃磺酸钠与环丙沙星在水溶液中的形成包络物的最佳条件。同时,利用荧光光谱法研究了包络物之间的主客体包络行为并测定了包络物的结合常数和结合比。实验结果表明,当向诺氟沙星、环丙沙星的水溶液中加入杯[8]芳烃磺酸钠溶液时,均出现荧光猝灭现象。接着向超分子包络体系中加入牛血清白蛋白(BSA)以后,荧光强度得到恢复。表明蛋白质可以与包络体系中的喹诺酮类药物竞争杯[8]芳烃磺酸钠,进一步说明可用于喹诺酮类药物的储存和定点释控。
第四部分利用荧光光谱以及紫外吸收光谱法研究了杯[n]芳烃磺酸钠与吩噻嗪类药物亚甲基蓝以及甲苯胺蓝之间的包络作用,通过与喹诺酮类药物包络的比较,以及不同空腔尺寸的杯芳烃磺酸钠对吩噻嗪类药物包络作用的比较,研究了杯[n]芳烃磺酸钠作为主体化合物与药物进行包络的主要作用方式。
第五部分以亚甲基蓝为探针测定了牛奶中蛋白质的含量,采用荧光光度法研究了杯[6]磺酸钠—亚甲基蓝—牛血清蛋白体系。讨论了杯[6]芳烃磺酸钠—甲苯胺蓝超分子体系的最佳形成条件,建立了一种灵敏度高的检测方法。方法用于实际样品测定中,结果令人满意。
第六部分对论文的工作进行了总结,并对以后的工作进行了展望。
Supramolecular Chemistry originated from the discovery of crown ethers and was further developed as host-guest chemistry and supramolecular chemistry by D. J. Cram and J. M. Lehn. Calixarene was the representative of the third generation supramolecular. Different functional groups were introduced to the calixarene in this paper. With their different electric, good water solubility and spectral activity of nature, not only water-soluble ability of calixarene was enhanced significantly, but also the application of calixarene derivatives in the spectrum and molecular recognition was enlarged. Water-soluble calixarene derivatives and spectral activity of calixarene derivatives were synthesized in this paper .In order to study the feasibility of the p-sulfoniccalix[8]arene as controlled-release drug delivery agents in pharmaceutical industry, the inclusion behavior between p-sulfoniccalix[8]arene and quinolones or quinolones drugs were investigated. This study demonstrated the potential application of calixarene derivatives in biology and pharmaceutics. There were some paragraphs in this paper as following.
The research significance of calixarene, the research of water-soluble calixarene derivatives and azobenzene calixarene derivatives, the applications of calixarene and its derivatives in molecular recognition, the main content and characteristic of this paper were summarized in first paragraph.
Tert-butylcalix[n]arene (n=4,8) and intermediate de-tert-butylcalix[n]arene were synthesized with one-step method in the second paragraph, and further benzene sulfonic acid and the acid azo introduced into the off-tert-butyl calixarenes, the synthesis of a calix[8]arene, calix sulfobenzylidene[n]arene (n=4,8). Infrared spectroscopy, ultraviolet spectroscopy, elemental analysis were used to characterize the structure of the synthesized product , the reaction process was tracked using thin layer chromatography, and the purity of the synthesized product was characterized with liquid chromatography. Finally, the product factors in the experiment were discussed.
In the third paragraph, the inclusion behavior between p-sulfoniccalix[8]arene and quinolones drugs were investigated by fluorescence spectroscopy. The optimum conditions of forming host-guest systems in aqueous solution were studied.Meanwhile, in order to discuss the mechanism of inclusion process, the various influence on the inclusion process, such as temperature, pH value, concentrations of host and guest compounds, surfactants, organic solvent were also examined. On the base of experimental results, the association constant K and combined ratio (n) were calculated. Subsequently, the addition of bovine serum albumin (BSA) solution into the host-guest system leads to the recovery of fluorescence intensity. It is indicated that BSA may destruct the SC8A-NFLX inclusion complex, and liberate the NFLX into solution.
In the fourth paragraph, the inclusion behavior between p-sulfoniccalix[n]arene and phenothiazine methylene blue and toluidine bule with fluorescence spectroscopy and UV absorption spectroscopy. The mechanism of inclusion process between p-sulfoniccalix[n]arene and quinolones drugs were discussed.
In the fifth paragraph, the protein in milk was determinated using methylene blue as the probe with fluorescence spectrophotometry of p-sulfoniccalix[6]arene-methylene blue -BSA system. The best formation conditions of the calix [6] arene-methylene blue supramolecular systems were discussed, and a low detection limit, high sensitivity detection method was established. The method was used in real samples and the experiment results were satisfactory
In the sixth paragraph, the jobs in this paper were summarized and the jobs in future were also discussed.
第一部分概述了杯芳烃的研究意义,水溶性杯芳烃以及偶氮杯芳烃衍生物的合成研究进展,杯芳烃及其衍生物的分子识别研究现状以及本论文研究的主要内容。
第二部分采用一步法合成了对叔丁基杯[n]芳烃(n=4,8)以及脱对叔丁基杯[n]芳烃,并将磺酸基以及对磺酸基苯偶氮基引入到脱对叔丁基杯芳烃上,合成了杯[8]芳烃磺酸钠和对磺酸基苯偶氮杯[n]芳烃(n=4,8)。利用红外光谱法、元素分析法等对合成产物的结构进行了表征,同时利用薄层色谱法跟踪反应过程,利用液相色谱法对合成产物的纯度进行了表征,并对实验过程中影响产率的主要因素进行了讨论。
第三部分利用荧光光谱法研究了杯[8]芳烃磺酸钠与诺氟沙星、杯[8]芳烃磺酸钠与环丙沙星在水溶液中的形成包络物的最佳条件。同时,利用荧光光谱法研究了包络物之间的主客体包络行为并测定了包络物的结合常数和结合比。实验结果表明,当向诺氟沙星、环丙沙星的水溶液中加入杯[8]芳烃磺酸钠溶液时,均出现荧光猝灭现象。接着向超分子包络体系中加入牛血清白蛋白(BSA)以后,荧光强度得到恢复。表明蛋白质可以与包络体系中的喹诺酮类药物竞争杯[8]芳烃磺酸钠,进一步说明可用于喹诺酮类药物的储存和定点释控。
第四部分利用荧光光谱以及紫外吸收光谱法研究了杯[n]芳烃磺酸钠与吩噻嗪类药物亚甲基蓝以及甲苯胺蓝之间的包络作用,通过与喹诺酮类药物包络的比较,以及不同空腔尺寸的杯芳烃磺酸钠对吩噻嗪类药物包络作用的比较,研究了杯[n]芳烃磺酸钠作为主体化合物与药物进行包络的主要作用方式。
第五部分以亚甲基蓝为探针测定了牛奶中蛋白质的含量,采用荧光光度法研究了杯[6]磺酸钠—亚甲基蓝—牛血清蛋白体系。讨论了杯[6]芳烃磺酸钠—甲苯胺蓝超分子体系的最佳形成条件,建立了一种灵敏度高的检测方法。方法用于实际样品测定中,结果令人满意。
第六部分对论文的工作进行了总结,并对以后的工作进行了展望。
Supramolecular Chemistry originated from the discovery of crown ethers and was further developed as host-guest chemistry and supramolecular chemistry by D. J. Cram and J. M. Lehn. Calixarene was the representative of the third generation supramolecular. Different functional groups were introduced to the calixarene in this paper. With their different electric, good water solubility and spectral activity of nature, not only water-soluble ability of calixarene was enhanced significantly, but also the application of calixarene derivatives in the spectrum and molecular recognition was enlarged. Water-soluble calixarene derivatives and spectral activity of calixarene derivatives were synthesized in this paper .In order to study the feasibility of the p-sulfoniccalix[8]arene as controlled-release drug delivery agents in pharmaceutical industry, the inclusion behavior between p-sulfoniccalix[8]arene and quinolones or quinolones drugs were investigated. This study demonstrated the potential application of calixarene derivatives in biology and pharmaceutics. There were some paragraphs in this paper as following.
The research significance of calixarene, the research of water-soluble calixarene derivatives and azobenzene calixarene derivatives, the applications of calixarene and its derivatives in molecular recognition, the main content and characteristic of this paper were summarized in first paragraph.
Tert-butylcalix[n]arene (n=4,8) and intermediate de-tert-butylcalix[n]arene were synthesized with one-step method in the second paragraph, and further benzene sulfonic acid and the acid azo introduced into the off-tert-butyl calixarenes, the synthesis of a calix[8]arene, calix sulfobenzylidene[n]arene (n=4,8). Infrared spectroscopy, ultraviolet spectroscopy, elemental analysis were used to characterize the structure of the synthesized product , the reaction process was tracked using thin layer chromatography, and the purity of the synthesized product was characterized with liquid chromatography. Finally, the product factors in the experiment were discussed.
In the third paragraph, the inclusion behavior between p-sulfoniccalix[8]arene and quinolones drugs were investigated by fluorescence spectroscopy. The optimum conditions of forming host-guest systems in aqueous solution were studied.Meanwhile, in order to discuss the mechanism of inclusion process, the various influence on the inclusion process, such as temperature, pH value, concentrations of host and guest compounds, surfactants, organic solvent were also examined. On the base of experimental results, the association constant K and combined ratio (n) were calculated. Subsequently, the addition of bovine serum albumin (BSA) solution into the host-guest system leads to the recovery of fluorescence intensity. It is indicated that BSA may destruct the SC8A-NFLX inclusion complex, and liberate the NFLX into solution.
In the fourth paragraph, the inclusion behavior between p-sulfoniccalix[n]arene and phenothiazine methylene blue and toluidine bule with fluorescence spectroscopy and UV absorption spectroscopy. The mechanism of inclusion process between p-sulfoniccalix[n]arene and quinolones drugs were discussed.
In the fifth paragraph, the protein in milk was determinated using methylene blue as the probe with fluorescence spectrophotometry of p-sulfoniccalix[6]arene-methylene blue -BSA system. The best formation conditions of the calix [6] arene-methylene blue supramolecular systems were discussed, and a low detection limit, high sensitivity detection method was established. The method was used in real samples and the experiment results were satisfactory
In the sixth paragraph, the jobs in this paper were summarized and the jobs in future were also discussed.
引文
[1] Jean-Marie Lehn. Supramolecular Chem is try -Scope and Perspectives Molecules, Super-molecules, and Molecular Devices (Nobel Lecture).Angew Chem, 1988, 27(1):89-112.
[2] Jean-Marie Lehn.超分子化学-概念和展望.北京:北京大学出版社, 2004.
[3]刘育,尤长城,张衡益.超分子化学.天津:南开大学出版社,2001.
[4]夏琳,邱桂学.化学科学的研究新领域—超分子化学.化学推进剂与高分子材料, 2007, 5 (1): 33-37.
[5] Kaneto Uekama, Fumitoshi Hirayama, Tetsumi Irie. Cyclodextrin Drug Carrier Systems. Chem. Rev. 1998, 98:2045-2076.
[6]钟志梅,姚俊学.杯芳烃及其衍生物的研究进展,内蒙古石油化工,2005(2):9-11.
[7]李勇,郭金梁,宋心琦.新型主体分子-杯芳烃类化合物.大学化学,1994,9(2): 1-8.
[8] Shinkai S, Mori S, Koreishi H, etal .Hexasulfonated Calix[6]Rene Derivatives: A New Class of Catalysts Surfac-tants and Host Molecules. J. Am Chem Soc, 1986, 108(9): 2409-2415.
[9] Shimojo K, Oshima T, Naganawa H, Goto M. Calixarene-Assisted Protein Refolding via Liquid-Liquid Extraction[J]. Biomacromolecules, 2007, 8(10): 3061-3066.
[10] Troisi F, Mogavero L,Gaeta C, Gavuzzo E, Neri P.Calixcyclitols: A New Class of Polar Hybrid Hosts Obtained by Oxygenation of Calixarene Phenol Rings. Org. Lett. 2007, 9(5): 915-918.
[11] Dieleman C, Steyer S, Jeunesse C, et al. Diphosphines based on an inherently chiral calix[4]arene scaffold: synthesis and use in enantioselective catalysisJ. Chem. Soc. DaltonTrans., 2001, 2508-2517.
[12] Consoli G.M.L, Granata G, LoNigro R, Malandrino G, Geraci C.Spontaneous Self-Assembly of Water-Soluble Nucleotide Calixarene Conjugates in Small Micelles Coalescing to Microspheres [J].Langmuir, 2008.
[13]王卉兰.杯芳烃的性质及应用.内蒙古石油化工,2005,7: 13-14.
[14]高博,冯亚青,周立山,等.杯芳烃包合作用的研究进展.有机化学,2004,24(7): 713-721.
[15]郭兵,冯亚青,周立山,等.新型主体分子-杯芳烃的研究进展[J].合成化学,2000,8(5): 395-399.
[16]王卉兰.杯[8]芳烃磺酸钠的合成及性质研究.江苏:扬州大学,2004.
[17] Shubkais, Arimurat, Arakik, etal. Syntheses and aggregation properties of new water-soluble calixarenes . J Chem Soc, Perkin Trans I, 1989, (11): 2039-2045.
[18]杨发福,蔡秀琴,郭红玉,等.新型杯[4]芳烃衍生物的合成及其氨基酸萃取性能.分子科学学报, 2006,22(2): 96-99.
[19] LuoJun, ZhengQi-yu, ChenChuan-feng.Facilesynthesis and optical resolution of inherently chiral fluores-cent calix[4] crowns: enantioselective recognition towardschiral leucinol.Tetrahedron, 2005, 61(35): 8517-8528.
[20]李园园,何锡文,张国柱,等.以含氨基酸1,3-桥联杯[4]芳烃为涂层的压电石英传感器对有机胺和有机醇的选择性识别研究[J].化学学报,2004,62(02): 194-198.
[21]李乾坤.核苷类杯芳烃衍生物的合成研究.上海:同济大学,2007.
[22]丁健桦,张晓敏,李建强.几种外向式杯[4]芳烃偶氮衍生物新试剂的合成及其吸收光谱性质.光谱实验室,2000,17 (6 ): 697-700.
[23]黄章杰,胡秋芬,杨光宇,等.新显色剂-[杯(4)芳烃偶氮]氨基喹啉的合成及其与金的显色反应.分析试验室,2003,22 (1) :75-77.
[24]刘爱林,傅崇岗,张立云,等.新型水溶有色主体分子对磺酸基苯偶氮杯[n]芳烃衍生物的合成及特性[J].化学试剂,2002,24 (6),331～334.
[25]张华承,郝爱友,申健.环糊精-杯芳烃偶合体系研究进展及前景展望.有机化学,2008,28 (6) :954～963.
[26] Wang J, Gutsche C. D. Complexation of Fullerenes with Bis-calix[n]arenes Synthesized by Tandem Claisen Rearrangement.J. Am. Chem. Soc, 1998, 120(47):12226-12231.
[27]朱蔚璞,苟鹏飞,沈之荃.含杯芳烃聚合物的合成与应用.化学进展,2008,20(5):720-728.
[28] Danil de Namor, A. F.; Chahine, S.J. Phys. Chem. B.; (Article); Solvation Effect of Guest, Supramolecular Host, and Host-Guest Compounds on the Thermodynamic Selectivity of Calix(4)arene Derivatives and Soft Metal Cations 2005; 109(38); 18096-18102.
[29] Saha, A.; Nayak, S. K.; Chottopadhyay, S.; Mukherjee, A. K Evidence of Reverse Micellization of a Calix[4]arene through a Study of Its Charge Transfer and Host-Guest Complexation with
[60]Fullerene.J. Phys. Chem. B.; (Article); 2004; 108(23); 7688-7693.
[30] ShinkaiS, Shirahama Y, TsubakiT, etal. CationicWater–solubleCalixarenes: New Host Molecules which Catal- yse BasicHydrolysis of a Phosphate Ester [J]. Chem.Soc, Perkin Transl, 1989(10): 1859-1 860.
[31] Shinkai S, Kawabata H,Matsuda T, et a.l Synthesis andInclusion Properties of n' eutral'Water-soluble Calixare-nes [J]. Bull Chem Soc Jpn, 1990, 63 (4): 1 272 -1 274.
[32] Hardie,M.J.Supramol.Chem.2002,14(1),7.
[33] BrouwerE.B.,Enright,G.D.; Ripmeester,J.A.J.InclusionPhenom. Mol.Recognit.Chem.1996, 24, 1.
[34] Nagasaki T, Fujishima H, Shinkai S. Calix[4]arene-Capped Tetraphenylporphyrin. Synthetic Approach to a Chiral Capped Porphyrin with Regular C4 Symmetry[J] .Chem. Lett, 1994,989.
[35] Nagasaki T, Fujishima H, TakeuchiM, Shinkai S. Design and synthesis of a C4-symmetrical hard–soft ditopic metal receptor by calixarene–porphyrin coupling[J]. J.Chem. Soc, Perkin Trans. 1995:1883-1888.
[36] Grazia M.L. Consoli, Giuseppe Granata, Eva Galante, Isabella Di Silvestro, Laura Salafia and Corrada Geraci .Synthesis of water-soluble nucleotide-calixarene conjugates and preliminary investigation of their in vitro DNA replication inhibitory activity[J].Tetrahedron, 2007, 63(44): 10758-10763.
[37] Shahabuddin Memon, Mustafa Tabakci, D. Max Roundhill and Mustafa Yilmaz .Synthesis and evaluation of the Cr(VI) extraction ability of amino/nitrile calix[4]arenes immobilized onto a polymeric backbone[J].Reactive and Functional Polymers, 2006,66(11): 1342-1349.
[38] Heng Xu, Gary R. Kinsel, Jiang Zhang, Meiling Li and Dmitry M. Rudkevich .Calixarene amino acids; building blocks for calixarene peptides and peptide-dendrimers[J].Tetrahedron, 2003, 59: 5837-5848.
[39] Yan X, Janout V, Hsu J.T, Regen S. L. A Polymerized Calix[6]arene Monolayer Having Gas Permeation Selectivity that Exceeds Knudsen Diffusion J. Am. Chem. Soc, 2002,24(37): 10962-10963.
[40] Koji Iwamoto, Hiroyasu Shimizu, Koji Araki, Seiji Shinkai .Correction.Synthesis and Optical Resolution of Calix[4]arenes with Molecular Asymmetry. Systematic Classificaton of All Possible Chiral Isomers Derivable from Calix[4]arene [J]. Am. Chem. Soc, 1993,15(25):12228.
[41] Bernardino, R. J.; Cabral, B. J. C.Structure, Conformational Equilibrium, and Proton Affinity of Calix[4]arene by Density Functional Theory J. Phys. Chem. A.; (Article); 1999; 103(45); 9080-9085.
[42]陈轶华,罗虹.杯芳烃受体的合成及其对氨基酸的识别.南华大学学报(自然科学版),2005,19(9): 99-101
[43] Fang Liu, Guo-Yuan Lu, Wei-Jiang He, Ming-Hua Liu and Long-Gen Zhu .Enantioselective recognition of calix[4]arene derivatives bearing chiral bicyclic guanidinium for D/L-phenylalanine zwitterions at the air–water interface[J].Thin Solid Films, 2004, 468(1-2): 244-249.
[44] W. Zielenkiewicz, A. Marcinowicz, J.Poznański,S.Cherenokand V. Kalchenko .Complexation of isoleucine by phosphorylated calix[4]arene in methanol followed by calorimetry, NMR and UV–VIS spectroscopies, and molecular modeling methods[J].Journal of Molecular Liquids, 2005, 121(1): 8-14
[45]黄志兵,李来生,王宇晓,等.对-二甲胺甲基-杯[8]芳烃与DNA相互作用的紫外-可见光谱.化学研究与应用,2004,16(6): 808-810.
[46]李来生,黄志兵,刘旭,等.亚甲基蓝作为光谱探针研究对-二甲胺甲基-杯[8]芳烃与DNA的相互作用.应用化学,2004,21(10): 1011-1015.
[47]李艳平,李来生,黄志兵,等.荧光法研究对羧基苯偶氮基杯[8]芳烃与诺氟沙星的作用.光谱学与光谱分析,2007,(1):108-112.
[48]李艳平,李来生,黄志兵,等.光谱法研究水溶性杯[8]芳烃对伊红的分子识别作用.南昌大学学报(理科版),2006,30(2):139-145.
[49]汤又文,颜景辉,乐善堂.下沿含苯磺酰基杯芳烃衍生物与Eu~(3+)配合物的光谱性质研究.中国稀土学报,2005,23(1):122-124.
[50]闫秋君,何瑜,宋功武.荧光光度法研究杯[6]与蛋白质的相互作用.湖北大学学报(自然科学版), 2006,28(1): 59-61.
[51]李来生,李艳平,黄志兵,等.用荧光法研究对-二甲氨甲基-杯[8]芳烃与牛血清白蛋白的相互作用.分析科学学报,2006,22(5): 505-509.
[52] Tatsuya Oshima, Akinori Suetsugu, Yoshinari Baba, Yuka Shikaze, Keisuke Ohto and Katsutoshi Inoue. Liquid membrane transport of cytochrome using a calix[6]arene carboxylic acid derivative as a carrier[J].Journal of Membrane Science, 2007,09,033.
[53] Karel K?enek, Markéta Kuldová, Katarína Hulíková, Ivan Stibor, Pavel Lhoták, Miroslav Dudi?, Jan Budka, Helena Pelantová, Karel Bezou?ka, Anna Fi?erováand Vladimír K?en N-Acetyl-d-glucosamine substituted calix[4]arenes as stimulators of NK cell-mediated antitumor immune response [J].Carbohydrate Research, 2007, 342(12-13): 1781-1792.
[54]双少敏,周叶红.荧光光谱法研究杯芳烃与B-胡萝卜素的饱和作用及其荧光分析应用.重点实验室建设,2006,9:15-17.
[55] Lu, Q. Study on the inclusion interaction of p-sulfonated calix[n]arenes with Vitamin K3 using methylene blue as a spectral probe[J].Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2007. 68(1): 15-20.
[56] Vishwanath D. Vaze, Ashwini K. Srivastava .Electrochemical behavior of folic acid at calixarene basedchemically modified electrodes and its determination by adsorptive stripping voltammetry[J].Electrochimica Acta 53 (2007) :1713–1721.
[57] Goto K, Yano Y, Okada E, Liu C.W, Yamamoto K Ueoka, R.Catalytic Specificity Exhibited by p-Sulfonatocalix[n]arenes in the Methanolysis of N-Acetyl-L-amino Acids[J]. J. Org. Chem., 2003, 68(3): 865-870.
[58] H. Nakayama T, Sherwood M, Miller D, Ueda M.Characterization and Lithographic Application of Calix[4]resorcinarene Derivatives[J].Ito, Chem. Mater,2008, 20(1): 341-356.
[59] N. Sieffert, and G. Wipff. Alkali Cation Extraction by Calix[4]crown-6 toRoom-Temperature Ionic Liquids. J. Phys. Chem. A, 2006, 110 (3), 1106-1117.
[60] Cun-Ji Yan, Hui-Juan Yan, Li-Ping Xu, Wei-Guo Song, Li-Jun Wan, Qi-Qiang Wang, and Mei-Xiang Wang.Adlayer Structures of Aza- and/or Oxo-Bridged Calix[2]arene[2]triazines on Au(Ⅲ) Investigated by Scanning Tunneling Microscopy (STM)[J]. Langmuir, 2007, 23 (15), 8021-8027.
[61] GUTSCHE CD, DHAWAN B, NOKH, etal. Calixarenes.4.the synthesis, characterization, and properties of the cal-ixarenes fromp-tert-butylphenol [J]. J Am Chem Soc, 1981, 103(13): 3782-3792.
[62]冯亚青,洪学传,李熙凤,等.杯芳烃的合成及其在聚丙烯中的抗热氧性能研究.塑料工业, 2000, 28(1): 323-338.
[63]耿天奇,曹端林,李永祥,等.杯[8]芳烃母体化合物的合成.现代化工, 2006, 26(7): 42-44.
[64] SeijiShinkai, Koji Araki, Takayuki Tsubaki, etal. New Syntheses of Calixarene–p -su1phonates and p-Nitroealixarenest. Chem.Socperkin Transl , 1987:2297.
[65] Seiji Shinkai, Seiichi Mori, Hiroshi Korershi, etal. Hexasulfonated Calix[6]arene Derivatives:A New Class of Catalysts, Surfactants, and Host Molecules. Am.Chem.Soe.1986, 108: 2409.
[66]刘爱林,傅崇岗,张立云,等.新型水溶有色主体分子对磺酸基苯偶氮杯[n]芳烃衍生物的合成及特性[J].化学试剂,2002,24 (6),331～334.
[67]叶红丽.环丙沙星在兽医临床上的应用[J].中国兽医杂志, 1995, 29:55-56.
[68]王绍宁,邓意辉,陈咏,等.荧光法测定小鼠体内各组织中环丙沙星的浓度[J].药物分析杂志,2003, 23 (3): 192
[69]尤启冬.药物化学[M].北京:化学工业出版社, 2004.
[70]陈国珍,黄贤智,许金钩.荧光分析法[M].北京:科学出版社, 1990.
[71]S. Shinkai, K. Araki, T. Matsuda, N. Nishiyama, H. Ikeda, J. Am. Chem. Soc. 112 (1990) 9053-9058.
[72]杜黎明,晋卫军,董川,等.喹诺酮类药物的质子化作用及互变异构现象与荧光特性的相关性研究[J].光谱学与光谱分析, 2001,21(14): 518-520.
[73]李来生,黄志兵,刘旭,等.亚甲蓝作为光谱探针研究对二甲氨甲基杯[8]芳烃与DNA间的作用.应用化学,2004,21(10):1011-1015
[74] Qin Lu, Jiashan Gu,Huapeng Yu,eatl. Study on the inclusion interaction of p-sulfonated calix[n]areneswith Vitamin K3 using methylene blue as a spectral probe Spectrochim. Acta Part A: Mol. Biomol. Spectrosc.2006.10.044.
[75]金贞玉.用吸收光谱研究甲苯胺蓝在表面活性剂中的聚合状态.光谱实验室.1999,16(1):108-110.
[76]王春,吴秋华,王志,等.槲皮素与牛血清白蛋白相互作用的研究.光谱学与光谱分析,2006,26(9):1672-1675
[77] Y. Liu, B.-H. Han, Y.-T. Inclusion Complexation of Acridine Red Dye by Calixarenesulfonates and Cyclodextrins: Opposite Fluorescent BehaviorChen, J. Org. Chem. 65 (2000) 6227
[78]高建华,翟海云,陈彬.杯[8]芳烃与铈形成的镧系超分子作荧光探针测定蛋白质.分析化学,2002,30(3):295-297
[2] Jean-Marie Lehn.超分子化学-概念和展望.北京:北京大学出版社, 2004.
[3]刘育,尤长城,张衡益.超分子化学.天津:南开大学出版社,2001.
[4]夏琳,邱桂学.化学科学的研究新领域—超分子化学.化学推进剂与高分子材料, 2007, 5 (1): 33-37.
[5] Kaneto Uekama, Fumitoshi Hirayama, Tetsumi Irie. Cyclodextrin Drug Carrier Systems. Chem. Rev. 1998, 98:2045-2076.
[6]钟志梅,姚俊学.杯芳烃及其衍生物的研究进展,内蒙古石油化工,2005(2):9-11.
[7]李勇,郭金梁,宋心琦.新型主体分子-杯芳烃类化合物.大学化学,1994,9(2): 1-8.
[8] Shinkai S, Mori S, Koreishi H, etal .Hexasulfonated Calix[6]Rene Derivatives: A New Class of Catalysts Surfac-tants and Host Molecules. J. Am Chem Soc, 1986, 108(9): 2409-2415.
[9] Shimojo K, Oshima T, Naganawa H, Goto M. Calixarene-Assisted Protein Refolding via Liquid-Liquid Extraction[J]. Biomacromolecules, 2007, 8(10): 3061-3066.
[10] Troisi F, Mogavero L,Gaeta C, Gavuzzo E, Neri P.Calixcyclitols: A New Class of Polar Hybrid Hosts Obtained by Oxygenation of Calixarene Phenol Rings. Org. Lett. 2007, 9(5): 915-918.
[11] Dieleman C, Steyer S, Jeunesse C, et al. Diphosphines based on an inherently chiral calix[4]arene scaffold: synthesis and use in enantioselective catalysisJ. Chem. Soc. DaltonTrans., 2001, 2508-2517.
[12] Consoli G.M.L, Granata G, LoNigro R, Malandrino G, Geraci C.Spontaneous Self-Assembly of Water-Soluble Nucleotide Calixarene Conjugates in Small Micelles Coalescing to Microspheres [J].Langmuir, 2008.
[13]王卉兰.杯芳烃的性质及应用.内蒙古石油化工,2005,7: 13-14.
[14]高博,冯亚青,周立山,等.杯芳烃包合作用的研究进展.有机化学,2004,24(7): 713-721.
[15]郭兵,冯亚青,周立山,等.新型主体分子-杯芳烃的研究进展[J].合成化学,2000,8(5): 395-399.
[16]王卉兰.杯[8]芳烃磺酸钠的合成及性质研究.江苏:扬州大学,2004.
[17] Shubkais, Arimurat, Arakik, etal. Syntheses and aggregation properties of new water-soluble calixarenes . J Chem Soc, Perkin Trans I, 1989, (11): 2039-2045.
[18]杨发福,蔡秀琴,郭红玉,等.新型杯[4]芳烃衍生物的合成及其氨基酸萃取性能.分子科学学报, 2006,22(2): 96-99.
[19] LuoJun, ZhengQi-yu, ChenChuan-feng.Facilesynthesis and optical resolution of inherently chiral fluores-cent calix[4] crowns: enantioselective recognition towardschiral leucinol.Tetrahedron, 2005, 61(35): 8517-8528.
[20]李园园,何锡文,张国柱,等.以含氨基酸1,3-桥联杯[4]芳烃为涂层的压电石英传感器对有机胺和有机醇的选择性识别研究[J].化学学报,2004,62(02): 194-198.
[21]李乾坤.核苷类杯芳烃衍生物的合成研究.上海:同济大学,2007.
[22]丁健桦,张晓敏,李建强.几种外向式杯[4]芳烃偶氮衍生物新试剂的合成及其吸收光谱性质.光谱实验室,2000,17 (6 ): 697-700.
[23]黄章杰,胡秋芬,杨光宇,等.新显色剂-[杯(4)芳烃偶氮]氨基喹啉的合成及其与金的显色反应.分析试验室,2003,22 (1) :75-77.
[24]刘爱林,傅崇岗,张立云,等.新型水溶有色主体分子对磺酸基苯偶氮杯[n]芳烃衍生物的合成及特性[J].化学试剂,2002,24 (6),331～334.
[25]张华承,郝爱友,申健.环糊精-杯芳烃偶合体系研究进展及前景展望.有机化学,2008,28 (6) :954～963.
[26] Wang J, Gutsche C. D. Complexation of Fullerenes with Bis-calix[n]arenes Synthesized by Tandem Claisen Rearrangement.J. Am. Chem. Soc, 1998, 120(47):12226-12231.
[27]朱蔚璞,苟鹏飞,沈之荃.含杯芳烃聚合物的合成与应用.化学进展,2008,20(5):720-728.
[28] Danil de Namor, A. F.; Chahine, S.J. Phys. Chem. B.; (Article); Solvation Effect of Guest, Supramolecular Host, and Host-Guest Compounds on the Thermodynamic Selectivity of Calix(4)arene Derivatives and Soft Metal Cations 2005; 109(38); 18096-18102.
[29] Saha, A.; Nayak, S. K.; Chottopadhyay, S.; Mukherjee, A. K Evidence of Reverse Micellization of a Calix[4]arene through a Study of Its Charge Transfer and Host-Guest Complexation with
[60]Fullerene.J. Phys. Chem. B.; (Article); 2004; 108(23); 7688-7693.
[30] ShinkaiS, Shirahama Y, TsubakiT, etal. CationicWater–solubleCalixarenes: New Host Molecules which Catal- yse BasicHydrolysis of a Phosphate Ester [J]. Chem.Soc, Perkin Transl, 1989(10): 1859-1 860.
[31] Shinkai S, Kawabata H,Matsuda T, et a.l Synthesis andInclusion Properties of n' eutral'Water-soluble Calixare-nes [J]. Bull Chem Soc Jpn, 1990, 63 (4): 1 272 -1 274.
[32] Hardie,M.J.Supramol.Chem.2002,14(1),7.
[33] BrouwerE.B.,Enright,G.D.; Ripmeester,J.A.J.InclusionPhenom. Mol.Recognit.Chem.1996, 24, 1.
[34] Nagasaki T, Fujishima H, Shinkai S. Calix[4]arene-Capped Tetraphenylporphyrin. Synthetic Approach to a Chiral Capped Porphyrin with Regular C4 Symmetry[J] .Chem. Lett, 1994,989.
[35] Nagasaki T, Fujishima H, TakeuchiM, Shinkai S. Design and synthesis of a C4-symmetrical hard–soft ditopic metal receptor by calixarene–porphyrin coupling[J]. J.Chem. Soc, Perkin Trans. 1995:1883-1888.
[36] Grazia M.L. Consoli, Giuseppe Granata, Eva Galante, Isabella Di Silvestro, Laura Salafia and Corrada Geraci .Synthesis of water-soluble nucleotide-calixarene conjugates and preliminary investigation of their in vitro DNA replication inhibitory activity[J].Tetrahedron, 2007, 63(44): 10758-10763.
[37] Shahabuddin Memon, Mustafa Tabakci, D. Max Roundhill and Mustafa Yilmaz .Synthesis and evaluation of the Cr(VI) extraction ability of amino/nitrile calix[4]arenes immobilized onto a polymeric backbone[J].Reactive and Functional Polymers, 2006,66(11): 1342-1349.
[38] Heng Xu, Gary R. Kinsel, Jiang Zhang, Meiling Li and Dmitry M. Rudkevich .Calixarene amino acids; building blocks for calixarene peptides and peptide-dendrimers[J].Tetrahedron, 2003, 59: 5837-5848.
[39] Yan X, Janout V, Hsu J.T, Regen S. L. A Polymerized Calix[6]arene Monolayer Having Gas Permeation Selectivity that Exceeds Knudsen Diffusion J. Am. Chem. Soc, 2002,24(37): 10962-10963.
[40] Koji Iwamoto, Hiroyasu Shimizu, Koji Araki, Seiji Shinkai .Correction.Synthesis and Optical Resolution of Calix[4]arenes with Molecular Asymmetry. Systematic Classificaton of All Possible Chiral Isomers Derivable from Calix[4]arene [J]. Am. Chem. Soc, 1993,15(25):12228.
[41] Bernardino, R. J.; Cabral, B. J. C.Structure, Conformational Equilibrium, and Proton Affinity of Calix[4]arene by Density Functional Theory J. Phys. Chem. A.; (Article); 1999; 103(45); 9080-9085.
[42]陈轶华,罗虹.杯芳烃受体的合成及其对氨基酸的识别.南华大学学报(自然科学版),2005,19(9): 99-101
[43] Fang Liu, Guo-Yuan Lu, Wei-Jiang He, Ming-Hua Liu and Long-Gen Zhu .Enantioselective recognition of calix[4]arene derivatives bearing chiral bicyclic guanidinium for D/L-phenylalanine zwitterions at the air–water interface[J].Thin Solid Films, 2004, 468(1-2): 244-249.
[44] W. Zielenkiewicz, A. Marcinowicz, J.Poznański,S.Cherenokand V. Kalchenko .Complexation of isoleucine by phosphorylated calix[4]arene in methanol followed by calorimetry, NMR and UV–VIS spectroscopies, and molecular modeling methods[J].Journal of Molecular Liquids, 2005, 121(1): 8-14
[45]黄志兵,李来生,王宇晓,等.对-二甲胺甲基-杯[8]芳烃与DNA相互作用的紫外-可见光谱.化学研究与应用,2004,16(6): 808-810.
[46]李来生,黄志兵,刘旭,等.亚甲基蓝作为光谱探针研究对-二甲胺甲基-杯[8]芳烃与DNA的相互作用.应用化学,2004,21(10): 1011-1015.
[47]李艳平,李来生,黄志兵,等.荧光法研究对羧基苯偶氮基杯[8]芳烃与诺氟沙星的作用.光谱学与光谱分析,2007,(1):108-112.
[48]李艳平,李来生,黄志兵,等.光谱法研究水溶性杯[8]芳烃对伊红的分子识别作用.南昌大学学报(理科版),2006,30(2):139-145.
[49]汤又文,颜景辉,乐善堂.下沿含苯磺酰基杯芳烃衍生物与Eu~(3+)配合物的光谱性质研究.中国稀土学报,2005,23(1):122-124.
[50]闫秋君,何瑜,宋功武.荧光光度法研究杯[6]与蛋白质的相互作用.湖北大学学报(自然科学版), 2006,28(1): 59-61.
[51]李来生,李艳平,黄志兵,等.用荧光法研究对-二甲氨甲基-杯[8]芳烃与牛血清白蛋白的相互作用.分析科学学报,2006,22(5): 505-509.
[52] Tatsuya Oshima, Akinori Suetsugu, Yoshinari Baba, Yuka Shikaze, Keisuke Ohto and Katsutoshi Inoue. Liquid membrane transport of cytochrome using a calix[6]arene carboxylic acid derivative as a carrier[J].Journal of Membrane Science, 2007,09,033.
[53] Karel K?enek, Markéta Kuldová, Katarína Hulíková, Ivan Stibor, Pavel Lhoták, Miroslav Dudi?, Jan Budka, Helena Pelantová, Karel Bezou?ka, Anna Fi?erováand Vladimír K?en N-Acetyl-d-glucosamine substituted calix[4]arenes as stimulators of NK cell-mediated antitumor immune response [J].Carbohydrate Research, 2007, 342(12-13): 1781-1792.
[54]双少敏,周叶红.荧光光谱法研究杯芳烃与B-胡萝卜素的饱和作用及其荧光分析应用.重点实验室建设,2006,9:15-17.
[55] Lu, Q. Study on the inclusion interaction of p-sulfonated calix[n]arenes with Vitamin K3 using methylene blue as a spectral probe[J].Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2007. 68(1): 15-20.
[56] Vishwanath D. Vaze, Ashwini K. Srivastava .Electrochemical behavior of folic acid at calixarene basedchemically modified electrodes and its determination by adsorptive stripping voltammetry[J].Electrochimica Acta 53 (2007) :1713–1721.
[57] Goto K, Yano Y, Okada E, Liu C.W, Yamamoto K Ueoka, R.Catalytic Specificity Exhibited by p-Sulfonatocalix[n]arenes in the Methanolysis of N-Acetyl-L-amino Acids[J]. J. Org. Chem., 2003, 68(3): 865-870.
[58] H. Nakayama T, Sherwood M, Miller D, Ueda M.Characterization and Lithographic Application of Calix[4]resorcinarene Derivatives[J].Ito, Chem. Mater,2008, 20(1): 341-356.
[59] N. Sieffert, and G. Wipff. Alkali Cation Extraction by Calix[4]crown-6 toRoom-Temperature Ionic Liquids. J. Phys. Chem. A, 2006, 110 (3), 1106-1117.
[60] Cun-Ji Yan, Hui-Juan Yan, Li-Ping Xu, Wei-Guo Song, Li-Jun Wan, Qi-Qiang Wang, and Mei-Xiang Wang.Adlayer Structures of Aza- and/or Oxo-Bridged Calix[2]arene[2]triazines on Au(Ⅲ) Investigated by Scanning Tunneling Microscopy (STM)[J]. Langmuir, 2007, 23 (15), 8021-8027.
[61] GUTSCHE CD, DHAWAN B, NOKH, etal. Calixarenes.4.the synthesis, characterization, and properties of the cal-ixarenes fromp-tert-butylphenol [J]. J Am Chem Soc, 1981, 103(13): 3782-3792.
[62]冯亚青,洪学传,李熙凤,等.杯芳烃的合成及其在聚丙烯中的抗热氧性能研究.塑料工业, 2000, 28(1): 323-338.
[63]耿天奇,曹端林,李永祥,等.杯[8]芳烃母体化合物的合成.现代化工, 2006, 26(7): 42-44.
[64] SeijiShinkai, Koji Araki, Takayuki Tsubaki, etal. New Syntheses of Calixarene–p -su1phonates and p-Nitroealixarenest. Chem.Socperkin Transl , 1987:2297.
[65] Seiji Shinkai, Seiichi Mori, Hiroshi Korershi, etal. Hexasulfonated Calix[6]arene Derivatives:A New Class of Catalysts, Surfactants, and Host Molecules. Am.Chem.Soe.1986, 108: 2409.
[66]刘爱林,傅崇岗,张立云,等.新型水溶有色主体分子对磺酸基苯偶氮杯[n]芳烃衍生物的合成及特性[J].化学试剂,2002,24 (6),331～334.
[67]叶红丽.环丙沙星在兽医临床上的应用[J].中国兽医杂志, 1995, 29:55-56.
[68]王绍宁,邓意辉,陈咏,等.荧光法测定小鼠体内各组织中环丙沙星的浓度[J].药物分析杂志,2003, 23 (3): 192
[69]尤启冬.药物化学[M].北京:化学工业出版社, 2004.
[70]陈国珍,黄贤智,许金钩.荧光分析法[M].北京:科学出版社, 1990.
[71]S. Shinkai, K. Araki, T. Matsuda, N. Nishiyama, H. Ikeda, J. Am. Chem. Soc. 112 (1990) 9053-9058.
[72]杜黎明,晋卫军,董川,等.喹诺酮类药物的质子化作用及互变异构现象与荧光特性的相关性研究[J].光谱学与光谱分析, 2001,21(14): 518-520.
[73]李来生,黄志兵,刘旭,等.亚甲蓝作为光谱探针研究对二甲氨甲基杯[8]芳烃与DNA间的作用.应用化学,2004,21(10):1011-1015
[74] Qin Lu, Jiashan Gu,Huapeng Yu,eatl. Study on the inclusion interaction of p-sulfonated calix[n]areneswith Vitamin K3 using methylene blue as a spectral probe Spectrochim. Acta Part A: Mol. Biomol. Spectrosc.2006.10.044.
[75]金贞玉.用吸收光谱研究甲苯胺蓝在表面活性剂中的聚合状态.光谱实验室.1999,16(1):108-110.
[76]王春,吴秋华,王志,等.槲皮素与牛血清白蛋白相互作用的研究.光谱学与光谱分析,2006,26(9):1672-1675
[77] Y. Liu, B.-H. Han, Y.-T. Inclusion Complexation of Acridine Red Dye by Calixarenesulfonates and Cyclodextrins: Opposite Fluorescent BehaviorChen, J. Org. Chem. 65 (2000) 6227
[78]高建华,翟海云,陈彬.杯[8]芳烃与铈形成的镧系超分子作荧光探针测定蛋白质.分析化学,2002,30(3):295-297
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |