CN108727257B - 一种用于检测镉离子的荧光化学传感器及制备方法 - Google Patents
一种用于检测镉离子的荧光化学传感器及制备方法 Download PDFInfo
- Publication number
- CN108727257B CN108727257B CN201810891600.XA CN201810891600A CN108727257B CN 108727257 B CN108727257 B CN 108727257B CN 201810891600 A CN201810891600 A CN 201810891600A CN 108727257 B CN108727257 B CN 108727257B
- Authority
- CN
- China
- Prior art keywords
- cadmium ions
- chemical sensor
- detecting
- fluorescence
- round
- 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
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/90—Plate chromatography, e.g. thin layer or paper chromatography
-
- 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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-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
- C09K2211/10—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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Immunology (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
一种用于检测镉离子的荧光化学传感器及制备方法,步骤1)将2,4‑二羟基苯甲醛和2‑氨基吡啶以质量百分比为1:1加入到圆底烧瓶A中,然后再向加入圆底烧瓶A中加入乙醇,将圆底烧瓶A置于油浴中,用磁力搅拌器将圆底烧瓶A中的反应物搅拌回流5~8小时;步骤2)用色谱法检测反应进行的程度,待完全反应之后,用旋转蒸发仪旋干,并放置在真空干燥箱中10~12个小时,制备的荧光化学传感器,对镉离子有高灵敏、高选择性的荧光增强型的选择性识别,而且产生的吸光度比值与镉离子的浓度在0μM到13μM范围内时呈良好的线性关系,即该探针在此范围内能很好的定量检测镉离子,此外,该化学传感器还可以用于检测河水样本中的镉离子。
Description
技术领域
本发明属于荧光化学传感器技术领域,具体涉及一种用于检测镉离子的荧光化学传感器及制备方法。
背景技术
镉是一种毒性很大的重金属,其化合物也大多具有毒性。近几年,被广泛地运用于化工,电镀,电子和核工业等各个技术领域。随着工业和科技的发展,镉在人类周围环境中的富集,通过大气、水、食品等进入人体,能够在有机体内和生物体的器官(肾、甲状腺、脾等)中累积,造成慢性中毒。长期接触镉,可增加多种疾病发病率,例如肾功能紊乱、肺活量减少和肺气肿等,危害人体健康。镉的广泛使用,对环境和人们的生活造成了很大的危害,因此,如何能够快速简洁的检测各种环境样本,工业废水以及生物组织中的镉离子的含量引起了人们的广泛关注。
传统的检测金属离子的方法有很多,如紫外-可见分光光度法(UV-vis)、原子吸收法(AAS)、高效液相色谱法(HPLC)、发射光谱法(AES)、电感耦合等离子体质谱法(ICP-MS)、化学发光法、电化学法等。但与这些方法相比,荧光分析法具有检测方便,快捷,成本低廉等优点。利用荧光分析法发展的荧光化学传感器具有选择性高,灵敏度高,制作成本低,响应时间短,不易破坏样品以及可以实现在线检测等特点,具有广泛的应用前景。
席夫碱化合物中含有由胺和活性羰基缩合而成的亚胺基团(-RC=N-),亚胺基团中的 N 原子有未成键的孤对电子,容易和金属离子结合生成配和物。席夫碱化合物合成的荧光探针具有良好的发光性质,可通过调节亚胺基团(-RC=N-)的 C=N 异构化,调节其荧光发射光谱。以2,4-二羟基苯甲醛与2-氨基吡啶为原料,合成一个基于席夫碱的检测镉离子的荧光化学传感器,该传感器对镉离子有较好的选择性,该传感器通过与镉离子配位,抑制了C=N 异构化和N原子的光诱导电子转移(PET)效应,使荧光增强。
发明内容
本发明的目的是提供一种用于检测镉离子的荧光化学传感器及制备方法,将2,4-二羟基苯甲醛与2-氨基吡啶反应合成得到基于席夫碱的检测镉离子的荧光化学传感器,该传感器通过与镉离子配位,抑制了C=N 异构化和N原子的光诱导电子转移(PET)效应,使荧光增强。可以检测水溶液中的镉离子含量,具有响应时间短,操作简便,抗干扰能力强的特点。
为了实现上述目的,本发明采用的技术方案是:
一种用于检测镉离子的荧光化学传感器,其特征在于,该荧光化学传感器的化学结构式为如下式(I):
一种用于检测镉离子的荧光化学传感器的制备方法,其特征在于,包括以下步骤:
步骤1)将2,4-二羟基苯甲醛和2-氨基吡啶以质量百分比为1:1加入到圆底烧瓶A中,然后再向加入圆底烧瓶A中加入10 mL乙醇,将圆底烧瓶A置于油浴中,用磁力搅拌器将圆底烧瓶A中的反应物搅拌回流5~8小时;
步骤2)用色谱法检测反应进行的程度,待完全反应之后,用旋转蒸发仪旋干,并放置在真空干燥箱中10~12个小时,制的化学式为式(I)的荧光化学传感器。
进一步,步骤1)中所述的油浴温度为80℃。
进一步,步骤2)中所述的旋转蒸发仪温度为50℃。
进一步,步骤2)中所述的色谱法用体积比为20:1的二氯甲烷和甲醇的组成的展开剂进行爬板检测。
本发明的有益效果是:
本发明提供的基于席夫碱的用于检测镉离子的荧光化学传感器(Probe 1)对镉离子有高灵敏、高选择性的荧光增强型的选择性识别,而且产生的吸光度比值与镉离子的浓度在0μM到13μM范围内时呈良好的线性关系,即该探针在此范围内能很好的定量检测镉离子,此外,该化学传感器还可以用于检测河水样本中的镉离子。
附图说明
图1是本发明检测镉离子的荧光化学传感器的激发和发射光谱图,其中a为Probe1的激发光谱图,b为Probe 1的发射光谱图;
图2是本发明检测镉离子的荧光化学传感器中加入镉前后的荧光光谱图。
图3是本发明检测镉离子的荧光化学传感器对于不同金属离子的选择性识别的紫外吸收光谱图;
图4是本发明检测镉离子的荧光化学传感器和该传感器在不同金属离子存在时在紫外灯激发下的效果图;
图5是向本发明检测镉离子的荧光化学传感器中滴加不同浓度镉离子时的吸收光谱图;
图6是向本发明检测镉离子的荧光化学传感器中滴加不同浓度镉离子时385 nm处的吸光度与362 nm 处的吸光度的比值(Abs385 nm/Abs 362 nm)与镉离子浓度的关系曲线图;
图7为镉离子浓度在0~13μM的范围内时,本发明检测镉离子的荧光化学传感器385 nm处的吸光度与362 nm 处的吸光度的比值(Abs 385 nm/Abs 362 nm)和镉离子的浓度的线性拟合关系图;
图8本发明检测镉离子的荧光化学传感器分别在河水,自来水和纯净水体系中的在紫外灯激发下的对比效果图。
具体实施方式
以下结合实施利对本发明进一步叙述,但本发明不局限于以下实施利。
实施例1:
荧光化学传感器probe1的合成:向100 mL 圆底烧瓶A中加入2,4-二羟基苯甲醛(1g,7.2 mmol),2-氨基吡啶(0.79 mL,7.2 mmol),并加入10 mL乙醇溶解,在80℃油浴中,磁力搅拌器搅拌回流6小时,待反应完全后,用旋转蒸发仪旋蒸,蒸发后放入真空干燥箱中干燥12小时。得到probe1(黄色粉末),0.96g,产率:54%。1H NMR (400 MHz, DMSO) δ 8.51(dd, J = 5.4, 1.9 Hz, 2H), 7.77 (td, J = 7.7, 1.8 Hz, 1H), 7.37 -7.19 (m,3H), 6.27 (dd, J = 8.4, 2.3 Hz, 1H), 6.14 (d, J = 2.3 Hz, 1H), 4.78 (s, 2H),3.40 -3.27 (m, 2H)。合成路线如下:
实施案例2:
将本发明的荧光化学传感器(10 μM)溶于CH3CN-H2O(7:3, v/v)的溶液中,用荧光光谱仪检测其激发以及发射光谱,如图1所示(图1(a)为Probe 1的激发光谱图,图1(b)为Probe 1的发射光谱图):本发明的荧光化学传感器的最大激发波长在350 nm处,最大发射波长在440 nm处。在该条件下加入镉离子(20μM),可看到荧光强度明显增强(参见图2)。
在CH3CN-H2O(7:3, v/v)的溶液中,加入Probe 1(0.1 mM),再分别加入0.1 mM Na+、Mg2+、Al3+、K+、Cr3+、Mn2+、Cu2+、Zn2+、Ag+、Hg2+、Pb2+及Cd2+的金属盐溶液,采用紫外可见分光光度法研究Probe 1对于金属离子的选择性识别,测试结果如图3, Probe 1(0.1 mM)在302nm和385 nm处有两个较强的吸收峰,加入镉离子(0.1 mM)后,385 nm 处的吸收峰降低,340nm处出现一个新的强吸收峰。而其它金属离子的吸收光谱基本没有变化。证明Probe 1对镉离子有选择性识别。在365nm的紫外灯照射下观察,荧光探针体系显现出明显的荧光增强信号,发射出蓝色荧光,而加入其他金属离子,荧光基本无变化(如图4)。
实施案例3:
在CH3CN-H2O(7:3, v/v)中,向含有0.1 mM Probe 1的溶液中逐渐滴加镉离子时,体系的吸收光谱图如图5,随着镉离子的不断加入,Probe 1体系原本处于385 nm处的吸收峰逐渐降低,而在340 nm处出现一个新的吸收峰。同时,在362 nm处出现了一个等吸收点,等吸收点的出现证明Probe 1和镉离子形成了新的配合物。如图6所示,在一定的范围内,385 nm处的吸光度与362 nm 处的吸光度的比值(Abs 385 nm/Abs 362 nm)随着镉离子(0~0.2mM)浓度的不断增大而不断减小,在镉离子浓度达0.1 mM时,吸光度的大小不再变化,达到饱和。当镉离子浓度在0~13 μM的范围内时,该体系的吸光度与镉离子的浓度呈良好的线性关系,即本发明荧光传感器在此范围内能很好的定量检测镉离子(参见图7)。
实施案例4:
该发明的荧光化学传感器可用于检测河水或自来水体系中是否存在镉离子,具体方法如下: 在CH3CN-H2O(7:3, v/v)中,其中水分别采用纯净水,自来水和河水,向含有0.1mM Probe 1的溶液中加入0.1 mM镉离子,在紫外灯下观察,可以直接看到所有加了镉离子的试剂瓶内都有明显的荧光现象(参见图8)。实验结果表明Probe 1在应用条件上具有广泛性,对测试环境的要求比较低,但却能够很好的表征体系中的镉离子,达到检测的目的。
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810891600.XA CN108727257B (zh) | 2018-08-07 | 2018-08-07 | 一种用于检测镉离子的荧光化学传感器及制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810891600.XA CN108727257B (zh) | 2018-08-07 | 2018-08-07 | 一种用于检测镉离子的荧光化学传感器及制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108727257A CN108727257A (zh) | 2018-11-02 |
CN108727257B true CN108727257B (zh) | 2021-07-16 |
Family
ID=63942430
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810891600.XA Active CN108727257B (zh) | 2018-08-07 | 2018-08-07 | 一种用于检测镉离子的荧光化学传感器及制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108727257B (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110003095B (zh) * | 2019-03-14 | 2020-12-01 | 陕西科技大学 | 具有AIE性质的Cd2+荧光探针及其制备方法和应用 |
CN110317175B (zh) * | 2019-06-26 | 2021-11-19 | 山西大学 | 一种萘衍生物及其合成方法和应用 |
CN112250674B (zh) * | 2020-10-27 | 2021-12-31 | 山西大学 | 一种2,3-二氨基吩嗪衍生物及其合成方法和应用 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104312193A (zh) * | 2013-10-14 | 2015-01-28 | 大连理工大学 | 溴氨酸芳胺化合成蒽醌型染料或色基的方法 |
CN104327532A (zh) * | 2013-10-14 | 2015-02-04 | 大连理工大学 | 溴氨蓝的制备方法 |
CN104326947A (zh) * | 2013-10-14 | 2015-02-04 | 大连理工大学 | 活性艳蓝k-gr中间体的制备方法 |
CN104326953A (zh) * | 2013-10-14 | 2015-02-04 | 大连理工大学 | 活性艳蓝kn-r中间体的制备方法 |
CN105622490A (zh) * | 2016-02-03 | 2016-06-01 | 齐齐哈尔大学 | 一种非对称氮氧配体及Ti、Zr、Hf配合物制备方法和应用 |
-
2018
- 2018-08-07 CN CN201810891600.XA patent/CN108727257B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104312193A (zh) * | 2013-10-14 | 2015-01-28 | 大连理工大学 | 溴氨酸芳胺化合成蒽醌型染料或色基的方法 |
CN104327532A (zh) * | 2013-10-14 | 2015-02-04 | 大连理工大学 | 溴氨蓝的制备方法 |
CN104326947A (zh) * | 2013-10-14 | 2015-02-04 | 大连理工大学 | 活性艳蓝k-gr中间体的制备方法 |
CN104326953A (zh) * | 2013-10-14 | 2015-02-04 | 大连理工大学 | 活性艳蓝kn-r中间体的制备方法 |
CN105622490A (zh) * | 2016-02-03 | 2016-06-01 | 齐齐哈尔大学 | 一种非对称氮氧配体及Ti、Zr、Hf配合物制备方法和应用 |
Also Published As
Publication number | Publication date |
---|---|
CN108727257A (zh) | 2018-11-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Yang et al. | A highly selective and sensitive fluorescent chemosensor for detection of CN−, SO 3 2− and Fe 3+ based on aggregation-induced emission | |
Mao et al. | An rhodamine-based fluorescence probe for iron (III) ion determination in aqueous solution | |
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 | |
CN108727257B (zh) | 一种用于检测镉离子的荧光化学传感器及制备方法 | |
Park et al. | A new coumarin-based chromogenic chemosensor for the detection of dual analytes Al 3+ and F− | |
He et al. | A fluorescent chemical sensor for Hg (II) based on a corrole derivative in a PVC matrix | |
Saikia et al. | Development of solution, film and membrane based fluorescent sensor for the detection of fluoride anions from water | |
Qian et al. | A highly selective chemosensor for naked-eye sensing of nanomolar Cu (II) in an aqueous medium | |
Venkatesan et al. | Spectrophotometric and RGB performances of a new tetraphenylcyclopenta-derived Schiff base for the quantification of cyanide ions | |
Bhatti et al. | New water soluble p-sulphonatocalix [4] arene chemosensor appended with rhodamine for selective detection of Hg2+ ion | |
Thakur et al. | Synthesis of triazole linked fluorescent amino acid and carbohydrate bio-conjugates: a highly sensitive and skeleton selective multi-responsive chemosensor for Cu (II) and Pb (II)/Hg (II) ions | |
Ma et al. | A ratiometric fluorescent sensor for zinc ions based on covalently immobilized derivative of benzoxazole | |
CN109705111A (zh) | 一种汞离子检测探针及其制备方法和应用 | |
Cui et al. | Design and synthesis of a terbium (III) complex-based luminescence probe for time-gated luminescence detection of mercury (II) Ions | |
CN110003095B (zh) | 具有AIE性质的Cd2+荧光探针及其制备方法和应用 | |
Bhalla et al. | Terphenyl based ‘Turn On’fluorescent sensor for mercury | |
He et al. | Rhodamine 6G-based chemosensor for the visual detection of Cu2+ and fluorescent detection of Hg2+ in water | |
CN111393461B (zh) | 一种基于bodipy的钯离子荧光探针化合物及其合成方法 | |
Wang et al. | Dipyrrolylquinoxaline-bridged Schiff bases: a new class of fluorescent sensors for mercury (II) | |
CN110713826B (zh) | 基于邻炔基苯并唑的铜离子检测探针及其制备方法和应用 | |
Guo et al. | Selective aqueous fluorescent probes for metal ions based on benzoyl hydrazone derivatives | |
Young | Selective fluorescent Hg (II) detection in aqueous solutions with a dye intermediate | |
CN110317175B (zh) | 一种萘衍生物及其合成方法和应用 | |
Wang et al. | A novel fluorescence probe based on p-acid-Br and its application in thiourea detection | |
CN113861067A (zh) | 一种可动态检测水中Fe3+及Al3+分子探针及应用 |
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 |