CN109293651B - 一种水溶液中检测锌离子的比率荧光探针化合物及其检测方法 - Google Patents

一种水溶液中检测锌离子的比率荧光探针化合物及其检测方法 Download PDF

Info

Publication number
CN109293651B
CN109293651B CN201811377158.5A CN201811377158A CN109293651B CN 109293651 B CN109293651 B CN 109293651B CN 201811377158 A CN201811377158 A CN 201811377158A CN 109293651 B CN109293651 B CN 109293651B
Authority
CN
China
Prior art keywords
aqueous solution
fluorescent probe
probe compound
compound
fluorescence
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
CN201811377158.5A
Other languages
English (en)
Other versions
CN109293651A (zh
Inventor
尹静梅
贾颖萍
崔颖娜
李慎敏
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.)
Dalian University
Original Assignee
Dalian 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 Dalian University filed Critical Dalian University
Priority to CN201811377158.5A priority Critical patent/CN109293651B/zh
Publication of CN109293651A publication Critical patent/CN109293651A/zh
Application granted granted Critical
Publication of CN109293651B publication Critical patent/CN109293651B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • 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
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • 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
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • 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
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
    • 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
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6432—Quenching

Abstract

本发明公开了一种水溶液中检测锌离子的比率荧光探针化合物及其检测方法，属于荧光探针领域。该锌离子荧光探针化合物的化学分子式为C20H16N3O3Cl，是以2‑(2’‑羟苯基)苯并噁唑化合物为母体结构经过衍生化得到的。此化合物对锌离子选择性好、检测范围较宽、灵敏度高、抗其它金属离子干扰能力强，适用于生物化学和环境化学等领域水溶液中Zn2+的检测。

Description

一种水溶液中检测锌离子的比率荧光探针化合物及其检测 方法
技术领域
本发明属于荧光探针领域，尤其是涉及一种用于水溶液中锌离子(Zn2+)检测的荧光探针化合物及其检测方法。
背景技术
锌是一种重要的微量元素，是人体中第二富集的过渡金属元素，广泛地分布于人体的细胞和体液中，在生理功能调节以及细胞构建中扮演着重要的角色[1]。人体内锌缺乏可引发各种疾病，如免疫系统功能障碍、厌食症、生长迟缓、糖尿病、阿尔茨海默氏症等，但人体摄入过量的锌会产生中毒现象，环境中过多的Zn2+也会造成污染，影响植物的生长发育，因此高选择性的识别和检测Zn2+，对生物学、临床医学、环境化学和农学等领域具有重要的意义。目前检测Zn2+的主要方法有原子吸收光谱法、色谱分析法、比色法、电化学法和荧光光谱法等。其中，荧光光谱法因具有原位、实时、灵敏、无损和选择性好等特点而备受关注。
2-(2’-羟苯基)苯并唑类(HBX，X＝O，S，NH)化合物是一类典型的ESIPT化合物，具有高的荧光量子产率和较大的Stoke位移值，消除了背景荧光的干扰和吸收与发射光谱的重叠，因此在荧光探针领域引起了极大的兴趣[2]，作为Zn2+荧光探针已得到了广泛的研究，然而许多基于HBX的Zn2+荧光探针化合物水溶性较差，往往是在有机溶剂中进行Zn2+的检测[3,4]或者在有机溶剂和水的混合溶液体系中识别锌离子[5]，限制了在生物学和临床医学检验等方面的应用，因此发展一种能够在纯水体系中对锌离子具有选择性好、灵明度高和快速响应的荧光探针具有重要的意义。
[1]Berg J M,Shi Y G.The galvanization of biology:a growingappreciation for the roles of zinc[J].Science,1996,271:1081-1085.
[2]胡睿,郭旭东,杨国强.激发态分子内质子转移化合物的性能及作为荧光化学传感器的应用研究[J].影像科学与光化学,2013,31(5):335-348.
[3]Tian Y Q,Chen C Y,Yang C C,et al.2-(2’-hydroxyphenyl)benzoxazole-containing two-photon-absorbing chromophores as sensors for zinc andhydroxide ions[J].Chem.Mater.,2008,20(5):1977-1987.
[4]吴玉防,崔颖娜,李慎敏,等.基于羟苯基苯并咪唑的Zn2+比率荧光探针[J].无机化学学报,2012,28(5):910-914.
[5]Xu Y Q,Xiao L L,Sun S G,et al.Switchable and selective detectionof Zn2+or Cd2+in living cells based on 3’-O-substituted arrangement ofbenzoxazole-derived fluorescent probes[J].Chem.Commun.,2014,50:7514-7516.
发明内容
为弥补现有技术的不足，本发明提供了一种含羟苯基苯并噁唑和吡啶氯盐结构单元的水溶性Zn2+比率荧光探针化合物及其在水溶液中对Zn2+的比率荧光检测方法，该探针化合物对水溶液中Zn2+浓度的检测范围较宽，选择性和灵敏度高，重现性好，并且其它干扰离子对检测结果无明显影响。
本发明采用如下技术方案：一种水溶液中检测锌离子的比率荧光探针化合物，N-(4-2’-苯并噁唑-3-羟苯基)氨甲酰基甲基吡啶氯盐(C20H16N3O3Cl)，具有如式Ⅰ所示的结构：
Figure BDA0001871030020000021
本发明探针化合物检测Zn2+浓度的方法为：
准确配制1×10-6～1×10-4mol/L的探针化合物水溶液，并向该溶液中加入Zn2+水溶液标准样品，配制成含Zn2+浓度为1×10-6～1×10-2mol/L的标准样品并测定荧光光谱，荧光峰强度变化lg(I458/I423)与Zn2+浓度lgc的趋势线方程为：
lg(I458/I423)＝－0.383lgc－1.4484(R2＝0.9910)。
其中I458/I423为458nm处和423nm处荧光峰强度比值；
c为Zn2+摩尔浓度。
本发明探针化合物对Zn2+的工作浓度范围8×10-6～1×10-3mol/L，且Na+，K+，Mg2+，Ca2+，Ba2+，Mn2+，Fe2+，Co2+，Ni2+，Cd2+和Pb2+对Zn2+浓度的测定无明显干扰。
本发明的探针化合物是水溶液中Zn2+检测的比率荧光识别探针，从而消除了荧光增强型探针等受外界不稳定带来的仪器的系统误差、背景误差等，使其灵敏度提高。本发明的探针化合物具有良好的水溶性，实现了水溶液中对Zn2+的荧光检测。该化合物对Zn2+检测具有较高的选择性，检测范围较宽，为8×10-6～1×10-3mol/L，具有很好的灵敏度，能够检测到ppm数量级的Zn2+，抗其它金属离子干扰能力强，适用于生物化学和环境化学等领域中Zn2+的检测。
附图说明
图1是本发明实施例1中探针化合物的水溶液在加入不同金属离子后的荧光吸收光谱图；
图2是本发明实施例2中探针化合物的水溶液在加入不同浓度的Zn2+后的荧光吸收光谱图；
图3是本发明实施例2中探针化合物在水溶液中458nm处和423nm处荧光峰强度变化lg(I458/I423)与lgc关系的工作曲线；
图4是本发明实施例3中不同金属离子与Zn2+共存时对混合体系荧光强度的影响。
具体实施方式
下面通过具体实施例详述本发明，但不限制本发明的保护范围。如无特殊说明，本发明所采用的实验方法均为常规方法，所用实验器材、材料、试剂等均可从化学公司购买。
实施例1
向3mL探针化合物N-(4-2’-苯并噁唑-3-羟苯基)氨甲酰基甲基吡啶氯盐的水溶液(浓度为3×10-5mol/L)中分别加入30μL不同金属离子水溶液(浓度为9×10-2mol/L)，充分混合后在328nm激发波长下测定各溶液的荧光吸收光谱(如图1)。结果表明，探针化合物对Na+、K+、Mg2+、Ca2+、Ba2+、Cd2+、Pb2+、Mn2+的响应很弱，Co2+、Ni2+、Fe2+能够使探针化合物的荧光发射轻微猝灭，而只有Zn2+在458nm处荧光发射峰猝灭的同时，在423nm处出现了新峰，呈现出比率荧光的特征，因此，探针化合物具备了作为检测Zn2+比率荧光探针的基本条件。
实施例2
配制浓度分别为1×10-1、1×10-2、1×10-3mol/L的Zn2+水溶液。首先，向样品池中加入3mL探针化合物N-(4-2’-苯并噁唑-3-羟苯基)氨甲酰基甲基吡啶氯盐的水溶液(3×10- 5mol/L)，依次滴加浓度为1×10-3mol/L的Zn2+水溶液24、3、3μL，充分混匀后在328nm激发光激发下扫谱；然后向样品池中加入3mL探针化合物的水溶液(3×10-5mol/L)，依次滴加浓度为1×10-2mol/L的Zn2+水溶液3μL，充分混匀后在328nm激发光激发下扫谱，共滴加10次；最后，向样品池中加入3mL探针化合物的水溶液(3×10-5mol/L)，依次滴加浓度为1×10-1mol/L的Zn2+水溶液3μL，充分混匀后在328nm激发光激发下扫谱,共滴加10次(如图2)。随着Zn2+浓度的增加，荧光光谱上458nm处荧光峰强度逐渐降低，且在423nm处荧光峰强度逐渐增强。以458nm处和423nm处荧光峰强度变化lg(I458/I423)作为纵坐标，lgc(c为Zn2+摩尔浓度)为横坐标做工作曲线(如图3)，趋势线方程：lg(I458/I423)＝－0.383lgc－1.4484(R2＝0.9910)。
实施例3
本实施例考察探针化合物对Zn2+识别的选择性。向3mL探针化合物的水溶液(浓度为3×10-5mol/L)中加入浓度为9×10-2mol/L的Zn2+水溶液30μL，然后再分别加入30μL Na+、K+、Mg2+、Ca2+、Ba2+、Mn2+、Fe2+、Co2+、Ni2+、Cd2+或Pb2+的金属离子水溶液(浓度为9×10-2mol/L)，充分混合后在328nm激发光激发下扫谱，不同金属离子与Zn2+共存时对混合体系荧光强度的影响如图4。实验结果表明，探针化合物作为荧光探针用于测定水溶液中的Zn2+灵敏度高，其它水中的离子对其测定结果干扰较少，结果稳定，可靠。
以上所述，仅为本发明创造较佳的具体实施方式，但本发明创造的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明创造披露的技术范围内，根据本发明创造的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明创造的保护范围之内。

Claims (2)

1.一种水溶液中检测锌离子的比率荧光探针化合物，其特征在于，该化合物含羟苯基苯并噁唑和吡啶氯盐结构单元，该化合物的结构式Ⅰ如下：
Figure FDA0002382765440000011
2.权利要求1所述的Zn2+比率荧光探针化合物检测水溶液中Zn2+浓度的方法，其特征在于，具体步骤为：
(1)准确配制1×10-6～1×10-4mol/L Zn2+比率荧光探针化合物水溶液，并向该溶液中加入Zn2+水溶液标准样品，配制成含Zn2+浓度为1×10-6～1×10-2mol/L的标准样品，测定荧光光谱；
(2)以458nm处和423nm处荧光峰强度变化lg(I458/I423)作为纵坐标，以lgc为横坐标做工作曲线，其中c为Zn2+摩尔浓度；
荧光峰强度变化lg(I458/I423)与Zn2+浓度lgc的工作曲线为：lg(I458/I423)＝－0.383lgc－1.4484，其中，相关系数R2＝0.9910。
CN201811377158.5A 2018-11-19 2018-11-19 一种水溶液中检测锌离子的比率荧光探针化合物及其检测方法 Active CN109293651B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811377158.5A CN109293651B (zh) 2018-11-19 2018-11-19 一种水溶液中检测锌离子的比率荧光探针化合物及其检测方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811377158.5A CN109293651B (zh) 2018-11-19 2018-11-19 一种水溶液中检测锌离子的比率荧光探针化合物及其检测方法

Publications (2)

Publication Number Publication Date
CN109293651A CN109293651A (zh) 2019-02-01
CN109293651B true CN109293651B (zh) 2020-06-16

Family

ID=65143536

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811377158.5A Active CN109293651B (zh) 2018-11-19 2018-11-19 一种水溶液中检测锌离子的比率荧光探针化合物及其检测方法

Country Status (1)

Country Link
CN (1) CN109293651B (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110117282B (zh) * 2019-05-13 2020-07-10 五邑大学 一种锌离子荧光探针化合物及其制备方法与应用
CN111825629B (zh) * 2020-08-12 2022-10-21 江西理工大学 一种苯并噁唑类荧光探针及制备方法及应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102925136A (zh) * 2012-10-23 2013-02-13 大连大学 一种Zn2+比率荧光探针化合物和制备方法及应用

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102925136A (zh) * 2012-10-23 2013-02-13 大连大学 一种Zn2+比率荧光探针化合物和制备方法及应用

Also Published As

Publication number Publication date
CN109293651A (zh) 2019-02-01

Similar Documents

Publication Publication Date Title
CN111687408B (zh) 一种荧光铜纳米团簇、制备方法及其应用
Zhao et al. A facile intracellular fluorescent probe for detection of hydrazine and its application
CN106905538A (zh) 一种含锌金属有机框架材料及其制备方法和应用
CN109293651B (zh) 一种水溶液中检测锌离子的比率荧光探针化合物及其检测方法
Aziz et al. Design of a highly sensitive and selective bulk optode based on fluorescence enhancement of N, N′-bis-(1-hydroxyphenylimine) 2, 2′-pyridil Schiff base: Monitoring of zinc (II) ion in real samples and DFT calculation
CN108398409B (zh) 一种荧光比率检测次氯酸根的方法
CN105548174B (zh) 一种光开关型测定溶液pH的探针方法
CN107643271B (zh) 一种水杨酸-Mn掺杂ZnS量子点复合纳米粒子比率型荧光探针及其制备方法和应用
CN113896901A (zh) 一种卤化铅基金属有机框架材料及其制备与应用、氨气传感器、及智能传感器件
CN103497189B (zh) 1-羟基-3,4:9,10-苝四羧酸二酰亚胺、其合成方法及在氟含量测定中的应用
CN109283163B (zh) 基于钙-金属有机骨架材料作为荧光探针检测l-半胱氨酸的方法
CN113402470B (zh) 一种多通道可逆比色汞离子荧光探针、制备方法与应用
CN110655919B (zh) 一种铜离子荧光探针及其制备方法与应用
CN111662279B (zh) 一种萘取代咔唑-苯并噻唑基腙类化合物及其制备方法和用途
CN110698390B (zh) 一种识别亚硫酸氢根的荧光探针及其制备方法和检测方法
CN108169196B (zh) 一种快速检测环境中氟离子的方法
CN110186888B (zh) 一种选择性定量检测碘离子的方法及应用
CN109574921B (zh) 一种检测醋酸根离子的荧光探针及其制备方法和使用方法
Wang et al. Optical fiber sensor for berberine based on fluorescence quenching of 2-(4-diphenylyl)-6-phenylbenzoxazole
CN108485651B (zh) 二乙胺乙酸盐荧光小分子用于定量检测多巴胺和Fe3+离子的方法
CN106957267B (zh) 一种新型检测钯的可逆比色比率菲并咪唑类荧光分子探针
CN106596542B (zh) 一种紫外荧光分子探针的合成及其对亚硝酸根的检测
CN109265412B (zh) 一种用于检测氟离子的探针化合物及其检测方法
CN115677592B (zh) 一种氨基配位型高选择性汞离子荧光探针、制备方法与应用
CN115246831B (zh) 一种Hg2+敏感性腙类衍生物及其制备和应用

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
EE01 Entry into force of recordation of patent licensing contract

Application publication date: 20190201

Assignee: Dalian Youke Instrument Co.,Ltd.

Assignor: DALIAN University

Contract record no.: X2023210000248

Denomination of invention: A ratio fluorescent probe compound for detecting zinc ions in aqueous solution and its detection method

Granted publication date: 20200616

License type: Common License

Record date: 20231129

EE01 Entry into force of recordation of patent licensing contract
OL01 Intention to license declared
OL01 Intention to license declared