CN111423427A - 一种快速检测三价镓离子的荧光探针及其合成方法和应用 - Google Patents
一种快速检测三价镓离子的荧光探针及其合成方法和应用 Download PDFInfo
- Publication number
- CN111423427A CN111423427A CN202010272360.2A CN202010272360A CN111423427A CN 111423427 A CN111423427 A CN 111423427A CN 202010272360 A CN202010272360 A CN 202010272360A CN 111423427 A CN111423427 A CN 111423427A
- Authority
- CN
- China
- Prior art keywords
- probe
- ions
- fluorescent probe
- application
- synthetic method
- 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.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur 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"
- 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
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only 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
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
-
- 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
- G01N2021/6417—Spectrofluorimetric devices
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Molecular Biology (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
本发明公开了一种快速检测Ga3+离子的荧光探针及其合成方法和应用。该探针由4‑甲基‑7‑羟基‑8‑醛香豆素与2‑噻吩甲酰肼经席夫碱反应制备而成,不但能够实现Ga3+离子荧光光谱的检测,而且具有响应时间短、检测特异性好、抗干扰能力强的优点。
Description
技术领域
本发明涉及一种快速检测三价镓离子的荧光探针及其合成方法和应用,属于分析测试领域。
背景技术
镓离子作为一种稀土元素离子,具有优良的光电性能,已经倍广泛用于金属催化、磷光材料、低温发光材料、太阳能电池、上转换材料和长余辉材料等。镓离子的广泛使用给环境安全和生物体的健康带来了一定潜在威胁。研究表明,镓会导致钙和磷酸盐在小鼠肾脏堆积,堵塞肾腔。而人类在服用浓度高于750mg/kg镓时也会表现出对肾脏的毒性。但是,低浓度的镓离子及其配合物可以用于恶性肿瘤,晚期佩吉特氏骨病和血钙过多综合征等疾病的治疗。因此,开发一种可靠、简便的方法来检测Ga3+离子是非常重要的。
目前报道的用于Ga3+离子分析测试的方法荧光计和中子活化法,测量前需要对样品进行浓缩,通过溶剂提取,提高了灵敏度,或需要进行种子活化,预处理时间长,难以实时检测。
发明内容
本发明的目的是针对上述缺陷,提供一种Ga3+离子荧光探针,能够实现对Ga3+离子的快捷检测。本发明提供的荧光探针具有以下化学结构:
本发明所述的荧光探针的合成方法为:在乙醇溶液中,加入7-羟基-4-甲基-8-甲醛香豆素与1~1.2倍摩尔量的2-噻吩甲酰肼,然后在60~90℃条件下搅拌4~6小时后,冷却,减压抽滤除去溶剂。
本发明所述的荧光探针应用于各种介质中Ga3+离子的荧光光谱检测。
试验结果表明:
(1)该探针结构简单,易于制备。
(2)该探针对Ga3+离子具有良好荧光响应性,响应时间短。
(3)荧光选择性好,抗干扰能力强。
本发明的有益效果是:
(1)本发明探针能够实现对Ga3+离子的荧光定量检测。
(2)检测过程短,响应迅速,3分钟就能完成与Ga3+离子的相互作用。
(3)检测性能优良,其它金属离子没有显现出显著的干扰性。
附图说明
图1探针(20μmol/L)与Ga3+离子(50μmol/L)作用后紫外吸光谱的变化。
图2探针对Ga3+离子的荧光选择性(激发波长360nm)。
图3探针对Ga3+离子荧光检测效果的抗干扰性能(激发波长360nm,荧光强度468nm)。
图4探针与不同浓度Ga3+离子作用后的荧光光谱。
图5探针对于Ga3+离子的荧光响应线性关系。
图6探针对于Ga3+离子的强光强度随时间的变化情况。
具体实施方式
下面通过具体实施例对本发明进行详细地说明。
实施例1探针的合成和结构表征
由2-噻吩甲酰肼与7-羟基-4-甲基-8-甲醛香豆素经缩合反应最终得到目标产物。
探针的合成探针路线如下:
合成步骤:
目标化合物-肼探针的制备:将7-羟基-4-甲基-8-甲醛香豆素(0.41g,2mmol))和2-噻吩甲酰肼(0.30g,2.1mmol)溶于15mL无水乙醇中,65~85℃搅拌3小时,冷却,抽滤,冷乙醇洗涤一次得浅黄色固体,产率81%。
通过核磁共振氢谱、碳谱和质谱确认该探针的结构。
1H NMR(500MHz,DMSO-d6)δ12.64(s,1H),12.49(s,1H),9.11(s,1H),7.96,7.95(d,J=5Hz,2H),7.75,7.73(d,J=8Hz,1H),7.29,7.28(d,J=5Hz,1H),7.00,6.98(d,J=10Hz,1H),6.28(s,1H),2.42(s,3H).13C NMR(126MHz,DMSO-d6)δ161.45,159.71,157.84,154.41,152.97,143.74,137.36,133.22,130.10,128.90,128.67,113.94,112.37,111.23,106.05,18.81.EI-MS calcd for C16H12N2O4S328.05,found 329.05([M+H]+).
实施例2探针对Ga3+离子紫外吸收光谱的影响
1.如图1所示,在N,N-二甲基亚砜与水体积比为1:1组成的磷酸缓冲溶液(pH 7.4)中,探针(20μmol/L)本身紫外吸收在360nm处,加入50μmol/LGa3+后,位于360nm处的紫外吸收峰蓝移到310nm。
2.如图2所示,在N,N-二甲基亚砜与水体积比为1:1组成的磷酸缓冲溶液(pH 7.4,在360nm激发波长下,探针(20μmol/L)的荧光强度非常微弱,加入50μmol/L各金属离子包括Li+,K+,Na+,Ag+,Hg2+,Zn2+,Cu2+,Ca2+,Co2+,Ni2+,Pb2+,Mg2+,Cr3+,Fe3+,Mn2+,Ba2+,Cd2+,Al3+,In3 +和Ga3+后,只有Ga3+离子能引起探针荧光强度的显著增强,说明探针对Ga3+离子具有良好的荧光选择性。
3.如图3所示,在360nm激发波长下,当探针(20μmol/L)与Ga3+(50μmol/L)共存时,浓度均为50μmol/L的其它各金属离子包括1:Li+,2:K+,3:Na+,4:Ag+,5:Hg2+,6:Zn2+,7:Ca2+,8:Co2+,9:Pb2+,10:Mg2+,11:Cr3+,12:Ni2+,13:Fe3+,14:Cu2+,15:Mn2+,16:Ba2+,17:Cd2+,18:Al3 +和19:In3+都不能引起探针荧光强度的显著降低,说明其它常见的金属离子对探针检测Ga3+离子没有显著的干扰,该探针具有良好的抗干扰性能。
4.如图4所示,在N,N-二甲基亚砜与水体积比为1:1组成的磷酸缓冲溶液(pH 7.4,探针(20μmol/L)的荧光强度Ga3+离子浓度(0,2,4,6,8,10,12,15,20,25,30,35,40,45,50μmol/L)的增加逐渐增强。
5.如图5所示,Ga3+离子浓度在2~12μmol/L的范围内,探针在468nm处的荧光强度与Ga3+离子浓度之间满足良好的线性关系:y=-81.5+46.6x(R2=0.9914)。表明该探针(20μmol/L)可以在2~12μmol/L的范围内对Ga3+离子浓度进行定量检测。
6.如图6所示,探针(20μmol/L)与50μmol/L Ga3+离子混合后,3分钟探针在468nm的荧光强度能够接近最大值,表明该探针对Ga3+离子响应迅速。
实施例3探针对水中Ga3+离子的检测
通过加标回收的方式,分别向自来水和池塘水中加入4μmol/L,6μmol/L和10μmol/L的Ga3+离子,用磷酸缓冲溶液及N,N-二甲基亚砜调节至N,N-二甲基亚砜与水溶液体积比1:1,在比色皿中测试其荧光强度,把荧光强度带入探针与Ga3+离子的线性方程(如图5)即可求得待测样品溶液中Ga3+离子的浓度。回收率达可到87.5~95.4%的范围。
综上,该探针可以用于对Ga3+离子的荧光检测,并且响应时间短,选择性好,抗干扰能力强,能够实现水溶液中Ga3+离子的检测。
Claims (3)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010272360.2A CN111423427A (zh) | 2020-04-09 | 2020-04-09 | 一种快速检测三价镓离子的荧光探针及其合成方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010272360.2A CN111423427A (zh) | 2020-04-09 | 2020-04-09 | 一种快速检测三价镓离子的荧光探针及其合成方法和应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN111423427A true CN111423427A (zh) | 2020-07-17 |
Family
ID=71556104
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010272360.2A Pending CN111423427A (zh) | 2020-04-09 | 2020-04-09 | 一种快速检测三价镓离子的荧光探针及其合成方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111423427A (zh) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108409726A (zh) * | 2018-01-17 | 2018-08-17 | 南通大学 | 一种香豆素2-肼基苯并噻唑席夫碱Cd2+荧光探针的制备及应用 |
CN109705110A (zh) * | 2018-12-21 | 2019-05-03 | 西南医科大学附属医院 | 一种高特异性检测gsh的荧光探针及应用 |
CN110950854A (zh) * | 2019-12-16 | 2020-04-03 | 温州医科大学 | 一种关-开型分子荧光探针cmtah及其制备方法与应用 |
-
2020
- 2020-04-09 CN CN202010272360.2A patent/CN111423427A/zh active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108409726A (zh) * | 2018-01-17 | 2018-08-17 | 南通大学 | 一种香豆素2-肼基苯并噻唑席夫碱Cd2+荧光探针的制备及应用 |
CN109705110A (zh) * | 2018-12-21 | 2019-05-03 | 西南医科大学附属医院 | 一种高特异性检测gsh的荧光探针及应用 |
CN110950854A (zh) * | 2019-12-16 | 2020-04-03 | 温州医科大学 | 一种关-开型分子荧光探针cmtah及其制备方法与应用 |
Non-Patent Citations (6)
Title |
---|
A KOTALI等: ""Synthesis of angular 7,8-pyridazinocoumarins via the transformation of a hydroxy group into a carbonyl group "", 《SYNTHESIS》 * |
KM RAJ等: ""Synthesis, spectroscopic characterization, electrochemistry and biological evaluation of some metal (II) complexes with ONO donor ligand containing benzo[b]thiophene and coumarin moieties"", 《JOURNAL OF MOLECULAR STRUCTURE》 * |
LIQIANG YAN等: ""A new turn on coumarin-based fluorescence probe for Ga3+ detection in aqueous solution"", 《SPECTROCHIMICA ACTA PART A: MOLECULAR AND BIOMOLECULAR SPECTROSCOPY》 * |
徐帆: ""香豆素基席夫碱化合物的设计合成及其对金属阳离子的光学识别性能研究"", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
苏策等: "一种香豆素类锌离子荧光探针的合成及性能", 《应用化学》 * |
谢雅: ""基于香豆素荧光探针的制备及性能研究"", 《中国优秀硕士学位论文全文数据库基础科学辑》 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Tang et al. | A highly selective and ratiometric fluorescent sensor for relay recognition of zinc (II) and sulfide ions based on modulation of excited-state intramolecular proton transfer | |
Xia et al. | Fast, high-yield synthesis of amphiphilic Ag nanoclusters and the sensing of Hg 2+ in environmental samples | |
CN108535231B (zh) | 基于双发射铕金属有机骨架材料检测磷酸根离子的方法 | |
CN108384018B (zh) | 一种mof配合物及其合成和在荧光识别铁离子的应用 | |
CN107602449B (zh) | 一种具有类石墨结构的锌配合物荧光探针的制备及应用 | |
CN113979998A (zh) | 基于1,8-萘酰亚胺为母体的铝离子检测荧光探针及其制备方法和应用 | |
CN110950854B (zh) | 一种关-开型分子荧光探针cmtah及其制备方法与应用 | |
CN109097026B (zh) | 一种纳米花状Al-MOF荧光探针材料及其制备方法与应用 | |
CN111393461A (zh) | 一种基于bodipy的钯离子荧光探针化合物及其合成方法 | |
CN109021000B (zh) | 一种检测过氧化氢的荧光探针、合成方法和应用 | |
Chu et al. | A new luminescent lanthanide supramolecular network possessing free Lewis base sites for highly selective and sensitive Cu 2+ sensing | |
Zeng et al. | The synthesis of two novel neutral receptors and their anion binding properties | |
CN114920762B (zh) | 一种有机杂化碘化亚铜双响应荧光探针材料及其制备方法 | |
CN111423427A (zh) | 一种快速检测三价镓离子的荧光探针及其合成方法和应用 | |
Yang et al. | Determination of Trace Terbium (III) with N, N, N′-Tri (3-indolemethanal) triaminotriethylamine Based on a New Fluorescence Enhancement System | |
CN114195682B (zh) | 一种可检测水中Ba2+的荧光分子探针及其应用 | |
CN112724137B (zh) | 一种苝酰亚胺衍生物及其制备方法和应用 | |
CN110981748B (zh) | 一种增强型偶氮Salen席夫碱荧光探针、其合成及其应用 | |
Sun et al. | A highly thermal and pH-stable fluorescence sensor for rapid detection of Hg 2+, Fe 3+, and tetracycline in aqueous solutions | |
CN110132911B (zh) | 基于复合物比率荧光探针的水样中总磷检测方法 | |
CN113979984A (zh) | 一种水溶性黄酮类铝离子荧光探针的制备方法及其应用 | |
Yang et al. | Fluorimetric determination of traces of europium (III) using a new chelator and acetate or phosphate in dimethylsulfoxide as enhancers | |
CN112521409B (zh) | 一种锌配合物及其应用 | |
Wu et al. | Two-dimensional Cd (ii) coordination polymer encapsulated by Tb 3+ as a reversible luminescent probe for Fe 3+ | |
CN115043855B (zh) | 一种检测重水中水含量的荧光探针及其应用 |
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 | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200717 |