用户名: 密码: 验证码:
一种放大荧光共轭聚合物的制备及应用研究
详细信息    本馆镜像全文|  推荐本文 |  |   获取CNKI官网全文
摘要
随着对放大荧光共轭聚合物研究的深入,其在各个领域的研究和应用受到日益关注,并发挥了很大的优越性。本论文首先详细介绍了荧光共轭聚合物的发展和应用,同时介绍了当前农残检测的各种手段和方法。在这些领域,我们主要做了如下工作:
     一、采用常规和微波两种方法合成了一种具有五迭烯刚性结构的非离子型放大荧光共轭聚合物。在原有方法基础上,对部分实验路线和操作流程进行了优化和改良;采用微波辅助合成方法,改善了合成此类化合物的反应条件,加快了反应速率,缩短了反应时间,结果表明本实验方法对该类合成反应具有良好的应用前景。
     二、研究了本论文所制备的各荧光物质的光谱性质,通过对TNT猝灭效应的研究,详细比较了荧光单体、常规和微波两种反应条件下的聚合产物的荧光性能,显示了放大荧光共轭聚合物荧光性能的优越性。
     三、重点介绍了该聚合物在农药残留检测方面的初步应用研究,通过向农药溶液中加入该荧光性物质来检测荧光光谱或强度变化,以实现检测农药残留的目的,结果显示该聚合物对部分农药具有很强的灵敏性反应,可以考虑应用到农药残留的荧光光谱检测中。此外,还介绍了其它几种物质对该聚合物的荧光性能影响,具有一定的理论研究意义。
Amplifying Fluorescent Conjugated Polymers(AFPs) as a good Luminescent material has many advantages. Such as: high luminescent intensity , stability, and also has the special“molecular-wire effect”which can greatly amplified the response signals. So in recent years, there are more and more attentions about it, which contains molecular design, synthesis, applications and so on. In this thesis, we studies on the preparation and applications of AFPs. For its fluorescent character, we also research the analysis of pesticide residue with AFPS.
     As anthracene and benzoquinone to be raw materials, though a serials of chemicall reactions in Microwave assistance. We obtaine the fluorescent monomer, that is 1, 4- diethynyl- 2, 3, 5, 6- bis (9, 10- anthracyl) benzene. Then added the other monomer 1, 4- bis (cetyloxy)- 2, 5- diiodobenzene for copolymerized reaction. In this step, we adopt two methods: traditional heat up and Microwave assistance heat up (MWS). The results reveal that MWS can accelerate largely, and this AFP has high fluorescent intensity and stability.
     Then we studies on the fluoresence character of fluorescent monomer and AFP. Through the quenching effect when add to TNT, it is obviously that the AFP has the higer sensibility than the monomer. In the meantime, there no remarkable difference between the AFP in MWS and the AFP in traditional condition. So we can say that MWS is a better way for this reaction.
     Finally, we research the fluoresence analysis method of pesticides residues. We add each kind of pesticide sample to the AFP solution, then detect the change of AFP’s flouresent intensity to test the suitable pesticide. This study observes that some pesticides are highly sensitive to the AFP’s fluoresence,for example: which contains two–NO2, decachloro-bi-4-cyclopentadien-1-yl,organic- phosphorus -pesticide, ester-pesticide and so on. So we can use AFP to test these pesticides. This method can be operated easily with a fast speed and be sensitive.
     Besides we also studies on the fluorescence effect of some other substances, such as GSH and surface-active agents. This provide a new example for the enhancement effect of flourescense, which has some signification for theoretic research.
引文
1 Burroughes J H, Bradley D D C, Brown A R. et al. Lightemitting-dioes based on conjugated polymers. Nature, 1990, 347(6293):539~541
    2 Macdiarmid A G, Mu S L, Somasiri N L D, et al. Electrochemcal characteristics of polyaniline cathdes and anodes in aqueouselectrolytes. Mol Cryst Liq Cryst, 1985, 121(1~4):187~190
    3 Pei Q, Yu G, Zhang C, et al. Light-emitting electrochemical- cells-reply, Science, 1995, 270(5237);719
    4 Zhou Q., Swager T. M., Fluorescent Chemosensors Based on Energy Migration in Conjugated Polymers: The Molecular Wire Approach to Increased Sensitivity, J. Am. Chem. Soc., 1995, 117, 12593-12602
    5 黄红梅, 王柯敏, 肖毅. 基于分子导线效应的聚苯乙炔吡啶荧光 共 轭 聚 合 物 传 感 信 号 放 大 研 究 , 科 学 通 报 , 2003, 48(11):1158~1162
    6 Zhou Q, Swager T M. Methodology for enhanced the sensitivity of fluorescent chemosensors: energy migration in conjugated polymer. J Am Chem Soc, 1995, 117(26):7017~7018
    7 Harrison B S, Ramey M B, Reynolds J R, et al. Amplified fluorescence quenching in a poly(p-phenylene)-based cationic polyelectrolyte. J Am Chem Soc, 2000, 122(35):8561~8562
    8 Fan C H, Plaxco K W, Heeger A J. High-efficiency fluorescence quenching of conjugated polymers by proteins. J.Am Chem Soc, 2002, 124(20):5642~5643
    9 Jiang B, Zhang Y, Sahay S, et al. Conjugated polymers containing pendant terpyridine receptors: highly efficient sensory materialsfor transition mental ions. SPIE Proceedings, 1999, 212~223
    10 Mcquade D T, Pullen A E, Swager T M. Conjugated polymerbased chemical sensors. Chem Rev, 2000, 100(7):2537~2574
    11 Swager T. M., The Molecular Wire Approach to Sensory Signal Amplification, Acc. Chem. Res., 1998, 31, 201-207
    12 金绪刚,龚克成, 共轭聚合物应用研究新进展,材料导报,1995,No.6,55-58
    13 Amplifying Fluorescent Polymers, Sensors & Instrumentation
    14 Swager T. M., The Molecular Wire Approach to Sensory Signal Amplification, Acc. Chem. Res., 1998, 31, 201-207.
    15 Thienpont H., Rikken G. L. J. A., Meijer E. E., et al., Saturation of the hyperpolarizability of oligothiophenes, Phys. Rev. Lett. 1990, 65, 2141-2144.
    16 WangB. , WasielewskiM. R. Design and Synthesis of Metal Ion-Recognition-Induced Conjugated Polymers: An Approach to Metal Ion Sensory Materials. J. Am. Chem. Soc., 1997, 119: 12-21
    17 Fan L. J. , Zhang Y. , JonesW. E. Design and Synthesis of Fluorescence "Turn-on" Chemosensors Based on Photoinduced Electron Transfer in Conjugated Polymers. Macromolecules, 2005, 38: 2844-2849
    18 Zhou Q. , Swager T. M. Fluorescent Chemosensors Based on Energy Migration in Conjugated Polymers: The Molecular Wire Approach to Increased Sensitivity. J. Am. Chem. Soc., 1995, 117: 12593-12602
    19 Tan C. Y. , PintoM. R. , Schanze K. S. Photophysics, aggregation and amplified quenching of a water-soluble poly(phenylene ethynylene). Chem. Commun., 2002: 446—447
    20 Wang, B.; Wasielewski, M. R. J. Am. Chem. Soc. 1997, 119, 12.
    21 Kim J., McQuade T. D., McHugh S. K. et al., Ion-Specific Aggregation in Conjugated Polymers: Highly Sensitive andSelective Fluorescent Ion Chemosensors, Angew. Chem. Int. Ed., 2000, 39, 3868-3872
    22 He F., Tang Y., Wang S., et al., Fluorescent Amplifying Recognition for DNA G-Quadruplex Folding with a Cationic Conjugated Polymer: A Platform for Homogeneous Potassium Detection, J. Am. Chem. Soc., 2005, 127, 12343-123469
    23 张彦,梅涛,孔德义等.爆炸物探测技术的研究概况及趋势[A].中国电子学会第八届青年学术年会 [C], 合肥:2002
    24 Yang J. S., Swager T. M., Fluorescent Porous Polymer Films as TNT Chemosensors: Electronic and Structural Effects, J. Am. Chem. Soc., 1998, 120, 11864-11873.
    25 Yang J. S., Swager T. M., Porous Shape Persistent Fluorescent Polymer Films: An Approach to TNT Sensory Materials, J. Am. Chem. Soc. 1998, 120, 5321-5322.
    26 Cumming C. J., Aker C., Fisher M., et al., IEEE Transactions on Geoscience and Remote Sensing, 2001, 39, 1119-1128.
    27 La Grone M., Cumming C., Fisher M., et al., Detection and Remediation Technologies for Mines and Minelike Targets V, P r o c e e d i n g s o f t he S PI E , 2 0 0 0 , 4 0 3 8 , 5 5 3 - 5 6 2 .
    28 Whitten, D.; Jones, R.; Bergstedt, T.; McBranch, D.; Chen, L.; Heeger, P. In Optical Sensors and Switches; Ramamurthy, V., Schanze, K. S., Eds.; Marcel Dekker: New York, 2001; p 189
    29 Song, X.; Wang, H.-l.; Shi, J.; Park, J.-W.; Swanson, B. I. Conjugated Polymers as Efficient Fluorescence Quenchers and Their Applications for Bioassays , Chem.Mater. 2002, 14, 2342-2347.
    30 Li, C.; Numata, M.; Takeuchi, M.; Shinkai, S. A Sensitive Colorimetric and Fluorescent Probe Based on a Polythiophene Derivative for the Detection of ATP, Angew. Chem., Int.Ed. 2005, 44, 6371-6374.
    31 DiCesare, N.; Pinto, M. R.; Schanze, K. S.; Lakowicz, J. R.,Saccharide Detection Based on the Amplified FluorescenceQuenching of a Water-Soluble Poly(phenylene ethynylene) by a Boronic Acid Functionalized Benzyl Viologen Derivative Langmuir, 2002, 18, 7785-7787.
    32 He, F.; Tang, Y.; Yu, M.; Wang, S.; Li, Y.; Zhu, D. Fluorescence-Amplifying Detection of Hydrogen Peroxide with Cationic Conjugated Polymers, and Its Application to Glucose S e n s i n g , A d V . F u n c t . M a t e r . 2 0 0 6 , 1 6 , 9 1 .
    33 Rininsland, F.; Xia, W.; Wittenburg, S.; Shi, X.; Stankewicz, C.;Achyuthan, K.; McBranch, D.; Whitten, D. Proc. Natl. Acad. Sci.U.S.A. 2004, 101, 15295.
    34 Kumaraswamy, S.; Bergstedt, T.; Shi, X.; Rininsland, F.; Kushon,S.; Xia, W.; Ley, K.; Achyuthan, K.; McBranch, D.; Whitten, D.Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 7511.
    35 Zhang, Tao; Fan, Hongliang; Zhou, Jianguang; Liu, Guoliang; Feng, Guodong; Jin, Qinhan. Fluorescent Conjugated Polymer PPESO3 Novel Synthetic Route and the Application for Sensing Protease Activities, Macromolecules, 2006, 39, 7839-7843.
    36 Gaylord, B. S.; Heeger, A. J.; Bazan, G. C. Proc. Natl. Acad. Sci.U.S.A. 2002, 99, 10954.
    37 Baker, E.S.; Hong, J. W.; Gaylord, B. S.; Bazan, G. C.; Bowers, M. T. J.For a detailed discussion of PNA-DNA complexes that is specifically related to sensory systems employing polymer , J.Am.Chem. Soc.. 2006, 128, 8484.
    38 Gaylord, B. S.; Heeger, A. J.; Bazan, G. C. DNA Hybridization Detection with Water-Soluble Conjugated Polymers and Chromophore-Labeled Single-Stranded DNA,J. Am. Chem. Soc. 2003,125, 896.
    39 Liu B., Bazan G. C., Interpolyelectrolyte Complexes of Conjugated Copolymers and DNA: Platforms for Multicolor Biosensors, J. Am. Chem. Soc., 2004, 126, 1942-1943.
    40 Hong J. W., Hemme W. L., Keller G. E., et al., Conjugated Polymer/DNA Interpolyelectrolyte Complexes for Accurate DNA Concentration Determination, Adv. Mater. 2006, 18, 878-882.
    41 Kushon S. A., Ley K. D., Bradford K., et al., Detection of DNA Hybridization via Fluorescent Polymer Superquenching, Langmuir, 2002, 18, 7245-7249.
    42 Wang S., Bazan G. C., Optically amplified RNA-protein detection methods using light-harvesting conjugated polymers, Adv. Mater. 2003, 15, 1425-1428.
    43 Liu B., Baudrey S., Jaeger,L., et al., Characterization of TectoRNA Assembly with Cationic Conjugated Polymers, J. Am. Chem. Soc. , 2004, 126, 4076-4077.
    44 Yusa S I , Karachi M ,Morishima Y. Fluorescence studies of the elf-organization of a cholesteral bearing poly-methacrylate in nehexane solution . J Polym Sci (A) ,1999 ,37 :47258.
    45 Winnik F M. Phase transition of aqueous poly-(N-iso-propylacrylamide) solution :a study by non-radiative energy transfer. olymer,1990 ,31 :2125-2134.
    46 Li FM ,Chen S J ,Li Z C ,et al. Vinyl monomers bearingchromophore moieties and their polymers. I initiation and photochemical behavior of Nacryloyl-N′- phenylpiper-azines and their polymers. J Polym Sci (A),1996 ,34: 1881-1888.
    47 Mendelsohn A S , Torkelson J M ,Monia O D. Fluorescence nonradiative energy transfer in bulk polymer and miscible and phase-separated polymer blends :a quantitative analysis including correlation effects. J Polym Sci (B) ,1994 ,32 :2667-2681.
    48 Fomine S , Pineda A ,Ogawa T , et al. Novel polymers containing fluorescein moieties. Polymer, 1995 , 27 (7) :712-728.
    49 Lee S A ,Yamashita T ,Horie K. Photoconductivity of a polyimide with an alicyclic diamine :charge carrier hoto generation in themixed layer packing arrangement . J.Polym Sci (B) ,1998 ,36 :1433-1442.
    50 Parker ID, J 1A pp l1 P hy s1, 1994, 75, 1656
    51 王运浩,江用文,成浩等.食品农药残留与分析控制技术展望,现代科学仪器,2003(1):8-12
    52 王玉秋,钱茜。浅谈农药污染及防治,山东环境,1999,89(2)
    53 金军,赵国栋,崔云等, 高效液相色谱/大气压电离质谱(HPLC/APIMS)在农药残留分析中的应用,化学通报,1999,(6):25
    54 黄德智,岳永德,汤锋。农药残留分析的研究进展,安徽农业科学,2002,30(4):523-52
    55 王爽,食品中农药残留分析方法的研究进展,贵州农业科学,2007,35(2):135-139
    56 KuashiKN , HnadaSK , Hnada5K.ChromatogrA , 1997 ,46(3~4):209
    57 朱梦栩,王勇. 大口径毛细管气相色谱柱测定茶叶中三氯杀螨醇的残留量,色谱,2000,18(l):64-66
    58 LinoCM , SilveiarMNID. ChormatogrA[J]. , 1997 ,769(2):275-283
    59 WangJH,QinagX,KuiJ.ChromatogrA.,1998,818(l):138-143
    60 FontJ,MarsalA.ChromatogrA.,1998,811(l~2):256-260
    61 CorreiaM,Delarue 一 MatosC,Alves.. Chromatographia,2000,889(l~2):59~67
    62 张莹,黄克强,李拥军. 气相色谱法测定茶叶中多种有机磷农药残留量,色谱.,2001,19(3):273~275
    63 NomrnaKNT , PnatonSHW. ChromatogrA. , 2001 ,907(l-2):247~255
    64 KirstensonEM,HvaerkateEGJ,SlooteCJ,etal.ChromatogrA,2001,917(1~2):277~286
    65 昊烈钧.气相色谱检测方法..北京:化学工业出版社,2000.17,93,25,23,49
    66 张莘民,纪云琴. GC/PID 分析有机污染物,中国环境监测,1997,13(6):53-55
    67 OlsonCW, AnalytiealAPPlieationNote,05111197,1993
    68 SunK,etal..ChromatogrA,2000,872:141
    69 SunK,etal.ChromatogrA,2000,872:179
    70 Paul M.Thomas , J.Environ.Sci.Health . Determination of nonsteroidal anti-inflammatory drugs caffeine , and triclosan in wastewater by gas chromatography,Mass Spectrometry[,2004, A39(8),1969~1978
    71 Chao Yan. Ctradient Elution in Capillary Eleactrochromatography . Anal Chem,1996 ,680 (2) :635 - 644.
    72 倪永年,邱萍. 电化学分析在有机农药残留量分析中的应用,分析测试学报.2003,22(2):103~106
    73 Pedorrm,Galve,zrRodriugrZe,etal.. Determination of the herbicide desmetryne in organised media by adsorptive stripping voltammetry,Talanta,2001,53(5):991~1000
    74 Sastyrea.IndinaJEnvironProt,1989,9(11):819-827
    75 Bourqurecl,Doguyamm,Gauterauzm. Int Environ Anal Chem.,1989,37(3):187-197
    76 Gadeem,Limajlcf,Deleure 一 Matose,Electrochemical oxidation of propanil and related N-substituted amides, Anal Chim Acta,2001,434(1):35-41
    77 Guiberteua eabnaillasa,GalenaodiZat,Mordaieznm,Resolution by polarographic techniques of atrazine–simazine and terbutryn–prometryn binary mixtures by using PLS calibration and artificial neural networks Analyst.,2000,125(5):909~914
    78 杨曼君.农药残留的免疫方法.农药科学与管理,1996 ,60 (4) :20-22
    79 Ngeh Ngwainbi J ,Foley D H ,Kuan S S. Parathion antibodies on piezoelec-tric crystals .J Am Chem Soc ,1995 ,108 :5 444 - 5 447.
    80 陈国珍,黄贤智。荧光分析法(第二版),科学出版社,1990。
    81 W . Bilger .U.Scheriber and O.L.Lange , Chlorophyll fluorescence as an indicator of heat induced limitation of photosynthesis. In Plant Response to Stress ,Spriger Verglag, Berlin, 1988:391-399
    82 夏锦尧。实用荧光分析法,中国人民公安大学出版社,1992:3-4
    83 刘蕊,王玉田。农药残留物浓度的光纤荧光测量系统的研究,燕山大学硕士生学位论文。
    84 周泽义,盖良京。中国食品中农药残留污染状况.资源生态环境网络研究动态,2001 , 12(1):24-28
    85 曲红云,张军民。当前国际上先进的农药残留分析技术.黑龙江农业科学,2000 ,(5):37-39
    86 夏祖学, 刘长军*, 阎丽萍, 杨晓庆. 微波化学的应用研究进展, 化学研究与应用, 2004, 16(4):441~444
    87 牛中奇,阎静,邵旺田.电磁波的生物效应,技术论坛,2001,7:8-12
    88 李缉熙,牛中奇.生物电磁学概论[M],西安,西安电子科技大学出版社,1990.
    89 金钦汉,戴树珊,黄卡玛.微波化学[M].北京,科学出版社,1999.
    90 Liu C P,Xu Y S,Hua Y X.Chin J Met Sci Technol,1990,6: 121
    91 华一新.第三届全国青年冶金学术会议暨国家自然科学基金委员会冶金学科第二届学术研讨会论文集,昆明理工大学,昆明,1994
    92 SWAGER T M. The molecular wire approach to sensory signal amplification. Accts. Chem Res,1998, 31:201-207
    93 FISHER M, CUMMING C, FOX M, et al. A man-portable chemical sniffer utilizing novel fluorescent polymers fordetection of ultra-trace concentrations of explosives emanating from landmines[A]. The 4th Int Symp on Technology and the Mine Problem[C]. Monterey, USA,2000,3
    94 Jye-Shane Yang and Timothy M. Swager*,et al. Fluorescent Porous Polymer Films as TNT Chemosensors: Electronicand Structural Effects. J. Am. Chem. Soc. 1998, 120, 11864-11873
    95 V.E. Williams and T.M. Swager*, et al.Iptycene-Containing Poly(aryleneethynylene)s. Macromolecules 2000, 33, 4069- 4073
    96 Christoph Weder and Mark S. Wrighton*,et al. Efficient Solid-State Photoluminescence in New Poly(2,5-dialkoxy-p-phenyleneethynylene)s. Macromolecules 1996, 29, 5157- 5165
    97 Timothy M. Swager,? Caroline J. Gil, and Mark S. Wrighton*,et al. Fluorescence Studies of Poly@-phenyleneethyny1ene)s: The Effect of Anthracene Substitution J. Phys. Chem. 1995, 99, 4886-4893
    98 Tao Zhang, Hongliang Fan, Jianguang Zhou,et al. Fluorescent Conjugated Polymer PPESO3 : A Novel Synthetic Route and the Application for Sensing Protease Activities. Macromolecules 2006, 39, 7839 -7843
    99 Yang, J.-S.; Swager, T. M., Fluorescent Porous Polymer Films as TNT Chemosensors: Electronic and Structural Effects, J. Am. Chem. Soc. 1998, 120, 11864-11873.
    100 Huang, W. Y.; Matsuoka, S.; Kwei, T. K.; Okamoto, Y., Aggre -gation and Gelation of Fully Conjugated Rigid-Rod Polymers. Poly(2,5-dialkyl-1,4-phenyleneethynylene)s, Macromolecules, 2001, 34, 7166-7171.
    101 Chen, L.; Xu, S.; McBranch, D.; Whitten, D., Tuning the Properties of Conjugated Polyelectrolytes through SurfactantComplexation, J. Am. Chem. Soc.;; 2000; 122(38); 9302-9303.
    102 Thünemann, A. F., Nanostructured Dihexadecyldimethyl ammonium-Poly(1,4-phenylene-ethinylene-carboxylate): An Ionic Complex with Blue Electroluminescence, Adv. Mater.,1999, 11, 127-130.
    103 Thünemann, A. F.; Ruppelt, D., Electroluminescent Polyelectrolyte-Surfactant Complexes Langmuir 2001, 17, 5098-5102.
    104 Lavigne J. J., Broughton D. L., et al., "Surfactochromic" Conjugated Polymers: Surfactant Effects on Sugar-Substituted PPEs, Macromolecules, 2003, 36(20), 7409-7412.

© 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