CN106977700B - 检测芳香胺水溶液的荧光共轭高分子传感体系、制备方法及应用 - Google Patents

检测芳香胺水溶液的荧光共轭高分子传感体系、制备方法及应用 Download PDF

Info

Publication number
CN106977700B
CN106977700B CN201710204310.9A CN201710204310A CN106977700B CN 106977700 B CN106977700 B CN 106977700B CN 201710204310 A CN201710204310 A CN 201710204310A CN 106977700 B CN106977700 B CN 106977700B
Authority
CN
China
Prior art keywords
fluorescence
aqueous solution
amine aqueous
conjugated
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710204310.9A
Other languages
English (en)
Other versions
CN106977700A (zh
Inventor
范丽娟
赵甲
赵一甲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou University
Original Assignee
Suzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suzhou University filed Critical Suzhou University
Priority to CN201710204310.9A priority Critical patent/CN106977700B/zh
Publication of CN106977700A publication Critical patent/CN106977700A/zh
Application granted granted Critical
Publication of CN106977700B publication Critical patent/CN106977700B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6402—Atomic fluorescence; Laser induced fluorescence
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/124—Copolymers alternating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/141—Side-chains having aliphatic units
    • C08G2261/1412—Saturated aliphatic units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1426—Side-chains containing oxygen containing carboxy groups (COOH) and/or -C(=O)O-moieties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/18—Definition of the polymer structure conjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
    • C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3328—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms alkyne-based
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/413—Heck reactions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/52—Luminescence
    • C08G2261/522—Luminescence fluorescent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/94—Applications in sensors, e.g. biosensors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1408—Carbocyclic compounds
    • C09K2211/1416—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1408—Carbocyclic compounds
    • C09K2211/1425—Non-condensed systems

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Biochemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)

Abstract

本发明公开了一种检测芳香胺水溶液的荧光共轭高分子传感体系、制备方法及应用。通过Sonogashira偶联反应合成了一种主链结构为芴基和对苯乙炔基共聚，且在侧链上具有两个悬垂的羧基和长烷基链的荧光共轭高分子，用于对芳香胺水溶液的快速响应和检测。本发明提供的高分子传感体系对其具有很高的选择性淬灭响应，这种选择性淬灭响应来源于聚合物主链结构上的芳香环与对苯二胺的π‑π作用以及羧基与氨基的协同作用。在荧光传感检测中，聚合物溶液与待检测有机胺水溶液等体积均匀混合，荧光响应即刻发生，检测过程迅速而高效。

Description

检测芳香胺水溶液的荧光共轭高分子传感体系、制备方法及 应用
技术领域
本发明涉及一种对芳香胺水溶液选择性响应的荧光共轭高分子及其制备方法，属于荧光传感材料技术领域。
背景技术
目前，人类工业活动中排放的含芳香胺及其衍生物的废水，比如对苯二胺（PPD）这一类在人造染发剂和凯夫拉纤维作前躯体的芳香胺，对于生态环境和人体健康的危害已经引起了人们的高度重视，必须严格加以监管。当前对人类生存环境中芳香胺的检测方法主要包括气相色谱分析，高效液相色谱法，气相-质谱联用分析法，但是这些常用的方法具有操作复杂、耗时长、待测样品预处理过程复杂等缺点。为了实现快速检测芳香胺的目的，近年来出现了毛细管电泳法，紫外光谱分析以及电化学法等。
荧光化学传感器由于具有高的灵敏度，低的检测限和操作简单的特点，成为了一个研究热点。然而，对于有机胺水溶液样品的荧光传感仍具有挑战性。在本发明作出之前，报道了一种应用于有机太阳能电池电极材料的聚合物（参见文献：Hui Jiang.; PrasadTaranekar.; John R. Reynolds.; Kirk S. Schanze. Angew. Chem. Int. Ed. 2009,48, 4313 – 4314），但具有相似结构的聚合物用于荧光传感检测还未见报道。
发明内容
本发明针对现有在芳香胺水溶液检测技术方面存在的不足，提供一种操作简便，效果明显的用于检测芳香胺水溶液的荧光共轭高分子传感体系、制备方法及其应用。
实现本发明目的的技术方案是提供一种检测芳香胺水溶液的荧光共轭高分子传感体系，它为侧链上具有两个悬垂的羧基和长烷基链的共轭高分子的DMF溶液，所述共轭高分子的结构式为：
。
所述溶液的浓度分别为5×10-6 M和5×10-5 M。
本发明技术方案中，制备如上所述的检测芳香胺水溶液的荧光共轭高分子传感体系的方法包括以下步骤：
（1）在无水无氧的条件下，按摩尔计，将一份2,5–二溴-对苯氧基二乙酸十二酯，一份9,9-二辛基-2,7-二炔芴，0.04份的碘化亚铜，0.07份三苯基磷二氯化钯加入至容器中，再加入30份经除水纯化处理的二异丙胺，247份经除水纯化处理的四氢呋喃；将混合物加热至85～95℃，搅拌，反应结束后，自然冷却至室温，抽滤，沉淀重结晶，得到浅黄色片状固体，记作PFPE-COOR：1H NMR (400 MHz, CDCl3, δ ppm): 7.5-7.7(m, 4H), 7.0-7.1(m, 4H),4.6-4.8(m, 4H), 4.15-4.30(m, 4H), 1.95-2.05(br, 4H), 0.5-1.75(m, 76H).。结构式为：
；
（2）按摩尔计，将一份PFPE-COOR，700份二氧六环和22.4份1M的四丁基氢氧化铵甲醇溶液加入到容器中，室温下搅拌后加入33份0.55M的高氯酸钠的水溶液继续搅拌，再将混合物沉淀重结晶，抽滤；将所得固体干燥得到黄色块状固体记作PFPE-COOH：1H NMR (400MHz, DMSO): 7.0-8.1(m, 8H),4.5-5.0(m, 4H), 1.95-2.05(br, 4H),0.4-1.5(m, 30H),13.0-13.2(s, 2H).，结构式为：
；
（3）将聚合物PFPE-COOH溶解在DMF溶剂中，得到共轭高分子的DMF溶液，即为荧光传感体系。
传感体系的浓度为5×10-6 M或5×10-5 M的
本发明技术方案还包括所述检测芳香胺水溶液的荧光共轭高分子传感体系的应用，将待检测物水溶液与共轭高分子的DMF溶液（聚合物PFPE-COOH的DMF溶液）按体积比1：1混合，用荧光分光光度计记录荧光光谱。
本发明提供了一种含芴构筑单元的荧光共轭高分子传感体系，该体系具有较强的荧光发射，最大发射波长在448 nm；该体系与苯胺，对苯二胺水溶液等体积混合后，荧光被显著淬灭，与二乙胺，三乙胺等脂肪胺水溶液等体积混合后，荧光轻微增强。
本发明提供的荧光共轭高分子传感体系PFPE-COOH的DMF溶液，对芳香胺的选择性响应，具体为：
对苯二胺水溶液能够将浓度为5×10-6 M的荧光传感体系的荧光强度淬灭85 %，能够将浓度为5×10-5 M的荧光传感体系的荧光强度淬灭95 %。
苯胺水溶液能够将浓度为5×10-6 M的荧光传感体系的荧光强度淬灭40 %，能够将浓度为5×10-5 M的荧光传感体系的荧光强度淬灭15 %。
与现有技术相比，本发明的有益效果在于：
1、本发明提供的共轭高分子的侧链上具有两个悬垂的羧基和长烷基链，利用羧基与氨基之间的酸碱相互作用，以及芳香环之间的π-π堆积作用，使聚合物荧光发射选择性响应，达到高灵敏度检测的目的。
2、本发明提供的传感体系所使用的聚合物合成简便，成本低廉，具有较高的荧光量子产率，适合大规模生产使用。
3、与现有芳香胺检测技术相比，本发明所使用的荧光共轭高分子传感体系对苯胺、对苯二胺等芳香胺具有较高的选择性淬灭响应，且淬灭快速明显，易于肉眼观察；同时，还具有待测样品预处理过程简便的特点。
附图说明
图1是本发明实施例提供的荧光共轭高分子传感体系中所使用的聚合物的合成路线图；
图2是聚合物PFPE-COOH紫外吸收和荧光发射谱图；
图3是5×10-5 M的荧光共轭高分子传感体系等体积加入去离子水和有机胺水溶液后的荧光发射谱图；
图4是5×10-6 M的荧光共轭高分子传感体系等体积加入去离子水和有机胺水溶液后的荧光发射谱图；
图5是5×10-6 M的荧光共轭高分子传感体系等体积加入去离子水和不同浓度的苯胺水溶液后的荧光发射谱图；
图6是5×10-6 M的荧光共轭高分子传感体系等体积加入去离子水和不同浓度的对苯二胺水溶液后的荧光发射谱图；
图7是5×10-6 M的荧光共轭高分子传感体系等体积加入去离子水和不同浓度的二乙胺水溶液后的荧光发射谱图；
图8是两种浓度的荧光共轭高分子传感体系与有机胺水溶液选择性响应柱状图。
具体实施方式
下面结合附图与实施例对本发明技术方案作进一步的阐述。
实施例1
本实施例提供一种荧光共轭高分子传感体系所使用的聚合物PFPE-COOH的合成，其合成路线参见附图1，具体步骤如下：
（1）将1摩尔2,5–二溴-对苯氧基二乙酸十二酯（记作M1），1摩尔9,9-二辛基-2,7-二炔芴（记作M2），0.04摩尔的碘化亚铜，0.07摩尔三苯基磷二氯化钯加入至100ml规格双颈烧瓶，双颈烧瓶用氩气通气除氧三次以上，每次五分钟。之后在氩气保护下快速加入30摩尔经除水纯化的二异丙胺，247摩尔经除水纯化的四氢呋喃。最后混合物使用油浴加热至90摄氏度以上，搅拌回流48小时，反应过程中使用氩气保护。反应结束后，关闭油浴锅，冷却至室温，抽滤，滤液逐滴滴入大量甲醇溶剂中，所得到的沉淀物用氯仿溶解，再次用甲醇沉淀，最终得到浅黄色片状固体，记作PFPE-COOR。1H NMR (400 MHz, CDCl3, δ ppm): 7.5-7.7(m,4H), 7.0-7.1(m, 4H), 4.6-4.8(m, 4H), 4.15-4.30(m, 4H), 1.95-2.05(br, 4H),0.5-1.75(m, 76H)。
（2）将1摩尔PFPE-COOR，700摩尔二氧六环和22.4摩尔四丁基氢氧化铵（1 M,甲醇溶液）加入至100ml规格的双颈烧瓶中，室温下搅拌24小时，之后加入33摩尔高氯酸钠的水溶液（0.55 M）继续搅拌1小时，然后将混合物加入至大量冰冻的丙酮中静置过夜，离心后将所得固体真空干燥得到黄色块状固体，记作PFPE-COOH。1H NMR (400 MHz, DMSO): 7.0-8.1(m, 8H),4.5-5.0(m, 4H), 1.95-2.05(br, 4H),0.4-1.5(m, 30H),13.0-13.2(s,2H)。
聚合物PFPE-COOH光物理表征，紫外吸收谱图和荧光发射谱图如附图2所示。
实施例2
本实施例提供一种对芳香胺水溶液有响应的荧光共轭高分子传感体系，其响应性测试过程如下：
1、制备荧光共轭高分子传感体系
使用AR级DMF试剂和实施例1制备的聚合物PFPE-COOH，配置浓度为5×10-6 M（或5×10-5 M）的聚合物PFPE-COOH溶液。
2、配置不同浓度的待测物水溶液
使用去离子水配置0.1 M的苯胺、对苯二胺、氨水、乙二胺、四甲基乙二胺、乙胺、三乙胺和二乙胺水溶液。
配置不同浓度的苯胺、对苯二胺和二乙胺水溶液。
3、荧光探针对各类有机胺的响应性实验
选取0.1 M的苯胺、对苯二胺、氨水、乙二胺、四甲基乙二胺、乙胺、三乙胺和二乙胺水溶液各2 ml，分别置于10 ml规格离心管内，然后向离心管内分别加入等体积5×10-6 M（或5×10-5 M）的聚合物PFPE-COOH溶液各2 ml，混合均匀后取适量体积混合物至石英比色皿，随后立即使用荧光分光光度计，激发波长为365nm，记录荧光发射光谱。结果参见附图3和 4。
从图3可看出，脂肪胺如乙二胺、三乙胺等水溶液轻微增强5×10-5 M的聚合物溶液的荧光，而芳香胺如苯胺、对苯二胺水溶液明显淬灭5×10-5 M的聚合物溶液的荧光，苯胺水溶液对聚合物溶液的荧光淬灭程度达到15%，对苯二胺水溶液对聚合物溶液的荧光淬灭程度达到95%。
从图4可看出脂肪胺如乙二胺、三乙胺等水溶液轻微增强5×10-6 M的聚合物溶液的荧光，而芳香胺如苯胺、对苯二胺水溶液明显淬灭5×10-6 M的聚合物溶液的荧光，苯胺水溶液对聚合物溶液的荧光淬灭程度达到40%，对苯二胺水溶液对聚合物溶液的荧光淬灭程度达到85%。
4、荧光传感体系对不同浓度的苯胺、对苯二胺和二乙胺水溶液的响应性实验
(1)选取不同浓度的苯胺水溶液各2ml分别置于10ml规格离心管内，然后向离心管内分别加入5×10-6 M的聚合物PFPE-COOH溶液各2 ml，混合均匀后取适量体积混合物至石英比色皿，随后立即使用荧光分光光度计，激发波长为365nm，记录荧光发射光谱。对苯二胺和二乙胺对比实验步骤与上述操作过程类似。结果参见附图5、 6和 7。
从图5可看出苯胺水溶液随着浓度的增加，对5×10-6 M的聚合物溶液荧光淬灭程度逐渐增加。
从图6可看出随着对苯二胺水溶液浓度的增加对5×10-6 M的聚合物溶液荧光淬灭程度同样逐渐增加。
从图7可看出，随着二乙胺水溶液浓度的增加，对5×10-6 M的聚合物溶液的荧光增强程度没有发生明显变化。
参见附图8，它是本发明提供的两种浓度（5×10-6 M、5×10-5 M）的荧光共轭高分子传感体系与有机胺水溶液选择性响应柱状图。

Claims (5)

1.一种检测芳香胺水溶液的荧光共轭高分子传感体系，所述芳香胺为对苯二胺或苯胺，其特征在于：它为侧链上具有两个悬垂的羧基和长烷基链的共轭高分子的DMF溶液，所述共轭高分子的结构式为：
。
2.根据权利要求1所述的一种检测芳香胺水溶液的荧光共轭高分子传感体系，其特征在于：所述共轭高分子的DMF溶液的浓度为5×10-6 M或5×10-5 M。
3.一种如权利要求1所述的检测芳香胺水溶液的荧光共轭高分子传感体系的制备方法，其特征在于包括以下步骤：
（1）在无水无氧的条件下，按摩尔计，将一份2,5–二溴-对苯氧基二乙酸十二酯，一份9,9-二辛基-2,7-二炔芴，0.04份的碘化亚铜，0.07份三苯基磷二氯化钯加入至容器中，再加入30份经除水纯化处理的二异丙胺，247份经除水纯化处理的四氢呋喃；将混合物加热至85～95℃，搅拌，反应结束后，自然冷却至室温，抽滤，沉淀重结晶，得到浅黄色片状固体；
（2）按摩尔计，将一份步骤（1）制得的浅黄色片状固体，700份二氧六环和22.4份浓度为1M的四丁基氢氧化铵甲醇溶液加入到容器中，室温下搅拌后加入33份浓度为0.55M的高氯酸钠的水溶液继续搅拌，再将混合物沉淀重结晶，抽滤，干燥，得到黄色块状固体；
（3）将步骤（2）制得的黄色块状固体溶解在DMF溶剂中，得到共轭高分子的DMF溶液，即为荧光传感体系。
4.根据权利要求3所述的一种检测芳香胺水溶液的荧光共轭高分子传感体系的制备方法，其特征在于：所述荧光传感体系的浓度为5×10-6 M或5×10-5 M。
5.按权利要求1所述的一种检测芳香胺水溶液的荧光共轭高分子传感体系的应用，其特征在于：将待检测物水溶液与共轭高分子的DMF溶液按体积比1：1混合，用荧光分光光度计记录荧光光谱。
CN201710204310.9A 2017-03-30 2017-03-30 检测芳香胺水溶液的荧光共轭高分子传感体系、制备方法及应用 Active CN106977700B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710204310.9A CN106977700B (zh) 2017-03-30 2017-03-30 检测芳香胺水溶液的荧光共轭高分子传感体系、制备方法及应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710204310.9A CN106977700B (zh) 2017-03-30 2017-03-30 检测芳香胺水溶液的荧光共轭高分子传感体系、制备方法及应用

Publications (2)

Publication Number Publication Date
CN106977700A CN106977700A (zh) 2017-07-25
CN106977700B true CN106977700B (zh) 2019-04-12

Family

ID=59338611

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710204310.9A Active CN106977700B (zh) 2017-03-30 2017-03-30 检测芳香胺水溶液的荧光共轭高分子传感体系、制备方法及应用

Country Status (1)

Country Link
CN (1) CN106977700B (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110003449B (zh) * 2019-03-27 2021-09-28 苏州大学 含吡咯并吡咯烷酮构筑单元的荧光共轭高分子、制备方法及应用
CN112414978B (zh) * 2020-03-18 2021-11-09 同济大学 一种多孔共轭聚合物及其在超低检测限选择性检测芳香胺中的应用
CN113024777B (zh) * 2021-02-22 2022-05-17 苏州大学 一种两亲性荧光共轭高分子、制备方法及应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101899021A (zh) * 2010-07-16 2010-12-01 中国科学院上海微系统与信息技术研究所 一类荧光化合物及其在检测痕量甲基苯丙胺中的应用

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2868842B1 (fr) * 2004-04-09 2006-05-26 Commissariat Energie Atomique Capteurs chimiques comprenant des polymeres conjugues fluorescents comme materiaux sensibles, et leur utilisation pour la detection ou le dosage de composes nitres

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101899021A (zh) * 2010-07-16 2010-12-01 中国科学院上海微系统与信息技术研究所 一类荧光化合物及其在检测痕量甲基苯丙胺中的应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Fluorescence Sensing of Amine Vapors Using a Cationic Conjugated Polymer Combined with Various Anions;Sebastien Rochat et al.;《Angew. Chem. Int. Ed.》;20141231;第53卷;9792-9796 *

Also Published As

Publication number Publication date
CN106977700A (zh) 2017-07-25

Similar Documents

Publication Publication Date Title
CN111423423B (zh) 一种比率型荧光探针在检测过氧亚硝基阴离子中的应用
CN106977700B (zh) 检测芳香胺水溶液的荧光共轭高分子传感体系、制备方法及应用
Fan et al. A fluorescent probe for the dual-channel detection of Hg2+/Ag+ and its Hg2+-based complex for detection of mercapto biomolecules with a tunable measuring range
CN111253935B (zh) 一种双通道检测极性和粘度的双光子荧光探针及其制备方法和用途
Sun et al. A turn-on fluorescent probe for cyanide based on aggregation of terthienyl and its application for bioimaging
US20170059573A1 (en) Method of detecting peroxynitrite using a complex of a saccharide and an arylboronate-based fluorescent probe
CN105001862A (zh) 利用芦荟为碳源制备碳量子点及柠檬黄检测方法
CN113024463B (zh) 一种1,8-萘酰亚胺类硫化氢荧光分子探针的制备和应用
Liu et al. A novel pyrene-based fluorescent probe for Al3+ detection
CN109867611A (zh) 一种用于红酒和活体内硫化氢检测的水溶性双光子硫化氢荧光探针及其制备方法和应用
CN111892923B (zh) 一种基于二腈乙烯基的双光子荧光粘度探针及其制备方法和用途
CN102977131B (zh) 一种半菁蓝素硼酸分子荧光探针及其制备方法和应用
CN108276383A (zh) 一种识别碘离子的荧光探针及其制备方法和识别方法
Zhang et al. A super large Stokes shift ratiometric fluorescent probe for highly selective sensing of ClO− in bio-imaging and real water samples
Wang et al. A fast-responsive two-photon fluorescent probe for detecting palladium (0) with a large turn-on fluorescence signal
Chen et al. Eu-Doped MOF-based high-efficiency fluorescent sensor for detecting 2, 4-dinitrophenol and 2, 4, 6-trinitrophenol simultaneously
Yang et al. Dual–channel colorimetric fluorescent probe for determination of hydrazine and mercury ion
CN108516979B (zh) 一种基于萘酰亚胺-罗丹明的化合物及其应用
Zhang et al. Merocyanine-based turn-on fluorescent probe for the sensitive and selective determination of thiophenols via a pKa shift mechanism
Wang et al. A novel chromophore reaction-based pyrrolopyrrole aza-BODIPY fluorescent probe for H2S detection and its application in food spoilage
CN109320537A (zh) 一种用于面粉和活体内过氧苯甲酰检测的可溶性双光子荧光探针及其制备方法和应用
Hong et al. Simple Pyrene Derivatives as Fluorescence Sensors for TNT and RDX in Micelles.
CN113582985B (zh) 一种线粒体靶向的pH和粘度双通道检测荧光探针及其制备方法和用途
CN103435625A (zh) 红光发射罗丹明类离子荧光探针及其应用
CN103923636B (zh) 对cl-20有传感功能的荧光小分子探针及制备方法、使用方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant